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MULLIKEN, Pa.D. Associate Professor of Organic Chemical Research, Massachusetts Institute of Technology Vol. I contains Classified Descriptions of about 2300 of the more important Compounds of Carbon with Hydrogen and with Hydrogen and Oxygen. Large 8vo, xlii+264 pages. Cloth, $5.00 net Vol. II, containing Classified Descriptions of themore Impor- tant Compounds of Carbon with the Elements Nitrogen, Hydro- gen, and Oxygen, Exclusive of the Dyestuffs. Price, $5.00 net Vol. III, which contained descriptions of the pre-war brands of **Commercial Dyestuffs,” is no longer on gale. Vol. IV, appearing during the year 1922, contains Classified Descriptions of about 3700 of the more important Compounds of the ‘‘ Higher Orders.’’ It deals chiefly with the Identification of the Organic Halogen and Sulphur Compounds, Price, $6.00 net A METHOD FOR THE IDENTIFICATION OF PURE ORGANIC COMPOUNDS foomor ole NMATIC ANALYTICAL PROCEDURE BASED See Pry SICAL sPROPERLIES AND Sie MICAL SR EAGIIONS Wiley rol | CONTAINING CLASSIFIED DESCRIPTIONS OF ABOUT 2300 OF THE MORE IMPORTANT COMPOUNDS OF CARBON WITH HYDROGEN AND WITH HYDROGEN AND OXYGEN BY Senne PARSONS ~ MULELEIKEN, “Pie b: Associate Professor of Organic Chemical Research at the Massachusetts Institute of Technology, Boston, Mass, FIRST EDITION TOTAL ISSUE, FOUR THOUSAND NEW YORK JOHN WILEY & SONS, Inc. Lonpon: CHAPMAN & HALL, Limitep THE GETTY RESEARCH INSTITUTE LIBRARY = » r “ § ' i ft cae | ee aoe are Copyright, 1904, q in rat li oe * BY SAMUEL PARSONS MULLIKEN Entered at Stationers’ Hall. bare a LAST 2 Ud ee ee ie j ve ee er! at Sire ‘ (ete ii ~ eee 1 press oF) Pate Oe A) Foe ee BRAUNWORTH & CO. 5/22 as | BOOK MANUFACTURERS, =~ 7 CHT 4a” yh " . 4 BROOKLYN; Ne'Ys © > © ° 2 . PREFACE. At the time of writing the only general and fairly systematic procedure for vhe identification of previously described organic compounds of all classes is that which may be conveniently designated the Method of the Empirical Formula, Jn following this procedure a determination of the percentage composition is first made. The molecular weight is next determined or conjectured. From these data an empirical formula is calculated. The properties of the substance are then compared with those of all the known compounds possessing this formula by refer- ence to their scattered literature, for which Richter’s ‘‘ Lexicon der Kohlenstoff- Verbindungen ”’ with its supplements now furnishes a very complete index. Resting, as it chiefly does, on the two fundamental properties, percentage composition and molecular weight—which alone among the chemical constants can be readily cal- culated for every compound in advance of its discovery—it is probable that this method will long remain the last resort in all earnest attempts to establish the identity of compounds which have been previously undescribed or very imper- fectly characterized through their physical and chemical properties. Nevertheless, when we turn to the great body of well-characterized compounds that occur with some frequency in the products of Nature, the useful arts, and the scientific labo- ratory, there is good reason to raise the question whether the Method of the Empir- ical Formula is from the practical standpoint a sufficiently satisfactory one. It is evidently not if any substitute can be found that will lead the analyst to the same results with less expenditure of time and effort, and without requiring unusual knowledge or skill on his part; and it is not to be denied that in these respects this method makes a very poor showing, ‘The indispensable key to its use is pro- ficiency in ultimate organic analysis, whose difficult technique is fully mastered only by long practice. The performance of the combustions, which must be made in duplicate to secure certainty, is at best a time-consuming operation; and even after reliable results have been obtained, it is further necessary, in order to fully identify a compound, to resort to a study of its physical properties, chemical behavior, and perhaps to a molecular-weight determination. The consequence of this has been that the identification of organic compounds by this general method has been practi- cally limited to its occasional employment in laboratories devoted to synthetic organic research, and that such identifications when attempted elsewhere are usu- ally accomplished, often with uncertain results, by the use of disconnected desultory tests. Through these considerations, and with the belief that a path of less resist- ance could be broken out for the analyst, the writer began more than eight years ago the studies whose first results appear in this volume. ili iv PREFACE The present method, as contrasted with that just described, gives fuller recog- nition to the important truths that percentage composition and molecular weight are merely two among many highly significant characteristics of every compound; and that without recourse to them, by the use of the more easily determined prop- erties like qualitative elementary composition, color, melting-point, boiling-point, solubility, specific gravity, alkali neutralizing power, and chemical behavior under prescribed conditions, entirely satisfactory identifications may be made —provided a sufficient number of these facts which are at the disposal of the systematist are carefully verified and suitably codrdinated in a classified system. The new method therefore rests, as will be more fully explained in the intro- ductory chapter, upon a classification designed to secure for the carbon compounds those advantages which have been already so long enjoyed in Botany and other branches of Natural History through the use of systematized descriptions of salient characteristics. The compounds, or chemical “species,’’ have been first grouped into “orders”? on the basis of their qualitative elementary composition; then into ‘genera’? (aldehydes, acids, phenols, etc.), usually on the basis of behavior in simple chemical tests; and, finally, arranged within each genus according to the increasing value of some readily-determined constant like the melting-point or boiling-point. The name of each species is followed in the tables by a brief specific characterization enumerating some of the simpler properties of the substance that have genuine analytical significance, and then, whenever possible, by detailed directions for preliminary and corroborative chemical tests which can be performed with small quantities of material. The phrase ‘‘More Important Compounds” used in the title is unavoidably indefinite; but the intention has been to admit all substances to the tables for which there is more than a remote chance that they may come into the hands of the analyst as unknown compounds. Such a list naturally includes: first, all com- pounds that may be isolated in a state of purity and without excessive difficulty from materials used in the arts, or from substances which occur somewhat abun- dantly in Nature; second, compounds of minor importance which may easily be formed in the laboratory as by-products in reactions between substances of more common occurrence; third, many rare compounds which have acquired a general scientific interest either on account of their properties or as representatives of peculiar types. Very few compounds that could be purchased in the market in a state of purity have been omitted except through oversight. The most important intentional omissions are: substances whose claims to recognition as distinct chemical species are not generally accepted; uncrystallizable syrups that cannot be distilled without decomposition; the oily and fatty glycerides; those glucosides and synthetic sugars of which specimens could not be obtained for examination. The claims for admission to this volume of every compound of carbon with hydrogen, or with hydrogen and oxygen, that receives mention in the second edi- tion of Beilstein’s great ‘‘ Handbuch der organischen Chemie” and in its supple- ments issued prior to January, 1902, have been separately passed upon, and about 2300 selected as deserving mention in the tables. All copied data used in the manuscript sent to the publisher have been twice compared with their source by the author and once by Dr. Heyward Scudder. PREFACE. us Obviously the attempt to establish an analytical system of the proposed char- acter on any less secure foundation than an extended first-hand study of a very large number of representative compounds so selected as to cover all important types, would be to invite the fate of ‘‘the foolish man which built his house upon the sand”’; for existing descriptions of the reactions of even the most familiar com- pounds very rarely state the experimental conditions and phenomena in terms that are immediately available for the purposes of a systematic analytical classification. The chemical tests that have been relied upon for arranging the chemical species in genera are therefore the result of many hundred original experiments made upon several hundred compounds in the laboratories of the Massachusetts Institute of Technology, the preparations used being supplied for the most part from the valu- able Institute collection. Yet in spite of the considerable labor expended in this way, since it has been physically impossible to examine personally every species described, it would be absurd to deny that some may be wrongly located in the classification. ‘To safeguard the analyst as far as possible against errors arising from such imperfect descriptions, every reasonable precaution that has suggested itself has been taken during the construction of the procedures and tables. The names of those compounds whose generic positions have been established by original experiments in the author’s laboratory are distinguished from others by being preceded by the mark 7, though it is not true that every property ascribed to a sub- stance thus marked is necessarily an original or guaranteed datum. Of the ‘num- bered specific tests’? it may, however, be said that each one has been performed at least several times in accordance with the directions contained in the manu- script; that they have all been used on more than one occasion; and that they have proved successful in the hands of two or more persons. The specific characterizations are all quite brief because the work is intended to be used as a compact practical analytical guide and index, and not as a band- book of descriptive Organic Chemistry; and because the value of a specific descrip- tion to the analyst never increases, beyond a certain point, directly 1n proportion to the number of properties and tests included—long descriptions often becoming unwieldy and confusing through suggesting too many alternatives of unequal merit. To obtain all the new material required for these pages single-handed would have proved a disheartening labor. The writer’s grateful acknowledgments are therefore due to the many friends (most of whom are or have been connected with the chemical department of the Massachusetts Institute of Technology) who have rendered assistance in the work. Some of the most important contributions from this source are recorded in the unpublished ‘‘thesis’’ investigations of the writer’s students. Valuable information has thus been furnished by Messrs. A. P. — Norris, C. L. M. Pettee, H. M. Loomis, H. Scudder, B. R. Rickards, A. R. 8. Booth, J. W. Brown, J. R. Odell, and Misses E. M. Chandler and A. F. Blood. The writer has also been ably assisted at different times by Dr. Paul Chapin and Messrs. A. C. Davis and Herbert Walker. To his friend, Dr. Heyward Scudder, the author’s thanks are however especially due for generous and untiring codperation during a considerable part of this undertaking. Many of the best methods, particularly among the ‘specific tests,” are the fruits of his research, or have been improved vi PREFACE, in consequence of his suggestions, while nearly the whole of the manuscript, as well as the proof-sheets, have received the benefit of his criticism. It is regretted that the necessary practice of omitting, for the sake of simplicity and compact- ness in tabulation, those bibliographical references which, while they have aided the writer, would: not be of obvious advantage to the analyst, has prevented that full acknowledgment of aid from many earlier investigators that would other- wise have been gladly rendered. In closing, a word should be added in regard to the proposed extension of this “Method” to the other organic compounds. It is planned to describe the carbon compounds containing nitrogen, or nitrogen and oxygen—exclusive of the dye- stuffs—in Vol. II, as Order II of the analytical system. Although the prepara- tion of material for Vol. II is quite far advanced, it is probable that Vol. III, which is to be devoted to the identification of the organic dyestuffs, will be ready for publication first. The completion of the system will then await the prepara- tion of a fourth volume to include the remaining “ orders.”’ refed wa 20 MASSACHUSETTS INSTITUTE OF TECHNOLOGY, December, 1903. CONTENTS, neg 6) csv wiles vee cle vine eh Nias dels ecele wealescevceenspeevaws ERENT TONGS 1G, 5s a's ao Ws vag Bll bra Tol etaases ciate wow ou dis A uls'e aba gley a'eivce a eo CHAPTER I, CLASSIFICATION OF COMPOUNDS AND THE ANALYTICAL PROCEDURE. ..........-2e00¢ Explanation of Classification.—Orders, Genera, Divisions, Sections, Species, 1-2. General Directions for Examination of Unknown Compounds.—Evidences of Homo- geneity; Examination of Physical Characteristics; Determination of Order; Determination of Genus; Tabular Summary of Generic Tests; Determina- tion of Division and Section; Determination of Species. 3-7. Examples illustrating the Analytical Procedure. 7-8. CHAPTER Ii. IRM oe Sale iy vgs sk bis 4 0.60 wc s biacy Dee wees © ol «GRC vB ohne ves Procedure jor Detection of the Elements in Organic Compounds.—Carbon and Ash Con- stituents; Sulphur, Nitrogen, and the Halogens; Ignition with Sodium; Sul- phur; Nitrogen; Nitrogen and Sulphur together; Pohsphorus; Halogens; Iodine; Bromine; Chlorine. CHAPTER III. reat send. 1s ORD, 1),—ALDEHYDES. .. 66 ecb bench ce seca renetteane Generic Characterization.—Generic Test 1; Observations on Test; Aldehyde Char- acteristics, 15-16. Analytical Tables.—Div. A (Solid Species), 17-18; Div. B (Liquid Species), 19-21. Numbered Specific or Semi-specific Aldehyde Tests.—(101)* Compounds reducing Tollen’s Reagent; (111) Acetaldehyde; (112) Acrolein; (113) Benzaldehyde; (114) Formic Aldehyde; (115) Furfurol. 22-25. CHAPTER IV. feeceutl qousorp. 1, Orv. I).—CARBOHYDRATES. «6.662 ie ss cee cere erie dees eas Generic Characterization.—Generic Test II; Generic Subdivisions; Carbohydrate Characteristics. 26-28. Analytical Tables—Section 1 (Soluble Species), 29; Section 2 (Insoluble Spe- cies), 31. Numbered Sectional and Specific Carbohydrate Tests——(201) Osazone Precipita- tions; (202) Reduction of Fehling’s Solution; (203) Furfurol; (204) Phloro- glucine Reaction; (205) Oxidations to Mucic or Saccharic Acids. 32-34. * The numerals in parentheses refer to test numbers—not pages. Vil 9-14 15-25 26-34 Vill CONTENTS. CHAPTER V. Genus; TTI (Sunorp, I, Orns D-—Actns os os a ols one ce ee ee Generic Characterization —Generic Test III; Observations on Test; Acid Charac- teristics; Generic Subdivisions. 35-388. Analytical Tables.—Div. A, Sec. 1 (Solid Soluble Species), 39; Div. A, Sec. 2 (Solid but not Soluble Species), 52; Div. B, Sec. 1 (Liquid Soluble Species), 73; Div. B, Sec. 2 (Liquid but not Soluble Species), 75. Numbered Specific or Semi-specific Tests —(301) Neutralization Equivalent; (302) a-Oxyacids; (303) Acids losing Carbon Dioxide at 200; (304) Unsaturated Acids; (305) Esters with characteristic Odors; (306) Metallic Salts; (307) Acid Anhydrides of Genus III; (811) Acetic, Propionic, Butyric, and Isobutyric Acids; (812) Benzoic Acid; (813) Cinnamic Acid; (314) Citric, Malic, and Tartaric Acids; (315) Formic Acid; (316) Glutaric Acid; (317) Oxalie Acid; (318) Phthalic Acid, Isophthalic Acid and Terephthalic Acid; (319) Salicylic Acid; (820) Succinic Acid. 77-86. CHAPTER VI. Genus IV (Suporp. I, Orv. I).— PHENOLIC COMPOUNDS... .....ccccccccvccceccces 4 Generic Characterization.—Generic Test IV. Observations on Test; Phenolic Char- acteristics. 87-90. Analytical Tables.—Div. A (Solid Species), 91; Div. B (Liquid Species), 104. Numbered Specific or Semi-specific Tests——(401) Ferric-chloride Colorations; (402) Phthaleine Fusion; (411) Hydroquinone; (412) a-Naphthol; (413) 68-Naphthol; (414) Phenol; (415) Phloroglucine; (416) Pyrocatechin; (417) Pyrogallol; (418) Resorcine; (419) Thymol. 107-110. CHAPTER VII. Genus V (SunorpD. I, Ornp. I1)—-ESTEeRs ......... sep eves +s+eee ces one Generic Characterization.—Generic Test V, 111; Saponification and Saponification Equivalent (Rapid Method), 111; Saponification to obtain both Acid and Neutral Products (Longer Method), 113; Examination of the most Important Neutral Saponification Products, 113; Examination of the Acid Products, 116; Observations on Test V. 117. Analytical Tables —Div. A (Solid Esters), 118; Div. B (Liquid Esters), 120. CHAPTER VIII. Genus VI (Suporp. I, Orv. J).—Acip ANHYDRIDES AND LACTONES...........cee0e Generic Characterization, 128. Analytical Tables.—Div. A (Solid Species), 129; Div. B (Liquid. Species), 131. CHAPTER IX. Genus VIL (Suporp. I, Orv. 1).—KETONES.. . 2... 52, Daa ce ele ce Generic Characterization.—Generic Test VII; Procedures 1 and 2; Observations on the Test. 133-135. Analytical Tables—Div. A (Solid Species), 136; Div. B (Liquid Species), 141. Numbered Specific or Semi-specific Ketone Tests —(701) Colorations with Sodium Nitroprusside; (702) Oxidations with Chromic Acid; (703) Pyrrol-red Reaction of 7-Diketones; (711) Acetone; (712) Acetophenone; (713) Benzoin; (714) Benzophenone; (715) Camphor. 146-150. 87-110 111-127 128-132 133-150 CONTENTS. ix CHAPTER X. Meee tiles BoRD. I, Ord. [).—ALCOHOLS .....0..00.. ccc cceccccncvemeccuccees 151-172 Generic Characterization.—Generic Test VIII; Procedures 1, 2, and 3; Observations on the Test. 151-154. Analytical Tables—Div. A, Sec. 1 (Solid ‘‘Soluble” Species), 155; Div. A, Sec. 2 (Solid and not ‘‘Soluble” Species), 158; Div. B (Liquid Species), with Sp. Gr. less than 0.90), 160; Div. B, Sec. 2 (Liquid Species, with Sp. Gr. greater than 0.90), 164. Numbered Specific or Semi-specific Tests —(801) The Iodoform Test; (811) Allyl Aleohol; (812) Benzyl Alcohol; (813) Butyl Alcohol; (814) Ethyl Alcohol; (815) Ethylene Glycol; (816) Glycerine; (817) Isobutyl Alcohol; (818) Iso- propyl Alcohol; (819) Methyl Alcohol; (820) Propyl Alcohol. 166-72. CHAPTER XI. Grnus IX (SusBorp. I, Orp. I) HYDROCARBONS, ETC ...........ce cece cccees ee eh 7o-2U3 Generic Characterization, and the Sectional Tests, 173. Analytical Tables—Div. A (Solid Species), 174; Div. B, Sec. 1 (Liquid Species. Sp. Gr. below 0.85, not giving Tests 901-903), 182; Div. B, Sec. 2 (Liquid Spe- cies, Sp. Gr. below 0.85, but attacked in Tests 901, 902, or 903), 184; Div. B, Sec. 3 (Liquid Species, Sp. Gr. above 0.85), 189. Numbered Specific or Semi-specific Tests —(901) Bromine Test for Unsaturation, etc.; (902) Action of Fuming Sulphuric Acid; (903) Action of Fuming Nitric Acid; (904) Colorations with Aluminium Chloride; (905) Oxidation of Side- chains (1) with Permanganate, (2) with Chromic Acid, (8) with Nitric Acid; (906) Test for C:CH Group; (907) Saturated Ethers of Div. B; (911) Ace- naphthene; (912) Anthracene; (913) Benzene; (914) Mesitylene; (915) Naphthalene; (916) Phenanthrene; (917) Pseudocumene; (918) Toluene; (919) m-Xylene; (920) p-Xylene; (921) o-Xylene. 195-203. CHAPTER XII. SUBORDER II oF OrpDER I.—CoLORED COMPOUNDS OF ORDER I...........cc cece ecces 204-216 Subordinal Characterization, 204. Analytical Tables.—Div. A, Sec. 1 (Solid Species of Determined Melting-point), 205; Div. A (Supplementary), Sec. 2, 212; Div. B (Liquid Species), 215. Numbered Specific Tests —No. 1011, Anthraquinone; 1012, Benzoquinone; 1013, a-Naphthoquinone; 1014, Phenanthrenequinone, 216. CHAPTER XIII. Seat) METHODS, APPARATUS, AND RWAGENTS. .....2..s000sccsscervnseecesenncss 217-237 Melting- and Boiling-points—Usual and Special Methods for Determining; Sources of Error and Corrections, 217-223. Thermometric Indications of Chemical Purity —Fractionation Tests; Sharpness Tests; Fusion and Boiling Intervals. 223-227. Specific Gravities—Determination with the Capillary Pyne or the Pipette, 227-229. Color.—Color Terminology; Pigmentary Color Standards; Color Symbols; Color Comparisons, 230-234. List of Special Reagents and Apparatus, 236-237, ALPHABETICAL INDEX.... weer ailetetaviarabee lols. ove Tevoreie<.larsosge.scele, breve re eteter sneverste steel sea etemnme Foraona: INpmx wi sc Wau oe een coe be sb cd sa oe a i j ne aie 4 7 est ee z bi) i . « we ‘A «Sly ME 2 en ar Oe ae tir a= . etd, x P| Ae. ac. alc. ald. alm. alk. anhyd. aq. as. b. p. Bu. d. a. d.w.m. delig. dil. TABLE OF ABBREVIATIONS. =above. Before a melting-point or boiling-point indicates that the change occurs above the tem- perature given. =about. Indicates that the value following is only approximate. (standing after the symbol for a metal)represents the acid residue of the acid in whose description it occurs; e.g., PbA, in a descrip- tion of benzoic acid would rep- resent lead benzoate. = acetic acid or acetate. =acid. = alcohol or alcoholic. = aldehyde. = almost. = alkaline. = anhydride. = water or aqueous. =asymmetrical. = boiling-point. =butyl, C,H,, without regard to structure of the radical. = benzene. =corrected (not necessarily correct) ; also cold. = chloroform. = concentrated. =crystals, crystalline, or crystallizes. =decomposes. Standing after a number indicates the tempera- ture at which a substance melts or boils with decomposition. Standing before a number it indi- cates the temperature at which decomposition occurs without necessarily implying that the substance either melts or boils. Standing before the name of a compound means dextro-gyra- tory. =decomposes above. Is used in the same way as d. = decomposes without melting. =deliquescent or deliquesces. =dilute. In expressions like ‘dil. ale. (8:1),” the first term of the numerical ratio between paren- theses always refers to the sub- stance directly mentioned, and the second term to the water used as diluent or solvent. = difference. =distils; also, may be distilled, without stating the tempera- ture. =difficultly soluble. See page 38. =ethyl, C,H;,. =ether, (ethyl oxide). =easily soluble. See page 38. Tr. floc. sol. Sef Sbl. w. m. =sublimes without melting. tbl. (Th. i.) volat. vol. w. st. wW. Zz. &. =from. = flocculent. = hot. = insoluble; also, in name of a com- pound, optically inactive. =in vacuo. = specific gravity. = granular. - =levo-qyratory. = | qu id. =ligroin. = meta. = microscopic. = methyl, CH. = miscible. = melting-point. = ‘neutralization equivalent.” fined on page 77.) =non-fusible. = non-volatile. = ortho. =ordinary atmospheric pressure. =ordinary room temperature. =oridize, oxidizes, or oxidation. = para. =pnenyl, C.Hs. = propyl, C,H, (without indicating the structure of the radical). = precipitate or precipitates. = part or parts. (De« = pulverulent. =rapidly heated. (See page 220.) =soluble. (See page 38.)—Before the name of a compound signi- fies symmetrical. = sublimes. = slightly decomposed. (Signifies that the substances melts or boils with slight decomposition at the temperature given.) = saponification equivalent. (Defined on page 113.) = solution. =softens. Indicates that the sub- stance softens at the tempera- ture stated. (Often followed by specification of the temperature.) =tabular crystals. = thermometer immersed in the vapor. = uncorrected. = unsaturated. =vicinal or adjacent. = volume. = volatile. = volatile with steam. =with. = €XCESS. xil SIGNS.—BIBLIOGRAPHICAL. SIGNS. [e]p Specific rotary power (using monochromatic sodium fight). For the carbohy- drates the values given are the ‘‘permanent” rotations at 20° C. obtained with aqueous solutions. [y]p Index of refraction (using monochromatic sodium light). “+ placed after a number in a column of boiling- or melting-points indicates that the substance melts or boils slightly above the temperature given. {[+]lor[—] placed before the name or symbol for a compound indicates that the substance is optically active. T placed before the name of a compound indicates that the position of the latter in the analytical system has been experimentally determined in the author’s laboratory. ‘The “specific descriptions” for such compounds are also based, for the most part, on experimentally verified data. BIBLIOGRAPHICAL. Abbreviation. Title. A. Liebig’s Annalen der Chemie. A. ch. Annales de chimie et de physique. A. ch. an. Annales de chimie analytique. Allen. Allen’s Commercial Organic Analysis, 3d Edition (Blackiston’s Son). Anl. The Analyst. Am. American Chemical Journal. Am. Soe. Journal of the American Chemical Society. Ar. Archiv der Pharmacie. B. Berichte der deutschen chemischen Gesellschaft. BL. Bulletin de la Société Chimique de Paris. C. Chemisches Centralblatt. Orr: Comptes rendus de |’ Académie des Sciences. Ch. Ind. Journal of the Society of Chemical Industry. Ch, Z. Chemiker Zeitung (Céthen). Cho N; Chemical Nevs. rT. (Fresenius’) Zeitschrift fiir analytische Chemie. G. Gazzetta Chimica italiana. lee (Hoppe-Seyler’s) Zeitschrift fir physiologische Chemie. J. Jahresbericht der Chemie. Jape: Journal fiir praktische Chemie. M. Monatshefte fur Chemic. Ph. Ch. Zeitschrift fiir physicalische Chemie. R Recucil des travaux chimiques des Pays-Bas. Soc. Journal of the Chemical Society of London. re see eee eee eee ee ee ee TT TT ee ee a EL ELLE LEE ELLE I SELL TCE IE) IDENTIFICATION OF ORGANIC COMPOUNDS. CHAPTER I. CLASSIFICATION OF COMPOUNDS AND THE GENERAL ANALYTICAL PROCEDURE. To facilitate their identification, the pure compounds or chemical species described in this work are systematically arranged in genera, orders, and various minor groups. The general analytical procedure can be applied intelligently only after the underlying principles of this classification are clearly understood. The order of any species is determined by its qualitative elementary compo- sition. Compounds made up of the same elements belong to the same order. The compounds of carbon and hydrogen, and of carbon, hydrogen, and oxygen, con- stitute Order I of the system, and are the only ones described in the present volume. Order I contains two suborders, Suborder I including all colorless, and Suborder IT all colored species. Tests having as their object the determination of the order of a species, i.e. tests for the elements, are called ordinal tests. ‘They will be fully treated in Chapter IT. . A genus is a group of species characterized by showing a common behavior in certain prescribed and carefully defined generic tests. With few exceptions generic tests are based on chemical reactions rather than differences in physical properties. The experimental details for each generic test are to be found at the beginning of the chapter devoted to the genus whose number it bears. Typographically generic tests are distinguished from other numbered tests by being printed in Roman instead of Arabic numerals. Test III, for instance, means the test prescribed (page 35) for the recognition of species of Genus III (Acids). The genera are so arranged that no species shall give the generic test for any genus preceding it in the same suborder. A concise summary of the generic tests of Suborder I, Order I, is given on page 5. All genera, including both solid and liquid species, contain two divisions. Division A contains the solid, and Division B the fluid species. Gaseous species are so few in number that they are treated in division B with the species that are liquid under the ordinary conditions of temperature and pressure. The “ divisions”’ of some genera are composed of smaller groups of species called sections. The term section is also, though less frequently, applied to small arti- ficial groups of species, like the two sections of Suborder II, when the chemical 2 CLASSIFICATION OF COMPOUNDS. relationships between the members of the group are not sufficiently intimate to warrant their erection into genera. Sectional tests when based upon chemical reactions are referred to by numbers, and described just before the true specific tests, and immediately after the tabulated descriptions of the species of the genus. The chemical species or compounds, the fundamental units in the classification, are, whenever practicable, arranged within their respective genera, divisions, or sections according to the numerical values of their melting-points, if they are solids; or of their boiling-points, under standard conditions, if they are liquids. Genus II of Suborder I, and Supplementary Section 2 of Suborder IJ, furnish the only examples in this volume, of groups of compounds whose arrangement within their respective sections of the tables is not dependent on the values of these constants. Specific tests are primarily designed to distinguish a species from others situated near it in the same subdivision of its genus, and in the regular course of analysis should follow the ordinal, generic, and sectional tests. Very few of them have much — significance if applied directly to an entirely unknown compound. It is conceivable, for instance, that there may be a number of organic liquids which will give a white crystalline derivative melting at 92°-93° when treated as directed in Specific Test 814; but if it is also shown that the unknown substance is a colorless compound of carbon, hydrogen, and oxygen belonging to Genus VIII, Division 2, and boiling at 78°, the proof that the species is ethyl alcohol is overwhelming. ‘The most satis- factory specific tests are usually those in which a few centigrams of a compound are quickly converted into a well-characterized derivative. The directions for many specific tests form a part of the specific characterizations of the tables, but some of the more important tests in each genus are described together immediately after the tables of the genus to which they relate, and referred to in the characterization by test numbers. In Order I, one hundred numbers are reserved for the description of the sectional, semi-specific, and specific tests of each - genus, the first ten numbers in each hundred being set aside for the sectional and semi-specific,* and the last ninety for the true specific tests. Any numbered test in Order I may be easily found without consulting the index, if it be remembered that the numeral denoting the hundreds in the test number (e.g. 3 in 321) is also the number of the genus to which the compound concerned in the test belongs. The last two numerals in the test number indicate the position of the test among its fellows. Test 302 will accordingly be recognized at a glance as either a sec- tional or semi-specific test of Genus III (Acids). By turning to page 78 it will be found to be a reaction for the recognition of a-hydroxy acids. In the same way Test 319 will be seen to be a specific test for some particular acid. It is actually a description of two reactions for the identification of salicylic acid. The tests connected with the nine genera of Suborder I, Order I, are assigned numbers 100-900. Suborder II, not being divided into genera, has its specific tests numbered as if it were the tenth genus of its order; i.e. they are represented. by the numbers 1000 to 1100. . Soe 4 * By a semi-specific test is meant one employing some general experimental procedure that leads to similar results with a number of compounds, but which enables a partial selec- tion between some of the species situated in the same smallest subdivi ision of a genus. ae 301, 302, and 303 are semi-specific tests. ‘ : aie GENERAL ANALYTICAL PROCEDURE. 3 GENERAL DIRECTIONS FOR THE IDENTIFICATION OF AN UNKNOWN COMPOUND. The numbered paragraphs in heavy type which follow form an analytical key to the use of the “ Method”. They indicate the successive considerations that should receive the attention of the analyst in the investigation of every unknown compound. With the explanatory remarks in ordinary type which accompany them, they give a comprehensive view of the general analytical procedure disen- cumbered of detailed descriptions of special operations and tests which can be more advantageously discussed elsewhere. It will be assumed that the reader has already acquainted himself with the classification of the ‘‘ Method ”’. I. PURITY. ESTABLISH A PRESUMPTION THAT THE UNKNOWN SUBSTANCE IS REALLY A PURE COMPOUND BEFORE ATTEMPTING TO IDENTIFY IT. IF IT IS NOT HOMOGE- NEOUS, PURIFY IT. THE CONSTITUENTS OF AN UNKNOWN ORGANIC MIXTURE CAN NOT BE SATISFACTORILY IDENTIFIED PREVIOUS TO THEIR SEPARATION. THE HOMOGENEITY OF COMPOUNDS WHICH EXIST ONLY IN THE FORM OF UNCRYSTALLIZABLE SYRUPS THAT CAN NOT BE DISTILLED WITHOUT SERI- OUS DECOMPOSITION, IS SO DIFFICULT TO ESTABLISH, THAT SUCH SPECIES ARE, AS A RULE, EXCLUDED FROM THE TABLES. To prove absolutely that a substance is chemically homogeneous, it would have to be shown that the physical and chemical properties of all the parts into which a given mass of it can be separated by methods of fractionation that do not affect it chemically, are identical; or, in other words, that no substance can be thus isolated from it whose melting-point, boiling-point, solubility, specific gravity, crystalline structure, chemical behavior, etc., is different from that of the original body. This absolute proof is of course impossible in practice. But if the properties whose identity in the several fractions has been ascertained are very few in number, they may still afford a presumption in favor of chemical homogeneity so strong as to closely approximate to the absolute proof, pro- vided they are judiciously selected and are of a kind that permit of exact measurement. The decision of the analyst as to just how many and what purity tests it will be profit- able to apply to any particular substance, will be influenced by a variety of circumstances, among which will be included the importance of the identification, the extent of his knowl- edge of the methods employed in the preparation and purification of the substance, and the quantity of material that is available. If the supply is so small as to barely suffice for the tests of the regular procedure exclusive of special homogeneity tests, there will be no alternative between abandoning the examination altogether, and hazarding the loss of all the substance in what may at the end prove to be fruitless experiments upon a mix- ture. Whenever it is decided in such a case to proceed with the examination, it must be remembered that the results will be worthless unless the final specific tests are most unequivocal. Of all the methods affording indications of purity, those which depend upon constancy or sharpness in melting- and boiling-point have been the most widely used. Indeed, it is altogether probable that for a majority of the organic compounds which have been described, the only direct evidence of purity that it has been considered necessary to secure, pre- liminary to the first ultimate analysis,—aside from that incidentally gained from their general appearance and behavior towards solvents—has been that furnished by these simple thermometric methods. The use and interpretation of these purity tests will be discussed somewhat fuliy in Chapter XIII (pp. 223-227). The truth of the proposition that “The constituents of an unknown mixture can not be satisfactorily identified previous to isolation,” may, at the first glance, appear to be 4 GENERAL ANALYTICAL PROCEDURE invalidated by the existence of direct tests for organic adulterants in foods, for abnormal constituents in the urine, and the like. These tests, however, all owe their usefulness to the fact that the mixtures to which they are applied—except as regards the compound sought—are, virtually, known mixtures, in the sense that the combined effect of all their customary constituents—known and unknown—upon the test, has been carefully ascer tained by previous investigations. Their value accordingly becomes problematical a soon as any substance not usually present in such a mixture is added to it. The preliminary treatment of unknown mixtures is, undoubtedly, that part of most organic analyses which makes the greatest demands on the originality and patience of the analyst. While the number and peculiarities in chemical behavior of the organic compounds are so great as to forbid the expectation that a general scheme for their separa- tion comparable in simplicity and comprehensiveness to that used in qualitative analysis for the elements can ever be realized, it is reasonable to anticipate that this important branch of Analytical Chemistry will eventually be so far systematized that much less will be left to chance and individual dexterity than at present. The omission from this volume of suggestions for methods of separation occurs, not because the importance of the matter has been underestimated, but because sufficient data for comprehensive and practical generalizations on the subject have not yet accumulated. It is, however, the author’s hope to present such recommendations as can be given for the systematic treatment of mixtures in a later volume. 2. PHYSICAL PROPERTIES. IF THE SUBSTANCE IS A SOLID, DETERMINE ITS MELTING-POINT; IF A LIQUID, ITS BOILING-POINT AND ITS SPECIFIC GRAVITY AT 20°/4°. IN EITHER CASE NOTE ITS ODOR, COLOR, TASTE, AND OTHER SALIENT PHYSICAL CHARAC- TERISTICS, AND DETERMINE ITS APPROXIMATE SOLUBILITY IN WATER. The determination of melting-points is discussed on pages 217-221. Most of the melting-points recorded in the tables are probably “uncorrected.” The boiling-points, on the contrary, are in general to be regarded as corrected for stem-exposure, and have been approximately reduced to their values under the standard pressure of 760 millimeters whenever possible. The determination of boiling-points is treated on pages 221-223. Whenever small distilling flasks are employed in making these determinations, the use of the asbestos diaphragm shown in Fig. 6 should never be neglected. The specific gravity of liquids, if the quantity available is very smail, is best determined by aid of the capillary pyknometer described on page 228. 0.2 cc. of the liquid will be enough to enable a satisfactory determination in this apparatus. Color comparisons should be expressed in terms of the color standard placed in the back cover of this volume and described on pages 230-234. The determination of solubility in water at the temperature of the laboratory may be quickly made by the approximate method of page 38. These tests are made so early in the procedure, because, unlike most of those which follow, they consume little or no material which can not be recovered, while the informa- tion which they furnish is almost certain to be required at some later period in the inyesti- gation. 3. ORDER. DETERMINE THE ORDER OF THE COMPOUND BY APPLYING THE ORDINAL TESTS IN THE SUCCESSION AND MANNER DIRECTED IN CHAPTER II, PAGE 9 ET SEQ. IF THE COMPOUND CONTAINS ANY ELEMENTS OTHER THAN CARBON, HYDROGEN, AND OXYGEN, IT IS NOT DESCRIBED IN THIS VOLUME. IF IT CONTAINS CARBON AND HYDROGEN, OR CARBON, HYDROGEN, AND OXY- GEN, AND IS COLORLESS, IT BELONGS TO SUBORDER I, ORDER I. _ IN THIS CASE TURN TO PARAGRAPH 4 BELOW. _ IF IT BELONGS TO ORDER I, BUT IS COLORED (ILE., BELONGS TO SUBORDER II), TURN TO PAGE 204, GENERAL ANALYTICAL PROCEDURE. 4) 4. GENUS. {For Species of Suborder I, Order I.}-APPLY GENERIC TESTS I-IX SUCCESSIVELY UNTIL THE GENUS OF THE COMPOUND IS ASCERTAINED. DO NOT VARY THE ORDER OF THE TESTS, NOR OMIT ANY WHICH ARE NOT KNOWN FROM THE CIRCUM- STANCES TO BE POSITIVELY UNNECESSARY. BEFORE PERFORMING ANY GENERIC TEST FOR THE FIRST TIME, READ CAREFULLY THE “OBSERVA- TIONS’? WHICH FOLLOW THE DIRECTIONS. THE PAGES ON WHICH DIREC- TIONS FOR THE SEVERAL GENERIC TESTS ARE TO BE FOUND, ARE GIVEN IN THE “TABULAR SUMMARY OF GENERIC TESTS” BELOW. When a generic test is subdivided into parts, a statement of the sequence in which they should be applied, or of the circumstances under which certain of them are to be omitted, is always conspicuously placed near the head of the chapter devoted to the genus. TABULAR SUMMARY OF GENERIC TESTS I-IX IN SUBORDER I, ORDER I. Test_ Number Condensed Description of Test. and Page. I (p. 15) Aldehydes.—A color reaction with a fuchsine solution decolorized by sulphur- ous acid. Requires 5 cgr. of substance. ‘Time about 3 minutes. II (p. 26) Carbohydrates——The Molisch color reaction with a-naphthol, followed by three short supplementary tests to exclude glucosides in case the proper color is obtained. The Molisch reaction requires 5 mgr. of substance and can be applied in 5 minutes. The supplementary tests, when made, require in all 11 cgr. of substance and can be applied in 5 minutes. Ii (p. 35) Acids.—A titration with decinormal sodium hydroxide and phenolphthalein, Requires 1 decigr. of substance. Time about 30 minutes when a neutrali- zation equivalent is determined; in other cases (cf. note on p. 35) 5 minutes. IV (p. 27) Phenolic Compounds.—The test has two parts: (1) a color test with ferric chloride consuming 5 to 10 mgr. of substance, which can be applied in less than 5 minutes; (2) a solubility test with aqueous alkali, which can be made with 10 cgr. of substance in 4 minutes. Part 2 is used only for solids that fail to give part 1. V and VI Esters and Anhydrides.—-A saponification experiment with 10 cgr. of substance, (pp. 111-128) which is heated with 2 cc. of alcoholic potash solution for 30 minutes. (During the heating, preparations for Tests VII and VIII will be made.) [A second longer-and more difficult saponification procedure (cf. p.113) with aqueous potash and a gram or two of substance is required when it is wished to isolate the neutral saponification products from an ester, and thus distinguish certainly between species of Genera V and VI. It is never applied when the first procedure has given a negative result; and its use is generally inadvisable when the total supply of substance does not exceed 2 grams. When omitted, Genera V and VI have to be treated as a single composite genus. ] VII (p. 133) | Ketones.—Solid compounds melting above 30° are tested with hot alkaline hydroxylamine solution; all compounds liquid at temperatures below 30°, with phenylhydrazine solution. The test with hydroxylamine requires 10 cgr. of substance; that with phenylhydrazine about 5 cgr. Time in either test about 15 minutes. VIII (p.151) | Alcohols.—To this genus belong: (A), all species not included in earlier genera that are soluble in less than 30 parts of water at 20°; (B), all compounds liquid below 75° that evolve hydrogen on treatment with sodium; (C), all compounds solid at 75° that are not acetylated by acetic anhydride under certain prescribed conditions. Test A has been already made in the pre- liminary examination. Tests B and C require about 20 egr. and 10 cgr. of substance respectively. Test B can be performed in 10 or 15 minutes; C can not be completed in less than about 50 minutes. [In dealing with insoluble solids time will often be saved by referring directly to the appro- priate division and section in the tables of both Genus VIII and IX with- out applying test C.] IX (p.173) | Hydrocarbons, etc.—Genus IX includes all species not giving Tests I to IX, . and hence has no special generic test of its own, 6 GENERAL ANALYTICAL PROCEDURE 5. GENERIC SUBDIVISIONS. TURN TO THE PROPER DIVISION (A FOR SOLIDS, AND B FOR LIOUIDS) IN THE TABLES OF THE GENUS. IF THE DIVISION CONTAINS SECTIONS, THE DE- SCRIPTIVE DIVISIONAL HEADINGS WILL INDICATE WHAT ADDITIONAL TESTS, IF ANY ARE NECESSARY, MUST BE MADE TO ASCERTAIN THE SECTION. AS the divisions in many genera are not subdivided, and as many of the sections are distinguished from one another by differences in solubility or specific gravity which are already known from the preliminary examination of paragraph 2, additional tests at this point are usually unnecessary. The following table gives a general view of the subdi- visions of the genera of Suborder I, together with page numbers oi each divisional heading. SUBDIVISIONS OF THE GENERA IN SUBORDER I, ORDER IL. ee ee ee Genus Page No. Number and of Division of Basis of Sectional Distinctions. Divisions. ead. Sections. Le 17 0 B 19 0 iA - 2 Solubility in water at 20°, with special chemical tests for III A 39 2 : Pp subsections. B 73 2.) IV A 91 0 B 104 0 Alger. 118 0 B 120 2 VIA 129 0 B 131 0 VII A 135 0 B 141 0 VIII A 155 2 Solubility in water at 20°. B 160 2 Sp. gr. (20°/4°) greater or less than 0.99. IX A 174 0 . B 182 3 Sp. gr. (20°/4°) in sections 1 and 2 less than 0.85; in 3 greater than 0.85. Sec. 1 is distinguished from 2 by chemical tests. 6. SPECIES. COMPARE THE PROPERTIES OF THE SUBSTANCE WITH THE PROPERTIES OF ALL SPECIES THAT MELT OR BOIL WITHIN FIVE OR TEN DEGREES OF ITS MELT- ING- OR BOILING-POINT AND ARE DESCRIBED IN THE SUBDIVISION OF THE GENUS TO WHICH IT HAS BEEN FOUND TO BELONG. The published data concerning melting- and boiling-points are, unfortunately, not always based upon exact determinations. (See page 217.) Hence the necessity for extending the inspection of the tables to include species that are described as melting or boiling a number of degrees from the temperature actually observed. The 5° limit is sufficient for most species whose melting- or boiling-points are below 150°; but the limit of 10° is none too large for compounds that melt or boil at 300°. When the recorded and observed temperatures are both ‘‘ corrected’’ ones, the limit may be safely much reduced. The mode of procedure in the few sections: in which the species are not arranged according to melting- or boiling-points, will always be sufficiently indicated in the sectional headings of the tables. The specific characteristics most serviceable in making a first partial choice between compounds having nearly the same melting-points or boiling-points arei properties like color, taste, and odor, which are obvious from a casual inspection; properties like specific gravity, solubility, boiling-point (for solids), refractive index, and neutralization equivalent, for which numerical values can be deter- GENERAL ANALYTICAL PROCEDURE. td mined quickly, or which are already known in consequence of the preliminary examination and the generic, divisional, and sectional tests that have been made; and, lastly, simple semi-specific tests, such as number 901 with bromine for unsatu- ration, or 302 with ferric chloride for a-oxyacids. Undue weight should not be attached to statements concerning crystalline form which are unaccompanied by exact crystallographic measurements; the general appearance of crystals of the same compound being often strongly influenced by the solvent, temperature, and other conditions accompanying crystallization. The final confirmatory specific tests of the tables are not all of equal merit ov conclusiveness. Many which have been inserted on the strength of apparently good authority, but not verified by the author, may be deficient in essential details. Those introduced by the words ‘‘ Apply Test —” or ‘‘ Identify by Test —” have been carefully studied in the author’s laboratory, and may be accepted as thoroughly reliable. The basis for the recommendation of such as begin with the phrase ‘‘ Gives Test —’ or ‘‘ Gives —in Test —” (e.g. ‘‘ Gives isophthalic acid in Test 905”’) is either experiments made in the author’s laboratory, or positive published statements that the result specified has been produced under conditions which it is reasonably certain will be supplied by the method of the numbered test cited. To complete the identification of any compound for which adequate specific confirmatory tests are not suggested in the tables, recourse to the original litera- ture of the body and its derivatives will frequently be necessary. These descrip- tions have now been made so accessible, and are so well summarized in “ Beilstein’s Handbuch ”’, that suggestions for the desired tests will often be quite readily found. Some general remarks on the selection of suitable derivatives for use in such impromptu specific tests are given on page 234. The properties of many of the species whose names appear in the chemical literature have, however, been either so imperfectly determined or described, that their identifica- tion by any purely analytical method, without some knowledge of the reactions leading to their formation, is an impossibility. All that can be done analytically with such com- pounds, when the quantity of material is limited, is to ascertain whether their percentage compositions and molecular weights harmonize with any hypothesis that we may be in a position to make concerning them. In such cases it will usually make little difference whether we begin or close the examination of the body with the determination of an em-. pirical formula; for when all has been done that is possible under the circumstances, the labor performed will be the same, whichever procedure is chosen. Substantial justifica- tion for the subordination of the method of identification by properties and reactions to that founded on the empirical formula, exists in one case only. This is met with when there are strong reasons for suspecting the unknown substance to be a new compound, or one very unlikely to appear in the tables of this work, and when its quantity is less than about two grams. It would then be unfortunate, in view of the anticipated failure of the attempt at identification by properties and reactions, to forego the possible advan- tages that might be derived from a knowledge of the empirical formula. EXAMPLES ILLUSTRATING THE ANALYTICAL PROCEDURE. The following examples of identifications by the procedure of this “Method” are the records of actual experiments made in a laboratory where the apparatus and reagents required were all in readiness. The contents of each numbered paragraph are a record of the results obtained by following that part of “General Directions for the Identification 8 ILLUSTRATIVE EXAMPLES. of an Unknown Compound” summarized in the paragraph in heavy type designated by the same number. The compounds being known to be pure, the description of operations begins with the examination of physical properties referred to in paragraph “‘(2),” page 4, of the ‘‘General Directions’’. EXAMPLE 1. (HYDROQUINONE. ) (2).—The compound crystallizes in thin colorless needles melting in a capillary tube at 168°-169° (uncor.). It is odorless; tastes faintly bitter-sweet; and is soluble in ap- proximately 20 parts of cold water. (Time 28 minutes.) (3).—Ignited on platinum foil it leaves no ash. The tests after ignition with sodium in the iron tube show the absence of sulphur, nitrogen, and the halogens. It is therefore to be considered a species of Order I; and, because colorless, of Suborder I. (Time 20 minutes.) (4).—It does not give Generic Tests I or II. In the titration of Generic Test III, some alkali is consumed, but the final color transition is not sharp, and the slightly alkaline solution soon acquires a brownish color. The substance is therefore not’an acid, but may be a phenol. Test IV-1 gives a yellow-orange coloration. Test IV-2 gives a solution that rapidly turns brown on standing. The compound is hence a phenol. Turn to the analytical tables of Division A, Genus IV. (Time 22 minutes.) (5 and 6).—Of the ten phenolic species in the tables (p. 99) that melt between 163° and 173°, hydroquinone (m. p. 169°) appears to be the only one easily soluble in cold water. (The solubility given is 17 parts of water at 15°.) ‘The solubility in alcohol and ether, taste, YO coloration with ferric chloride in Test 401, power to reduce silver-nitrate solution on warming, and browning of the alkaline solution in the air, are found to be all properties of the substance which agree with those described for hydroquinone. The final confirmatory Test 411 (cf. p. 108) is next applied, and by oxidation with ferric-chloride solution, quinone is obtained. The quinone is recognized by its odor, and by conversion into quinhydrone, which forms green-black needles melting to a dark-red liquid at about 170°, after previously beginning to soften at about 150°. (Time 40 minutes.) All the tests in the identification of hydroquinone were completed within 1 hour and 50 minutes, and 0.85 gram of hydroquinone was consumed. EXAMPLE 2, (MESITYLENE.) (2)—The compound is a colorless liquid which boils sharply between 163° and 163.5° (uncor.). Its specific gravity (determined in a capillary pyknometer (cf. p. 228) of known capacity, at 25°/4°) is 0.860. Its odor is aromatic; its taste slightly burning. It is in- soluble in cold water. (Time 30 minutes.) (3).—Ash constituents, sulphur, nitrogen, and the halogens are absent. The com- pound is to be sought among the species of Suborder I, Order 1. (Time 18 minutes.) (4) —Negative results are obtained in Generic Tests I, III, IV-1, VI, VII, and VIII, which are the only ones required for liquids. The compound must therefore be sought in Section 3 of Division B, Genus X (Liquid Hydrocarbons with Specific Gravity greater than 0.85 at 20°/4°). (Time 1 hour and 7 minutes.) Turning to the sections designated, it is found that of the six species mentioned with boiling-points between 159° and 169°, only two, p-methylethylbenzene, of B. P. 162°, mesitylene of B. P. 164.5° (cor.), and possibly tert. butylbenzene, B. P. 168°-8.5°, have specific gravities approximating that of the unknown compound. Specific Test 914 (cf. p. 201) for mesitylene is therefore applied, and a white crystalline nitro derivative melting at 235° (uncor.) is obtained. The formation of this derivative, trinitromesitylene, proves the unknown substance to be mesitylene. (Time 60 minutes.) All the tests in this identification of mesitylene were completed in two hours and fifty-five minutes, with an expenditure of 0.87 gram of substance. CHAPTER II. ORDINAL TESTS. DIRECTIONS FOR THE DETECTION OF THE ELEMENTS IN AN ORGANIC COMPOUND. To determine the Order in which an unknown chemical species belongs usually involves a systematic qualitative examination for its component elements. This examination can be safely omitted only when the analyst’s knowledge of the origin of the compound is so complete that it is in itself demonstrative proof that certain elements must be, and alone can be, present. The qualitative procedure that will be given in this chapter makes provision for the detection of all the elements * that are of common occurrence in pure organic compounds, and will ensure the ready determination of the order of all species to be included in the ‘‘ Method”. Whenever a complete qualitative examination is called for, the several tests should be applied in the order in which they appear in the following lettered paragraphs: (a) Ignition Test for Carbon and Ash Constituents.—If reducible metals are probably absent, ignite a little of the substance on platinum foil; otherwise in a porcelain crucible. If the substance burns with a flame, or leaves a black carbon- aceous residue which gradually burns away, it may be considered organic. Care must, however, be taken not to mistake a permanent black residue consisting of a metallic oxide, like copper oxide, or of a reduced metal, like platinum, for carbon. If an incombustible ash is formed, incinerate a larger quantity of the substance in a crucible, and make a complete qualitative examination of the ash by the usual analytical methods. Should the ash contain a metallic element, it is probable that the original compound is a salt of some organic substance of acidic character. Since the ‘“Method”’ only provides for the identification of metallic salts through the acids from which they are derived, it will be necessary, in dealing with a salt, to isolate its acid in a state of purity, preparatory to the location of the latter in the tables. (a’) Ignition Test for Carbon and Hydrogen.—It is rarely necessary to make any other test for carbon than that already given under (a); but the following more exact method is occasionally required: Place 0.1 gram of the substance mixed with five times its bulk of freshly ignited, dry, powdered copper oxide in an ignition-tube of hard glass, having an internal diameter of about 5 mm., anda length of 12 cm. Fill half the space remaining above the mixture with granulated copper oxide, and connect the open end of the tube with a bent gas-delivery tube leading into a narrow test-tube containing a few cubic * Oxygen and hydrogen form important exceptions to this general statement. A simple qualitative test for oxygen in combination, although much to be desired, is at present lacking. A test for hydrogen might always be applied, but the numerical preponderance of the hydrogen- containing species is so great—the present volume being without a single example of a coms pound in which this element is missing—that its general employment is unnecessary. % 10 ORDINAL TESTS. centimeters of baryta solution. Support the ignition-tube in a horizontal position, and begin by heating that portion which contains the granulated copper oxide nearly to the temperature at which the glass begins to soften. This may be conveniently accomplished by use of a single Bunsen burner whose flame has been extended by a wing-top spreader. Next heat the mixture of substance and copper oxide by a second burner held in the hand, manipulating the flame so as to decompose the substance very gradually. The condensa- tion of drops of water on the glass at the cold end of the tube indicates the presence of hydrogen in the substance; the precipitation of barium carbonate in the test-tube, the presence of carbon. The above test, when applied to sulphur compounds, gives a precipitate of barium sulphate. In this case, allow the precipitate to settle without exposing to the air; decant the clear solution; cover the precipitate with a concentrated solution of potassium per- manganate; acidify with dilute sulphuric acid; and test the gas evolved for carbon dioxide. (The permanganate serves to oxidize the sulphur dioxide, thus preventing its escape when the solution is acidified.) SULPHUR, NITROGEN, PHOSPHORUS, CHLORINE, BROMINE, AND IODINE. Before applying the tests for these elements it is necessary to bring them into inorganic combination by fusing the organic substances containing them with metallic sodium. The analysis is then easily and quickly accomplished with an insignificant expenditure of material, even in the unusual case when all six elements are simultaneously present, and the product of the fusion consists of a mixture of alkaline sulphide, cyanide, (sulphocyanide), phosphide, chloride, bromide, and iodide. The manipulations connected with these tests, when once learned, will be found to offer no difficulties. The reliability of the process has been established by several years’ practical trial in the author’s laboratory. (b) Directions for the Ignition with Sodium.—Prepare an ignition-tube 8-10 em. in length from a piece of hard-glass * combustion tubing. Support it in an * The employment of an iron or steel instead of a glass tube is usually permissible and preferable. Iig. 1 represents such a tube in use, suspended by the flange A through the per- forated asbestos-board screen B. The dimensions of these tubes should be: length, 9 cm.; internal diame- ter, 1.3 cm.; thickness of walls, 16 mm, They may now be obtained from the firm of Eimer & Amend of New York, by whom they are for sale under the name of ‘‘Tron Ignition-tubes for Use in Organic Analysis.” Unlike glass tubes they may be used for many successive fusions. After each experiment they should be allowed to stand filled with strong hydrochloric acid for several minutes, and then thoroughly cleaned by use of a test- tube brush and water. The manipulations in the test. are the same as with glass tubes, except that an iron tube may be rapidly cooled after the ignition by the application of cold water to its outer surface, as soon as. its temperature falls below visible redness. The time required to complete a test is thus materially shortened; and even when the tubes are iron castings, this practice, in the writer’s experience, has not» been the cause of any accidents. [As the opacity of the iron tube makes it. impossible to observe just when the free sodium is com- pletely destroyed after adding alcohol to it, the operator using this method should always be on his guard against the slight explosions that will follow a premature treat-. ment of the residue with water.] Since it is well known that nitrogen is fixed as cyanide. Fie. 1. when a mixture of sodium, iron powder, and carbona- ceous matter is strongly ignited with free access of air, it might be anticipated that iron would ORDINAL TESTS. 11 exactly vertical position by a narrow metal clamp whose jaws are protected by being wrapped about by one or two layers of asbestos paper permanently wired on. Warm the closed end of the tube gradually before adding the sodium to lessen the danger of cracking the glass. Then drop in the sodium, which should be freshly cut from a large piece that has.been wiped free from all adhering oil by filter-paper. The sodium should weigh about a quarter of a gram, and will be of about the size of a pea. Place a burner flame directly underneath the tube and heat its lower end quickly to redness. As soon as the purple vapor of the melted metal is seen to form a layer more than a centimeter in depth, allow five drops of the substance if a liquid, or an equivalent quantity in fragments if a solid, to fall at intervals of one or two seconds directly upon the red-hot bottom of the tube without touching its side walls. The ensuing decomposition is almost instantaneous, and is some- times accompanied by slight but harmless explosions. The face of the operator should not be brought too close to the mouth of the tube during the reaction.* When the ignition-tube has become cold, remove the excess of sodium by adding 3 cc. of alcohol. Immediate addition of water is liable to cause explosions. As soon as the reaction between alcohol and sodium ceases, stir with a glass rod, and then pour cold water in cautiously, in small portions, until the tube is about two-thirds full. Finally stir again with a glass rod and rinse into a test-tube. Boil and filter. Dilute the alkaline filtrate, which will be nearly colorless if the fusion has been satisfactory, to about 20 ce. Separate portions of this filtrate, which will be designated as ‘‘S,’’ will be used in making the following tests: (c) Tests for Sulphur.—To | cc. of the alkaline ‘‘ solution 8”’, add two or three drops of a dilute sodium-nitroprusside solution. The presence of sulphur will be indicated by the immediate appearance of an intense, but not very permanent, purple coloration.—[It is best to prepare the reagent at the time when it is to be used, by dissolving a small crystal of nitroprusside in a little distilled water. Nitroprusside solutions do not keep well, though in the dry condition the sodium salt is very stable. ] As an alternative test for sulphur, prepare a clear alkaline solution containing lead, by mixing two or three drops of lead-acetate solution with several cubic prove an unsatisfactory substitute for glass in these ignition tests. But experiments have shown that even when the ignition is prolonged (unnecessarily) for five minutes after the addition of the last portion of the organic compound, only a scarcely perceptible blue stain is formed on the filter-paper in test (d) for nitrogen. ‘The tests for sulphur and halogens are not interfered with by the iron. The use of an iron tube is, however, not permissible when the test jor phosphorus is to be applied; for sodium appears always to take up some phosphorus or silicon when ignited in contact with cast iron. * The preliminary examination and the ignition test (a) will have given warning of danger if the substance under examination is a high explosive. Accidents from other compounds, if ordinary caution is observed, need not be feared. Liquids are best dropped into the tube from a medicine-dropper or small pipette. If the liquid is very volatile, its introduction will be much facilitated by passing the ignition-tube through a tight-fitting circular hole cut in the middle of a square screen of asbestos-board. This. screen, resting on the iron ring of a lamp-stand, shields the hand and dropper from the heat of the flame, and at the same time may be made to serve as a substitute for the clamp which would otherwise be used for holding the ignition-tube in position. The same screen may be used with tubes of smaller diameters if the tube 1s first fitted with a circular disc or washer cut from heavy asbestos paper. When in use, such a tube will be suspended from a point near the upper end by its washer, which will rest on the upper surface of the asbestos-board screen. By employing such screens, liquids whose boiling-points are very near the temperature of the labora- tory may be successfully treated. An improvement in the method for testing for nitrogen in small quantities of volatile or explosive substances in given in Vol. II, p. 3. 12 ORDINAL TESTS. centimeters of a solution of sodium hydroxide [1:10], and add to 1 ce. of ‘‘S.” The presence of sulphur will be shown by the appearance of a black precipitate of lead sulphide. (d) Test for Nitrogen.—Boil 2 cc. of solution ‘‘S”’ for a minute or two with five drops of sodium-hydroxide solution and five drops of ferrous-sulphate solution. Then add just enough dilute hydrochloric acid to dissolve the precipitate of iron hydrates, and finally, a slight excess of ferric-chloride solution. A single drop of the last-named reagent will be enough, unless the solution should happen to contain much sodium sulphide, which would act on the ferric salt as a reducing agent. If no blue precipitate appears at once, allow the mixture to stand for a few minutes; then throw on a filter and wash with water. Presence of nitrogen will be indicated by a precipitate of Prussian blue. This precipitate, if scanty, may remain for some time in suspension, giving a turbid greenish appearance to the solution, which, in the absence of nitrogen, should merely show a pale yellow color due to the iron salts that have been added. After filtration, the Prussian blue in such a mixture will appear as a precipitate, or a very pronounced blue stain on the filter-paper. Test (d), so far as known, is universally applicable to all nitrogenous com- pounds except the diazo salts. These bodies when heated lose their nitrogen as a gas at such a low temperature that none of it reaches the sodium in a form that is convertible into cyanide. Diazo salts are, however, so well characterized by their physical and chemical properties, that they are not likely to be mistaken for species of the non-nitrogenous orders. (e) Test for Nitrogen and Sulphur when Present together.—Faintly acidify 1 cc. of ‘‘S ” with hydrochloric acid, and add two or three drops of ferric-chloride solution. A red coloration (ferric sulphocyanide) indicates the presence of sul- phur and nitrogen. This test may be omitted when (c) and (d) have both given a positive result. When a sufficient excess of sodium is used * for the fusion, no sulphocyanide will ever be met with at this point, as, at the temperature of the fusion, sulpho- cyanides are decomposed by the alkali metal to form sulphide and cyanide. It therefore rarely happens that sulphur and nitrogen are not detected by tests (c) and (d). (f) Test for Phosphorus.—Boil 1 cc. of solution ‘‘S” with 3 ec. of concen- trated nitric acid. Cool; mix with two volumes of the ordinary acid ammonium- molybdate reagent; warm to 50°; and allow to stand for ten or fifteen minutes. A pulverulent yellow precipitate indicates phosphorus—(in the absence of arsenic). A portion of the phosphorus originally combined as sodium phosphide is lost as phosphoretted hydrogen when the solution ‘‘S” 1s prepared from the fused mass. Enough, however, remains to give a satisfactory phosphomolybdate pre- cipitate in test (f). (g) Tests for Halogens.—Two cases are to be distinguished :— (1) When sulphur and nitrogen are both absent, acidify 1 cc. of solution ‘‘S ” with nitric acid and add silver nitrate. If a precipitate of silver halide appears, * Cf. Tauber, Ber. 32, 3150. ORDINAL TESTS. 13 place the remainder of ‘‘S ” in a very small porcelain dish; add dilute sulphuric acid to faint acid reaction; and boil down to one third of the initial volume. The boiling is to remove alcohol, which may interfere with test (i), in which chromic acid is employed. Dilute the concentrated solution to 20 cc. Under the name of solution ‘‘ H”’ it will be used for tests (h), (i), and (j). (2) If evther sulphur or nitrogen has been found, prepare solution “ H’’ first, and use 1 cc. of it instead of “S” in making test (1) with silver nitrate. In the preparation of “H” the sulphur will usually have been completely expelled as hydrogen sulphide, and the nitrogen as hydrocyanic acid, so that if no precipitate is obtained, it will be safe to conclude that the halogens are all absent. : To detect several halogens in presence of one another, the following analytical scheme, based on the principles used in Carnot’s method for their quantitative separation, is recommended as direct and reliable. The complications and mistakes which are liable to occur in using other procedures when a solution contains sulpho- cyanide, or when all hydrocyanic acid and sulphuretted hydrogen have not been removed in the preparation of ‘‘ solution H,” are here rendered impossible in conse- quence of the complete oxidation or expulsion of the disturbing compounds that occurs during the operations in the test for bromine in (i). (h) Test for Iodine.—Place ‘solution H”’ in a 50-cc. separatory funnel, add 3 drops of the nitrosyl-sulphate solution whose preparation is described in the foot- note,* and shake out thoroughly with 5 cc. of carbon disulphide. If iodine is present it will be liberated and taken up by the disulphide, which will acquire an amethys- tine purple color. Shake out with fresh portions of the disulphide until the last portion added is removed colorless. Then add two or three more drops of the nitrosyl-sulphate solution, and repeat the operations described until it is certain that all the iodine has been removed. (i) Test for Bromine.—After the separation of iodine by the method described in the last paragraph, filter the solution through a wet filter to remove the last of the carbon disulphide and transfer to a 75- or 100-cc. round-bottomed flask. Support the latter in a slightly inclined position by means of a clamp, and add to its contents 0.7 grm. of powdered potassium dichromate (free from chloride) and 6 cc. of dilute sulphuric acid. Rinse out the neck of the flask with a little distilled water. Drop in an ebullator tube (cf. p. 223), and then boil the solution briskly over a free flame. Just before boiling begins, insert a short roll of fluorescein * Nitrosyl-sulphuric Acid Solution —Grind together in a mortar 15 grms. of starch and an equal weight of water. Pour the thick cream into a 300-ce. distilling-flask, heated by a boiling water-bath, and then add to it 30 cc. of pure nitric acid (sp, gr. 1.35). The flask is to be pro- vided with a dropping-funnel, and with a delivery-tube for conveying the oxides of nitrogen that will be evolved, into 30 cc. of concentrated sulphuric acid, in which they are to be absorbed. The sulphuric acid should be placed in a small flask surrounded by cold water. A small empty bottle should be interposed between the distilling-flask and the sulphuric acid to condense most of the water and nitric acid that pass over with the gases. Heat the mixture in the flask until a vigorous evolution of gas sets in. When this begins to slacken, gradually admit into the flask through the dropping-funnel 60 cc. more of the nitric acid of 1.35 specific gravity, and continue the heating as long as the oxides of nitrogen are given off freely. The product is a nearly saturated solution of nitrosyl-sulphuric acid in sulphuric acid. In a closed bottle it _ keeps indefinitely. 2H.SO,+N,0; =H,0 + 2NO.0.S0,.0H. 14 ORDINAL TESTS. paper * for half its length into the mouth of the flask. If the solution contains bromide, bromine vapors will be liberated. These vapors mixed with the hot steam change the lemon-yellow color of the test-paper to a rose-pink. Chlorine is not set free. The test with fluorescein must be repeated at intervals of two minutes, using fresh portions of the test-paper each time, until it is certain that the last trace of bromine has been expelled. (j) Test for Chlorine.—Dilute “H,” after the removal of iodine and bromine, to at least 50 cc.; add 2 or 3 cc. of dilute nitric acid; bring to a boil and test for chlorine with silver nitrate. If a precipitate which remains reddish after washing is formed, it is probably colored by silver chromate. In such a case it should be redissolved in a little warm ammonia, and after dilution reprecipitated by nitric acid. The precipitate, if silver chloride, will now be white. DETERMINATION OF THE SUBORDER. The colorless species of every order form its first suborder, and its colored species its second suborder. ‘The position in the classification of compounds that are only very slightly colored is fixed by rules stated on page 204. * Fluorescein Paper.—This is prepared by soaking filter-paper in a filtered solution con- taining one part of fluorescein in two hundred parts of 50 per cent acetic acid. The paper, which should then have a clear lemon-yellow color, is quickly air-dried, cut in strips, and pre- served in stoppered bottles. It keeps well when not exposed to bright sunlight. The change in color produced in this paper in test (i) by the mixture of bromine vapor and dry steam is due to the formation of eosine (tetrabromfluorescein). CHAPTER IIL Gi NiUisy I MEDI el a ADI sks) OF SUBORDER I, ORDER I. (Colorless Compounds of Carbon, Hydrogen, and Oxygen.) This genus is by definition made to include all species of the suborder which give . Generic Test I. The definition admits to the group in addition to the true aldehydes those acetals that are partially hydrolyzed to aldehydes under the conditions of the test, but excludes the aldose carbohydrates. GENERIC TEST I. ADD 0.05 GRM. OF THE FINELY POWDERED SUBSTANCE, IF IT IS A SOLID, OR ONE DROP, IF IT IS A LIQUID, TO 5 CC. OF A FUCHSINE ALDEHYDE REAGENT * THAT HAS BEEN PREPARED BY THE METHOD DESCRIBED BELOW. IF THE SUBSTANCE DISSOLVES, ALLOW THE SOLUTION TO STAND TWO MINUTES AND THEN OBSERVE THE COLOR. IF THE SUBSTANCE DOES NOT DISSOLVE, SHAKE THE TEST-TUBE CONTAINING IT GENTLY FOR TWO MINUTES AND THEN OBSERVE THE COLOR. NEVER APPLY HEAT. THE APPEARANCE OF A DISTINCT PINK, RED, PURPLE, OR BLUE COLORATION IN THE SOLUTION WITHIN THE TIME LIMIT INDICATES THAT THE COMPOUND TESTED SHOULD BE SOUGHT FOR IN THE TABLES OF THIS GENUS. IF THE SUBSTANCE IS A SOLID, AND NO COLORATION IS OBTAINED, PASS ON TO GEN- ERIC TEST II; IF A LIQUID, TO GENERIC TEST III. Observations on Generic Test I. Soluble aldehydes usually color the fuchsine reagent within a few seconds; those which are difficultly soluble and of high molecular weight sometimes require the full two minutes. Solid substances which for any reason are suspected to be polymerized aldehydes should be boiled with 5 cc. of water containing a drop of strong hydrochloric acid, if no color appears within the time limit, and a few drops of the cooled solution then added to the reagent. Enough of the compound (e.g. metaldehyde) may thus be depolymerized to give a good reaction. Ordinary acetone and some other soluble ketones prepared by destructive distillation gradually redden the reagent if added to it in large quantity, or allowed * (The Fuchsine Aldehyde Reagent.—Dissolve 0.2 grm. of rosaniline, or, if the free base can not be obtained, of the hydrochloride or acetate, in 10 cc. of a freshly prepared, cold, saturated aqueous solution of sulphur dioxide. Allow the solution to stand until all signs of pink dis- appear and it becomes colorless or pale yellow. This will require several hours. ‘Then dilute with water to 200 cc. and preserve for use in a tightly stoppered bottle. This reagent keeps well if not unnecessarily exposed to air and light, and should always be kept on hand. The directions for its preparation should be followed with care, since any large increase of sulphurous acid above the quantity specified diminishes its sensitiveness so much as to render it unserviceable in testing for the less reactive aromatic aldehydes like sali- cylic aldehyde, vanilline, etc. A reagent that has been in use many months and is found to have lost sensitiveness may be re-sensitized by the cautious addition of sodium acetate, stop- ping at the moment when a faint pink coloration begins to appear, and then discharging this color by a few drops of the oxidized solution held in reserve for the purpose. In this connec- tion it should be stated, by way of caution, that free alkali, or the alkali salts of any weak acid, organic or inorganic, will redden the reagent like an aldehyde. It is also reddened by heat or when exposed in small quantities to the air for some hours at the ordinary temperature. Min- eral acids greatly diminish its sensitiveness. | 15 16 CHARACTERISTICS OF THE ALDEHYDES. to remain in contact with it for a number of minutes; but the color is due chiefly, if not wholly, to the presence of traces of aldehydes or acetals. The limits set upon the quantity of material used, and the time allowed for the development of a distinct coloration, are, therefore, both conditions that must not be disregarded. The reaction is so delicate that the traces of aldehydes occurring as impurities in many commercial preparations may make trouble if their preliminary purification is neglected. But if the conditions prescribed for the test are carefully observed, the best commercial preparations of bodies belonging to other genera rarely give any color within two minutes.* General Physical and Chemical Characteristics of the Aldehydes. Nearly all aldehydes of the liquid division are distinguished by characteristic odors, which, for the more volatile species, may be described as ethereal and at the same time irri- tating or pungent; and for the higher boiling ones, as aromatic, fragrant, or spicy. The solid aldehydes are either odorless or have odors similar to those of the higher boiling liquid aldehydes, though as a rule less intense. Genus I is notable chemically for the great reactivity of its species. Brief contact with small quantities of concentrated mineral acids, aikalies, or certain metallic salts often causes gradual or sudden polymerization of aldehydes to more stable “para” or “meta” modifications, which would entirely fail to give aldehydic reactions were it not for their tendency to dissociate to some slight extent, under the influence of reagents, to the parent compounds. Since the liquid aldehydes are gradually oxidized to acids by exposure to the air, commercial preparations of the species of Division 2 will often be found to react acid towards litmus or phenolphthalein. Aldehydes are readily oxidized by alkaline permanganate in Test 304, and by ammoniacal silver nitrate in Test 101. The latter reaction, which is accompanied by the formation of a silver mirror, or a precipitate of finely divided metallic silver, is a simple and valuable test. Aldehydes usually dissolve in concentrated sulphuric acid with decomposition. Hot solutions of caustic alkali attack them with greater or less ease, according to the species, forming salts of organic acids that are sometimes accompanied by other products. Bro- uiine reacts with them readily, hydrobromic acid being evolved. Metallic sodium attacks them much as it does alcohols or phenols, hydrogen being sometimes liberated. Phenylhy- drazine, hydroxylamine, and aniline condense with them to hydrazones, oximes, and anils, compounds which often crystallize well and are very valuable in the identification of in- dividual species. Phenylhydrazine, applied in the manner directed in generic Test VII-2 for ketones, is also a very sensitive general reagent for the detection of the carbonyl radical in aldehydes; but many species in the genera intervening between I and VII likewise react with it. Towards certain reagents like sodium bisulphite, many aldehydes, as well as ketones, act like unsaturated compounds. A concentrated bisulphite solution, when vigorously shaken in a test-tube with an equal volume of a liquid aldehyde, or with a concentrated ethereal solution of a solid aldehyde, frequently evolves heat and solidifies, either at once, or after being cooled and shaken, to a thick crystalline magma of the composition R.C.H(OH)(SO,Na), from which the original aldehyde may be recovered by treatment with an alkali or an acid. A negative result from this test does not prove that a sub- stance is not an aldehyde, for many bisulphite addition-products are too soluble in water to appear as precipitates, while others do not combine readily with the reagent. Many ketones, moreover, show the same behavior with the reagent as aldehydes. * Thus, among the alcohols prepared by Kahlbaum, benzyl and allyl alcohols were the only ores which were found to be sufhciently contaminated with an aldehyde to give this test. COLORLESS COMPOUNDS CONTAINING C, H, AND 0 [SUBORDER I OF ORDER II. GENUS I, ALDEHYDES. DIVISION A,—SOLID ALDEHYDES. Melting-point (C.°). 35 37 37 40 44-5 45-6 51 ‘52 52-5 52-53 5A 56 58-5 59-60 61 63-5 80-81 ALDEHYDES.—Colorless and Solid. o-Methoxybenzoic Ald., MeO.C,H,.CHO.—After fusion remelts at 3°.—I. aq.; e. S.eth.;s. alc. B. p. 248°-4° C. Acetylsalicylic Ald., o-C,H,0.0.C,H,.CHO.—B. p. 253° (sl. dec.). Cryst. mass v. s. alc, or eth. { Piperonal (Heliotropine), CH,.0,.C,H,.CHO.—B. p. 263°. Odor of helio- trope! Ndl. fr. h. aq.; s. 500-600 pts. c. aq.; e. s. ale. or eth.—}t Warm 0.1 grm. gently with nitric acid (sp. gr. 1-40); precipitate nitro comp. with cold water; cryst. fr. h. aq.; m. p. of dry, pale-yellow silky ndl. 95-5°. Propionylpropionic Ald.,Et. CO.CHMe.CHO.—B. p. 164-6°. Tbl. s. aq.; v. s.alec. Alc. sol. dark violet w. FeCl. Lauric Ald., C,,H,;.CHO.—Cryst. mass. t Metacrolein, (C,H,O),.—Cryst.; odor spicy.—Distill. Pass irritating acro- lein vapors liberated into 2 cc. aq., and apply Test 112. Furfuracrolein, C,H,O.CHO.—B. p. a. 200° w. dec.—Cinnamon odor.—D. s, aq.; e. s. ale. or eth.; s. glacial Ac. containing aniline w. green color! I, 2, 3-Irimethylbenzoic Ald., Me,.C,H,.CHO.—Nadl. fr. dil. alc. Myristic Ald., C,,H,;.CHO.—B. p. 168°-169° (22 mm.). Polycenanthylic Ald., (C,;H,,0)z.—I. aq.; v.s. alc. oreth. Dist. gives cenan- thylic aldehyde. o-Oxy-p-toluic Ald., Me.C,H,(OH)CHO.—B. p. 222°-3°.—Violet w. FeCl;.— Sol. in ammonia w. deep-yellow color. o-Oxy-m-toluic Ald., Me.C,H,(OH)CHO.—B. p. 217°-8°.—Deep-blue color w. FeCl,.—Ammon. sol. deep yellow, + Palmitic Ald:, C,,H;,.CHO.—B. p. 192°-3° (22 mm.). Pearly scales d. s. ¢. eth. Paraisobutyric Ald., (C,H,O),.—B. p. 195°C. Ndl. fr. aq. or alc. Heated w. H,SO, gives isobutyric aldehyde. 8-Naphthoic Ald., C,,H,.CHO.—Lits. fr. h. aq.; v. s. alc. or eth. Stearic Ald., C,,H,,-CHO.—B. p. 212°-3° (22 mm.). Scales fr. eth. + Vanilline, C,H,.(Me0)(OH)(CHO)(3 : 4: 1).—Slender ndl. fr. h. aq.; s. in 20 pt. h. aq. or in 90-100 pt. c. aq; e. s. alc., eth., or CHCl, Strong vanilla odor! Taste at first burning, then like vanilla! Aq. sol. (1 : 200) gives immediate blue coloration w FeCl, in Test 401.—Dissolve 0.05 grm. in 10 cc. aq. Add 2 drops conc. HCl and 2 drops FeCl, sol. (1:10). Boil one minute. Filter hot. Wash. Boil residue w. 5 cc strong alcohol. Filter; dry at 100° and determine melting-point The product, dehy- drodivanilline, forms slender, nearly colorless, silky microcrystalline ndl. melting w. dec, at abt 304° (uncor.). o-Aldehydobenzoic Ac., CO,H.C,H,.CHO.—Lits. v.s. aq., ale. oreth. Ag salt ervst. in ndl. fr. h. aq —NH, gas passed into alc. sol. gives cryst. comp. m. p. 187°. [Gives Test I w. the fuchsine reagent, (A. 239, 82) ] m-Oxybenzoic Ald., HO.C,H,.CHO.—B. p. 240° Ndi. fr. h. aq.—Sol. violet w. FeCl,; gives ppt. w. Pb.Ac,. Heating w. X’s acetic anhydride gives diacetate, m. p. 76°. Trimethyl-o-oxybenzoic Ald., Me,.C,H(OH).CHO.—Pale-yellow ndl.; i. aq. or KOH; s. ale. or eth. Sublimes. nen nnn ae 17 18 Melting-point (C.°). 110 Sbl. 112-15 115 115-16 Sbl. abt. 120 128 130 164-6 175 179 180 221-2 234 237-8d. 243-4 247 248-9 260d. 285 GENUS I, DIV. A, (ORDER I, SUBORDER I.) ALDEHYDES.—Colorless and Solid. p-Oxy-o-toluic Ald., Me.C,H,OH.CHO.—ThbIl.s. h. aq.; e.s. ale.,oreth. Rose red w. FeC],. Ammonia sol. colorless. + Metaldehyde, (C,H,O,)7.— I. aq.; d.s. eth., ale. Dist. w. dil. H,SO, gives acetaldehyde (Test 111). For behavior toward reagents cf. remark on page 15. : p-Oxy-m-toluic Ald., Me.C,H,(OH)CHO.—Pr. fr. aq.—Blue-violet color w. FeCl;. . p-Oxybenzoic Ald., HO.C,H,.CHO.—Sbl. undec. D.s. c. aq.; e. s. ale., eth, Pale-violet color w. FeCl,.—For derivative cf. Paal, Ber. 28, 2409. + Paraformaldehyde (commercial), (CH,O)z.—Odor and reactions like form- aldehyde. White amorphous powder.—Apply Test 114-1. Disalicylic Ald., C,,H,,O;—Sbl. undec. Almost i. aq. or KOH; e.s. alc., eth. Cold conc. H,SO, gives salicylic ald. Dialdane, C,H,,0;.—Cryst. v. d. s. aq., eth.; e. 8. h. alec. m-Aldehydobenzoic Ac., CO,H.C,H,.CHO.—Cu salt green-blue ndl. Weel Go. ee Helicine, C,,H,,0;—(Cryst. w. }H,O, which is lost at 100°.) Small ndl. s. 64 pt. aq. at 8°: i. eth_—No color w. FeCl;. Dil. min. acids hydrolyze to dextrose and salicylic aldehyde. Opt. act. (v-)m-Aldehydosalicylic Ac., (HO)(CO,I1).C,H,.CHO.—Sbl. yellow color in NaOH—Sol. red w. FeCl. Metapropionic Ald., (C;H,O)z.—‘Sbl. fr. 160°. I. aq.; v.d.s. ale. Aldehydovanillic Ac., MeO.C,H,.(OH)(CO,H)(CHO).—Silky ndl. v. d. s. ¢. aq.; s. eth.—Yellow sol. in NaOH. Dingy-violet color w. FeCl. p-Aldehydo-m-oxybenzoic Ac., CHO.C,H,(OH)CO,H.—Ndl. d.s. h. aq.; e.s, ale. or eth.—Sol. in NaOH is deep vellow.—Gives violet color w. FeCl,. Aldehydo-(v)-oxyisophthalic Ac., CHO.C,H,.(OH)(CO,H),.—S, h. aq.; e. s, eth.—Sol. cherry-red w. FeCl,;.NaOH sol. colorless! m-Aldehydo-p-oxybenzoic Ac., CHO.C,H,(OH)CO,H.—D.s.aq.; e.s.eth. Aq. sol. brick-red w. FeCl,. NaOH sol. deep yellow! p-Aldehydocinnamic Ac., CHO.C,H,.C,H,.CO,H.—Sbl. in Ifts. D. s, eth. (a-)m-Aldehydosalicylic Ac., CHO.C,H;(OH)CO,H.—D. s. h. aq.; e. s. eth. ‘NaOH sol. colorless. FeCl, gives red color to aq. sol. Aldehydo-(a)-oxyisophthalic Ac., CHO.C,H,OH.(CO,H),.—Nd1. fr. h. aq., e. s. eth. Does not sublime. Blood-red color w. FeCl,. Alkali solutions are yellow w. green fluorescence. p-Aldehydobenzoic Ac., CHO.C,H,.CO,H.—Sbl. in small ndl. aq.—Ndl. fr. aq. Oxime 5. baa we D. s. ath or h, COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I}. Boiling-point WON 20-8 45-5 48 -8c. GENUS I, ALDEHYDES. DIVISION B,—LIQUID ALDEHYDES. ALDEHYDES.—Colorless and Liquid. t Acetic Ald.. Me.CHO.—G. 0-8056°/,. Odor pungent-ethereal, stifling! Misc. w. aq., alc., or eth_— Apply Test 111! { Methylal, CH,.(OMe),.—G. 0-8721°/,. Odor alcoholic.—E. s. aq.— Apply formic aldehyde Test 114-1 to dil. aq. sol. t Propionic Ald., Et.CHO.—G. 0-80667°/,. S.in 5 pts. aq. at 20°. Odor pun- gent.—Warm w. 2 pts. phenylhydrazine; wash hydrazone w. dil. acetic acid; then heat w. an equal wt. ZnCl, at 180°. Disgusting skatol odor is produced. t Acrolein, CH, :CH.CHO.—G. 0-84. Vapor excessively irritating; in traces provokes flow of tears. EE. s. aq.—Polymerizes to i. solid so readily that it can not long be preserved liquid.—Apply Test 112! Propargyl Ald., CH:C.CHO.—E. s. aq. Very irritating to mucous mem- branes. Gives orange ppt. with ammon. Cu,Cl, sol! { Isobutyric Ald., C,H,.CHO.—G. 0-79387°/,. S.in9 vol aq.—NaHSO, comp. pearly Ifts. rather d. s. aq. Dimethylacetal, Me.CH.(OMe),.—G. 0-866 at 22°. n-Butyric Ald., Pr.CHO.—G. 0-8170°/,. S. in 27 pt. aq.—NaHSO, comp. e. s. aq. or alc. Trimethylacetic Ald., Me,.C.CHO.—G. 0-7927 (18°). Methylene-diethyl Ether, CH,.(OEt),.—G. 0-851 (0°). S. in 11 vol. aq.— Not acted on by h. KOH. + Isovalerianic Ald., C,H,.CHO.—G. 0-82 (0°). Odor when free fr. valerianic ac. sweet and aromatic. Shaken w. conc. ammonia solidifies to cryst. comp. (m. p. 56°-8°). + Formic Ald., (commercial ‘‘40 per cent solution” in water). Distillation leaves white residue of ‘‘ paraformaldehyde” in flask. Odor pungent. Apply Test 114! n-Valerianic Ald., C,H,.CHO.—G. 0-82 (11.2°). + Acetal, Me.CH.(OEt),.—G. 0-8314”°/,. Odor agreeable and refreshing—not irritating.—S. in 18 vol. ec. aq. The dil. aq. sol. if first mixed with a few drops of HCl gives acetaldehyde (Test 111). (Boiling with NaOH gives no acetaldehyde.) a-Crotonic Ald., Me.CH:CH.CHO.—G. 1-033°/,. Odor fruity, then irritat- ing. Absorbs O, and adds Br, easily. Tetramethylene Ald., C,H,.CHO. Tiglic Ald., Me.CH:CMe.CHO.—G 0-87 (15°). Odor like bitter almonds. S. in 40-50 pt. aq. Air oxid. easily. Isobutylacetic Ald., C,H,.CH,.CHO.—Odor aromatic. + Paraldehyde, (C,H,O),.—G. 0-9992 at 15°. M. p. 10°.5. Odor ethereal, agreeable. S. in 10 pt. aq. Heated with a very little conc. H,SO, gives off acetic aldehyde freely. Pure, does not give acetic aldehyde (Test 111) distinctly. Solidified by freezing mixture. M. p. +-12.5° n-Caproic Ald., C;H,,.CHO.—G. 0-8498 at 0°. Methylethylacrolein, Et.CH:CMe.CHO.—G. 0-8577 at 20°. Almost i. aq, Odor penetrating. en nt EID EL ne ee 19 20 Boiling-point (C2). 146:8 155 160-2 161 161 -2d. 166- 2c. 169-6 169-70 170-1d. 179-5 186-8d. 186-8 187 (th. i.) 188-92 193-4 196-5e 199 200 204 205-8 208 208-9 210-8c. 228-9 230 230 235 235—40 GENUS I, DIV. B. (ORDER I, SUBORDER I.) ALDEHYDES.—Colorless and Liquid. Ethylidenedipropyl Ether, CH,.CH.(OPr),.—G. 0-825 at 22°. I. aq.; s. cone. Cl 1. Reduces ammon. AgNO; sol.—Not attacked by hot KOH. { G@nanthic Ald., C,H,,.CHO.—G. 0-84957°/,. Odor aromatic. Ethyl Methylformylacetate, CO,Et.CH.Me.CHO.—Gives intense red-violet coloration w. FeCl. } Furfurol, C,H,0.CHO.—G. 1-1594”/,. Darkens on exposure to light. Odor remotely ‘resembles that of bitter almonds and cinnamon. —Apply Test 15. [Glycid, cf. Genus VIII.} Dist. w. dee. giving acrolein (Test 112). Propylidinedipropyl Ether, Et.CH.(OPr);.—G. 0-8495 at 0°. Isocapric Ald., C)H,,.CHO.—G. 0-828 at 0°. NaHSO, gives no comp. Parapropionic Ald., (C,H,O),.—I. aq. _ Dist. w. a drop or two of cone. H,SO, gives much propionic ald. 4‘, °-Dihydrobenzaldehyde, C,H,O.—G. 1-0327 at 0°. Oil w. penetrating odor. + Benzaldehyde, Ph.CHO.—G. 1-0504."°/,.. Bitter-almond odor. S. in abt. 300 pt. aq.—Apply Test 113. Levulinic Ald., Me.CO.(CH,),.CHO.—G. 1-0156 at 16°. ‘‘Odor aldehydic.” Misc. w. aq. —Reduces Fehling’s sol. in the cold. Colored red by cone. FES) Tetrahydrobenzaldehyde, C,H,,O.—G. 1-0091 at.0°. J. aq. Odor like ace- tone and bitter almonds. Reduces Fehling’s sol. in cold. Methylfurfurol, Me.C,H,O.CHO.—G., 1-1087 at 18°. 5. in 30 pt. aq.—1 drop in 5 ce. ale. +1 ce. conc. sulphuric acid gives green color. Conc. ammonia gives the furfuramide (m. p. 86—7°, ndl. fr. dil. alc.). : Diisovalerianic Ald., C,)H,,0.—G. 0-861 at 0°.. I. aq.; \e. s. ale. Odor aromatic. Phenylacetic Ald., Ph.CH,.CHO.—G. 1-085. Phenylhydrazone ndl. irgr m. p: 537. t Salicylic Ald., o-HO.C,H,.CHO.—G. 1-173 at13°. Odorfaint aromatic. D. S. 2057 Vass ale. or eth, Aq. sol. gives w. FeCl, intense violet color was vert into the phenylhydrazone. / m-Toluic Ald., Me.C,H,.CHO.—G. 1-037 at 0°. Bitter-almond sad Pre- pare corresponding phenylhydrazone, m, p. abt. 90°. o-Toluic Ald., Me.C,H,.CHO.—M. p. of oxime 48°—49°, p-Toluic Ald., Me.C,H,.CHO.—Odor pepper-like.—M. p. of oximes 79°-80°, and 108°-110°. } Citronellal, C,H,,.CHO.—G. 0-8538 at 17.5°. Strong geranium-like odor! Opt. active. Identify by conversion into its semicarbazide of mp. 84°. (Cf. Ber. 31, 3307.) Hydrocinnamic Ald., Ph.C,H,.CHO. (v)-o-Oxy-m-toluic Ald., Me.C,H,OH.CHO.—M. p.17°. D.s. aq.; e. 8. eth._— Sol in ammonia yellow. Sol. in FeCl, bluish. . Ethylidene-diisoamyl Ether, Me.CH.(OC,H,,),.—G. 0-8347 at 15°. { Citral, C,H, ,.CHO.—G. 0-8972 at 15°. Odor of oil of lemon! Opt. active, —Identify by converting into the semicarbazide of m. p. 164° (cf. Ber. 31, 3331). m-Oxybenzoicaldehydemethylether, MeO.C,H,.CHO.—G. 1-11877°/,. Formsa_ d.s. NaHSO, comp. ; £-Diisobutylene Ald., C,H,,0.—G. 0-9575 at 0°. Thick oil of agreeable odor. Resinified by h. NaOH sol. { Cuminic Ald., p-Me,.CH.C,H,.CHO.—G. 0-9832 at 0°. Odor aromatic and characteristic. Gives terephthalic ac.( cf. Test 318).—Color reaction with H,SO0, (A. 137, 104).. + Phenylhydrazone deriv. white but unstable (m. p. 127° 139°), I, 3, 5-Lrimethylbenzoic Ald., Me,.C ‘A, -CHO. | GENUS I, DIV. B. 21 (ORDER I, SUBORDER I.) a hae ALDEHYDES.—Colorless and Liquid. 245 m-Oxybenzoicaldehyde-ethylether, EtO.C,H,.CHO.—G. 1-07687°/,. Yellow oil. 248c. + Anisic Ald., p-MeO.C,H,.CHO.—G. 1-1228 at 18°. M. p. 0°. Odor aro- matic. Hot ale. KOH gives anisic ac. and anisic alecohol.—f Prepare the phenylhydrazone, a pearly-white ppt., m. p. 120° (uncor.). Procedure exactly as in Test 113-1, except that only half the quantity of dilute alcohol there prescribed should be used in each operation. 279 Dicenanthylic Ald., C,,H,,0.—G. 0-8494 at 15°. Oil with faint odor. [Important aldehydes that can be distilled only under reduced pressure. ] 128-30 (20 mm.)| { Cinnamic Ald., Ph.C,H,.CHO.—G. 1-0497%*/,. Odor like cinnamon, © - changed by shaking w. excess of permanganate sol. [1 : 10] to odor of benzaldehyde.—t Prepare the phenylhvdrazone by method given in Test 113-1, except that the product should be boiled up three times with 15 ce. of 50 per cent alcohol, instead of twice with 12cc. This hydrazone is yellow (YT1-YT2), and melts at 168° (uncor.). SS SS SS NUMBERED SPECIFIC AND SEMI-SPECIFIC ALDEHYDE TESTS. [TESTS 101-200.] 101. Compounds Reducing Silver from Tollen’s Reagent. Place 1-2 drops, or about 0.05 grm., of the finely powdered substance in a test-tube with 2-3 cc. of the reagent (whose preparation is described below *). Shake and allow to stand without warming for about five minutes. A black or brownish-black precipitate of metallic silver, or a silver mirror adhering to the walls of the tube, shows that the compound has silver-reducing power and may be an aldehyde. Outside of Order I, Genus I, many scattered species reduce silver from Tollen’s reagent. Representative bodies of this description are glucose among the carbohydrates, and hydroquinone among the polyacidic phenols. So far as it is known, this reaction fails among the aldehydes only in the case of a few aromatic oxy-aldehydes like salicylic aldehyde and vanilline. It is generally a very delicate and satisfactory reaction. 111. Acetaldehyde. (Properties tabulated on p. 19.) 1. Boil 1 ce. of a clear aqueous solution of the aldehyde that is concentrated enough to have a distinctly pungent odor with 5 cc. of sodium hydroxide solution (1:10) for a minute or two. The solution, which at first assumes a clear-yellow color, soon becomes turbid, opaque, and yellow orange (YOSI) from separation of finely divided acetaldehyde resin. At the same time a peculiar, penetrating and rather persistent odor is given off. Although many other aldehydes give colorations to boiling soda solution, and emit odors during treatment, this reaction when applied comparatively, or when the odor and color are both familiar from earlier experience, is a delicate and characteristic preliminary test. Propionic aldehyde, which resembles acetaldehyde more closely in its physical proper- ties than any other species in its genus, gives a somewhat similar odor and turbidity; but the turbidity is less conspicuous in dilute solutions, is nearly white instead of yellow- orange and entirely disappears if the boiling is long continued. Half a drop of acet- aldehyde, for instance, when boiled with 5 cc. of the soda solution is enough to give the test as described; while three drops of propionic aldehyde under the same circumstances give only a milky-white precipitate which disappears on continued boiling with emission of astrong lemon-like odor. The lemon odor is usually noticeable in testing acetaldehyde, but is not the dominant odor. | * Tollen’s Ammoniacal Silver Nitrate Reagent.—This reagent is prepared by mixing equal volumes of a 10 per cent solution of silver nitrate in ammonia, and of a 10 per cent aqueous sodium hydroxide solution. ‘The ammonia solution used for dissolving the silver nitrate should be a mixture of one volume of the most concentrated aqua ammonia of commerce (sp. gr. 0.90) with one volume of water. The solution of silver nitrate in the diluted ammonia should always be kept in stock, but must not be mixed with the caustic soda until it is needed for an experi- ment, since the mixture on long standing deposits a highly explosive black precipitate. It also gives a black precipitate immediately, and without the addition of any reducing compound, when heated to boiling. It is a much more senstive reagent for aldehydes than a simple solu- tion of silver nitrate in ammonia. 22 NUMBEPED SPECIFIC TESTS OF GENUS I 23 2. Shake in a three-inch test-tube 0.18-0.25 grm. of @-naphthol, 2 drops of concen- trated hydrochloric acid, and about 2.0 ce. of glacial acetic acid, until the naphthol is nearly all dissolved. Add one drop of the aldehyde and shake again. Heat at 50°-60° for about five minutes. Then boil for one minute. Cool and shake vigorously until a crystalline precipitate separates. Because of its tendency to form supersaturated solutions, this precipitate sometimes comes down slowly. Allow to stand until the precipitate has begun to settle. Filter through a small filter wet with glacial acetic acid. Wash with 1 ce. of cold glacial acetic acid. Bot with a mixture of 3 cc. alcohol and 1 cc. of water for half a minute or so. Most of the precipitate will remain undissolved. Cool thoroughly and Shake. Filter. Wash with 1 ce. of cold dilute alcohol (1:1). Dry 15-30 minutes at 100°. The product in this test—which is not directly applicable to very dilute solutions of © acetaldehyde—is ethylidene-f-dinaphthyl oxide, melting at 172.5°-173.5°. 112. Acrolein. (Properties tabulated on p. 19.) The following tests for acrolein are to be applied to dilute aqueous solutions strong enough to possess a distinctly irritating odor. (Such a solution, for instance, as is obtained from the distillation of one drop of glycerine with acid potassium sulphate in Test 816-2.) 1. Add 2 cc. of the acrolein solution to 5 cc. of the fuchsine aldehyde reagent pre- pared as described under Test I. (Addition of sodium acetate will never be necessary.) Allow the mixture to stand overnight at the ordinary temperature. It will then appear opaque by reflected light with a deep violet-blue color like cobalt glass. In very thin layers the color will be approximately VR. Add to the blue solution an equal volume of hydrochloric acid, sp. gr. 1.2. Within half a minute the color will change to an impure OYS2. Gradually dilute 2 cc. of this solution to 30 cc. with water. The color on _ dilution will change, passing through yellow-green and blue-green to about VB of the color standard (the comparison being made against a white background in a test-tube about 2 cm. in diameter). These color changes, collectively, distinguish acrolein from all other common volatile aldehydes, although the initial coloration alone is not characteristic. A dilute acetalde- hyde solution, such as would be obtained in applying the distillation test for glycerine (Test 816) to a drop of ethylene glycol, gives a quite similar coloration at the beginning ' of the test, but this fades, sometimes almost to colorlessness, on standing overnight, while the surface of the solution becomes covered with a thin cantharides-green scum. At the end of the experiment when an acetaldehyde solution is used, after the treatment with acid and dilution with water, the final color will be an exceedingly pale tint of VR, having an intensity about half or one third of the VRT2 of the standard. 2. Mix one drop of the acrolein solution with six drops of a cold saturated alcoholic solution of gallic acid, and dilute with water to 2 ce. Pour the mixture gently down the side of an inclined test-tube containing 3 cc. of pure concentrated sulphuric acid, in such a manner that the two liquids shal! not mix. Allow to stand for some minutes. = + 200° (approximately).— Unless so much starch is present as to give a blue color, a very dilute sol. of I in KI produces a strong brown coloration. Unlike gum arabic it does not give Test 204 with phloroglucine.—For additional tests cf. Allen, vol. 1, p. 419. Saccharose (Cane-sugar), C,,H,,0,,.—Colorless monoclinic cryst. s. in 4 pt. c. aq.; d.s.c¢. alc.; ! 100 cc. c. abs. methy] ‘alc. dissolve 0-4 grm.—M. p. abt. 160°-70° d.—_{a]p>= + 66°-5. Taste very sweet.—In Test 201 the yellow osazone ppt. begins to separate fr. the hot sol. if the heating is continued for abt. 30 min.—Oxid. by Test 205 gives saccharic ac., but no mucic ac. + Raffinose, C,,H,,0,,+5H,0.—Ndl., losing all aq. at 110°; when anhydrous melts at 118°-19°.— S. in 7 pt. aq. at 20°; 100 cc. abs. methyl alc. dissolve 9-5 grm. of the anhydrous sugar (dif. fr. saccharose); alm. i. c. ethyl alc.—Taste not noticeably sweet.—[a], = + 104-5°. In Test 201 the yellow osazone does not separate fr. the hot sol. unless the heating is con- tinued for abt. 60 min—Oxid. by Test 205 gives both saccharie and mucic acids. f Gum Arabic.—Although not a true chemical species, this substance gives many of the reac- tions of this section and may be sometimes sought at this point. It consists in part of calcium arabate, and is a hard gum having a fairt odor and insipid mucilaginous taste. tt dissolves slowly in about 2 pts. of c. aq. to a thick transparent mucilage, but is i. in alc. It gives Generic Test II, and Specific Tests 203 and 204.—It gives no osazone ppt. in the h. sol. after 20 min. heating in Test 201, and gives little or no ppt. in Test 202 with Fehling’s sol —Oxid. by Test 205 gives mucic ac_—Ammonium oxalate and ammonia ppt. calcium oxalate fr. the aq. sol. For other tests cf. Allen, vol. 1, p. 426. , 9 30 GENUS II, CARBOHYDRATES. SECTION 1. Subsection C. [Test 201 gives a yellow or orange- yellow precipitate from the hot solution within 20 minutes. All species also give a heavy red precipitate with Fehling’s solution in Test 202. | SU BSECTIONAL PROCEDURE.—Apply Test 203. If no test for furfurol is obtained, see dextrose and galactose. If, on the other hand, furfurol is formed, apply Test 204 with hydrochloric acid and phloroglucine. If the precipitate from Test 204 is of a dark-purple color, see arabinose and xylose; if brown, see levulose, sorbinose, and rhamnose. { d-Glucose (Dextrose or Grape-sugar), C,H,,0,.—Ndl. or crusts fr. ale. (m. p. 146°), or in tbl. w. 1H,O fr c. aq. (m. p. abt. 85°-90°).—Anhydrous dextrose is s. in 1-2 pt. aq. at 17-5°; d. s. c. 90% alc., but v. s. h.; i. eth—{a]p>=+52-8°. Tastes half as sweet as cane-sugar. In Test 201 a heavy yellow ppt. of the osazone [m. p. 204°—-5° (r. h.)] separates suddenly from the hot sol. after abt. 4-5 min. heating! ‘Test 205 gives saccharic but no mucic ac. + d-Galactose, C,H,,0,.—Small hexagonal tbl. fr. abs. ale., m. p. 168° (r. h.); cryst. fr. aq. w. 1H,0O, m. p. abt. 118°-20°. E. s. c. aq.; d.s. c. ale—la]>=+80-3°. Tastes about as sweet as dextrose.—Test 201 gives a heavy yellow to orange-yellow ppt. of the osazone, m. p. abt. 196° (r. h.), separating fr. the hot sol. after about 15-19 min. heating! Oxid. by Test 205 gives mucic ac. ! ‘ | + 1-Arabinose, C,H, ,0;.—Pr. fr. alc., m. p. abt. 160°. V.s. c. aq.; v.d.s. ale.; i. eth—{a])= +104°-5°. The orange-yellow osazone, m. p. 160°, separates fr. the hot sol. in Test. 201 after abt. 10 min. heating; unless the sugar is very pure the osazone often separates in part in the form of brownish-yellow oily drops. Test 204 gives a purplish-black ppt.— Arabinose is best distinguished from xylose by preparing the p-bromphenylhydrazone as described by Fischer [Ber. 27, 2491]. } Xylose, C,H,,0;—Ndl. v. s. c. aq.; alm. i. c. alc. or eth.; m. p. abt. 150°-3°._{a], = + 18.7°. —The orange-yellow osazone, m. p. abt. 160°, separates fr. the hot sol. in Test 201 after abt. 7 min. heating. Test 204 gives a purplish-black ppt.—t Xylose may be quite easily distinguished from arabinose by conversion into cadmium xylonate by the method of Ber- trand [Bull. Soc. [3], 5, 556]. + d-Fructose (Levulose), C,;H,,0,.—Somewhat hygroscopic cryst. or crusts fr. ale.; m. p. 94°! Also in ndl. w. $H,O fr.aq. V.s.aq.; s. 5 pt.c. abs. alc.; s. eth./—_la]p=—90-2°. Tastes as sweet as cane-sugar.—A heavy yellow ppt. of the osazone, m. p. 204° (r. h.), separates from the hot sol. after abt. 2 min. heating in Test 201.—Gives dark, rusty-brown ppt. in Test 204. { Sorbinose, C,H,,.0,.—Rhombic cryst. s. in 4 pt. c. aq.; d.s.h. ale.; m. p. 164°!_(a], = —43-4°. Tastes as sweet as cane-sugar.—The yellow osazone, m. p. abt. 164° (r. h.), separates from the hot sol. in Test 201 after abt. 34 min. heating; it usually separates partly in the form of oily drops, but is easily purified by recryst. from a mixture of acetone and ether.—Test 204 gives a dark, rusty-brown ppt. { Rhamnose (Isodulcite), C,H,.0,+ H,O.—Hard, glassy cryst. fr. aq. or alc., m. p. below 100°. S. in 2 pt. c. aq.; v. d. s. c. ale—[a},=+9-43°. Tastes faintly sweet.—The osazone separates from the hot sol. in Test 201 after abt. 9 min,, as a heavy yellow ppt. (ndl. fr. bz., m. p. abt. 180° d.). GENUS II, CARBOHYDRATES. SECTION 2. 31 SECTION 2. CARBOHYDRATES WHICH EITHER ARE NOT SOLUBLE IN TEN PARTS OF COLD WATER, OR WHICH DISSOLVE, GIVING SOLUTIONS THAT REMAIN STRONGLY OPALESCENT AFTER FILTRATION. { Starch, (C,H,,0,)2.—Ordinary air-dried starch is a white, tasteless powder, containing about 18% of water. Under the microscope it is seen to consist of granules showing concen- trically stratified structure whose size and shape are often characteristic of the plant by which they were produced. (For details concerning the microscopic identification, cf. Allen, vol. I, p. 405.)—Starch is undissolved and unacted upon by c.aq., alc.,or eth. = —39-5°. Easily hydrolyzed by h. dil. HCl, chief product being levulose. Does not reduce Fehling’s sol. (Test 202). Test 201 gives a yellow osazone which begins to sep- arate from the hot sol. after abt. 25 min. heating. Gives no coloration with dil. I sol. } Glycogen, C,H,,0,,—White amorphous powder, m. p. abt. 240°. E. s. c. aq. to intensely yoogen, ©4195 phous p } . opalescent sol.! This opalescence is not destroyed by repeated filtration, but is removed by addition of acetic acid. I. ale—{a]o>=198°.—Test 202 w. Fehling’s sol. gives no ppt. Test 201 gives no ppt. of osazone after heating for one hour. f{ Commercial Dextrin.—Cf. Subsection B. (Filtered sol. in c. aq. often somewhat milky; usually reduces Fehling’s sol.) SECTIONAL AND SPECIFIC CARBOHYDRATE TESTS. [TESTS 201-300.] 201. Osazone Precipitation. Place in a dry test-tube having an internal diameter of 13 mm., 0.100 grm. of the carbohydrate, 0.200 grm. of pure phenylhydrazine hydrochloride* (cf. Note below), 0.300 erm. crystallized sodium acetate, and 2.00 cc. of distilled water. The errors in measurement should not much exceed 1: per cent. Close the tube loosely with a cork stopper to prevent evaporation, and stand it upright in a tall narrow beaker containing two or three inches of water that is already briskly boiling. Note the exact moment of immersion. Shake the tube occasionally without, however, removing it from the beaker. If a precipitate finally separates, note the number of minutes that have elapsed up to the moment; of its appearance. The precipitate usually separates out quite suddenly, so that duplicate experiments will generally give results that agree within about half a minute. Note also whether the precipitate is white, yellow, or orange-yellow, and whether it is crystalline, flocculent, or tends to rise to the surface in oily drops. The properties enumerated are all used either as subsectional or as specific tests in the tables. If a melting-point of the osazone is desired, and it will often be found an important specific constant, cool the hot solution; collect the precipitate on a very small filter; wash with a little cold water; dissolve in the smallest possible volume of boiling 50 per cent alcohol, and filter hot. If the quantity of precipitate which separates on cooling permits, recrystallize once more in the same manner. Dry the precipitate, first on a bit of porous tile, or between filter-papers, and finally at 100°, and determine the melting-point in a bath whose temperature is rising rapidly. The fact that the rate of osazone formation 1s very shes: for the various sugars was first clearly indicated by Marquenne,t but seems not to have been hitherto very gener- ally known or taken advantage of by analysts. The conditions for the test in its present form are so planned that the monosaccharide sugars (the pentoses and hexoses) all give precipitates in from thirty seconds to twenty minutes. Of the polysaccharide sugars, some, like maltose, give products which do not separate until the hot solution is cooled; others, like saccharose, are gradually hydrolyzed to monosaccharides, which then oe the corresponding osazones, but naturally require a longer time for the reaction than when the simple sugar was originally present. The times given in the table for the appearance of precipitates in different cases are based on experiments by several observers, and except for xylose and mannose, several. distinct preparations were used for examina- * [Note on Phenylhydrazine Hydrochloride.—This salt, unless very pure and dry, rapidly decomposes and darkens on keeping. Only a perfectly white and dry salt should be used for the foregoing test. Although the commercial hydrochloride often fails to meet these require- ments, a very satisfactory reagent is easily prepared by dissolving a light-colored sample of phenylhydrazine in twelve volumes of strong alcohol, and then precipitating out the hydro- chloride by the addition of a sufficient excess of the most concentrated hydrochloric acid. Wash the precipitate thoroughly on a suction-plate, first with alcohol and ether, and then with ether, until it is snow-white throughout. Dry on filter-paper in a warm place ‘for half an hour, and then for at least an hour at 100°. Such a preparation, if white at the start, may be preserved for many months if placed in a tightly stoppered bottle, and not freely exposed to the light]. + Compt. rend. 112, 799. 32 NUMBERED SECTIONAL AND SPECIFIC. TESTS OF GENUS II. 33 tion.’ Variations of a minute or two from the stated time-values will occasionally occur however, and this should not be overlooked when it is a question of selecting between two species whose values lie. close together. The precipitates are all phenylosazones, 1.¢., di-phenylhydrazones, except that from mannose, which is a simple phenylhydrazone, and is easily distinguished from’ its associates in being white instead of yellow. 202. Reduction of Fehling’s Solution. __ Add eight drops of Fehling’s Solution * to a solution of approximately 0.03 grm. of the carbohydrate in 3 ce. of water. Boil for two minutes if no precipitate appears before. Arabinose, xylose, rhamnose, mannose, glucose, galactose, fructose, sorbinose, malt- os¢, and lactose give almost immediately a red to yellow-orange precipitate of cuprous oxide on heating. Inulin, raffinose, saccharose, and gum arabic give only a scanty yellowish turbidity after two minutes’ boiling. Glycogen, starch, and cellulose give no precipitate after two minutes’ boiling. The behavior of commercial dextrin is quite variable. 203. Aniline Acetate Test for Carbohydrates giving much Furfurol with Acid. Dissolve 0.3-0.4 grm. of the carbohydrate in 5 cc. of hydrochloric acid prepared by mixing one volume of an acid of sp. gr. 1.20 with three volumes of water. Boil for one minute. Then insert a cylindrical roll of freshly prepared aniline-acetate paper,t two inches long, for half its length into the upper end of the test-tube from which the vapors of steam and furfurol are issuing. Continue the boiling one minute longer if necessary. Certain carbohydrates of Section 1, Subsection C, viz., arabinose, xylose, rhamnose, fructose, and sorbinose, give enough furfurol when thus treated to communicate a bright pink color to the test-paper. The other carbohydrates of this subsection do not occasion noticeable colorations. The coloration sometimes appears in streaks and blotches, but often covers the entire surface of the paper. 204. Color Reactions with Phloroglucine. Boil 3 ce. of the phloroglucine reagent described below {t with about 0.03 grm. of the carbohydrate in a small test-tube. Note the color when boiling is about to begin. Continue to boil until the color ‘darkens very considerably, and the solution begins to appear slightly turbid. This will occur within a minute from the moment when boiling begins. Pour the hot solution without delay onto a wet filter, and rinse the scanty pre- cipitate with a little cold dilute alcohol. Note-the color of the precipitate while moist; it is the most characteristic result of the test. This test is used to distinguish between certain carbohydrates of Section 1, Subsec- tion C. The first coloration on heating with arabinose and sylose is a pure red to violet-red * Preparation of Fehling’s Solution.— Dissolve 34.64 grms. of pure crystallized copper sulphate in distilled water, and dilute the solution to 500 cc. Dissolve 70 grms. of caustic soda of good quality, and 180 grms. of the best crystallized Rochelle salt (potassium-sodium tartrate) in about 400 cc. of water, and dilute to 500 cc. Keep the solutions in separate bottles, and prepare the Fehling’s solution fresh before each series of experiments by mixing the two together in equal volumes. + Preparation of Aniline Acetate Paper.—This is prepared as required for use by wetting strips of thick filter-paper in a mixture of 5 cc. of aniline and 10 cc. of 50 per cent acetic acid, pressing out all excess of the solution between blotting-papers. It should be used while still slightly moist. Xylidine-acetate paper, which has also been recommended by Schiff [A. 239, 380] for the detection of furfurol, is somewhat more sensitive than the paper prepared from aniline acetate. The latter is, however, thoroughly satisfactory for use in the present test. { Preparation of Phloroglucine Reagent—This reagent is made by shaking an excess of powdered phloroglucine with a mixture of equal volumes of concentrated hydrochloric acid and water, until the solution is saturated. The clear solution, unless freshly prepared, is slightly yellow, but remains serviceable for many months and should be kept in stock. 34 NUMBERED CARBOHYDRATE TESTS. (R-VR), which rapidly intensifies and darkens. The color of the precipitate varies according to the duration of the boiling from a very dark purple (VRT2 or RVT2) to black if the boiling is too long continued. With rhamnose, fructose, and sorbinose the first colora- tion is yellow-orange (YO), quickly passing through dark orange to dingy brown. The precipitate is of a rusty brown, or dark broken shade of yellow-orange or orange (YO or O), which will easily be changed to a dull black if the boiling is too long continued. 205. Oxidation to Mucic or Saccharic Acid. Galactose is the only hexose yielding mucic acid on oxidation with dilute nitric acid, and glucose the only one, with the exception of the artificial sugar gulose, that gives sac- charic acid. The reaction has the merit of being applicable to carbohydrate mixtures, as well as to the simple sugars and their polysaccharide and glucoside derivatives. Several grams of the carbohydrate must be oxidized to ensure satisfactory results if saccharic acid isto be sought. The method is fully described by Gans and Tollens, A. 249, 215 (1888), and more briefly by Allen, Vol. I, p. 270.. A close adherence to all details given in these directions is necessary. CHAPTER V. GENUS III. ACIDS OF SUBORDER I, ORDER I. (Colorless Compounds Containing Carbon, Hydrogen, and Oxygen.) This large and important genus includes all non-aldehydic species of the suborder that contain the carboxyl radical, together with a few acid anhydrides and easily sapon- ified esters that show the same behavior as acids when titrated with decinormal alkali by the method of Generic Test III. Many compounds whose solutions in water or alcohol — redden blue litmus, including a few like “carbolic acid,” are popularly known as acids, but are too feebly acidic to meet the requirements of this test. Such species are accord- ingly treated elsewhere, most of them in Genus IV. GENERIC TEST III. APPLY PROCEDURE 1 OF THIS TEST FIRST TO EVERY COMPOUND, SOLID OR LIQUID, REGARDLESS OF SOLUBILITY. APPLY PROCEDURE 2 ONLY TO SOLID COM- POUNDS INSOLUBLE IN WATER WHICH IT IS FOUND DO NOT TITRATE LIKE ACIDS IN PROCEDURE 1. PROCEDURE 1, (Titration in Water.)* Weigh out accurately about 0.10 grm. of the dry substance, finely powdered if it is a solid, into a beaker of 50 cc. capacity. Add 10-15 cc. of cold distilled water, and one drop of a solution of phenolphthalein made by dissolving one part of the indicator in three hundred parts of 50 per cent alcohol. Place the beaker on a sheet of white paper, and titrate cautiously with decinormal soda or baryta until the pink color produced by an excess of one drop of the alkali, after exact neutralization, persists for more than one minute when the solution is constantly stirred. PROCEDURE 2. (Titration in Alcohol.)* If less than 2 cc. of the alkali were required for neutralization in Procedure 1, and if the substance at the same time did not go into solution, and is a solid, repeat the titration, replacing the distilled water by about 25 cc. of strong alcohol of the best * Shorter Alternative Procedure.—Whenever the substance is not very valuable and is not believed to be an acid, it is allowable to take a small unweighed pinch, or three drops (about 0.1 grm.) of the substance for the titrations. If not more than three or four drops of alkali gre neutralized, or if the color transition in the end reaction is not ‘‘sharp,” the time otherwise required for weighings and calcu- lations will be saved. 35 36 GENUS III. ACIDS. quality, using three or four drops of phenolphthalein instead of one, and disregard- ing any precipitate that may form.—[The best commercial alcohol usually reacts acid. This acidity should be exactly neutralized by alkali in each experiment before adding the substance to be titrated.] Any compound that consumes more than 2 cc. of decinormal alkali in either titration, and that also gives a sharp and normal color transition in the end reaction, should be sought in Genus III. The sharpness of the color transition, and the alkali consumption, are phenomena of codrdinate importance. The phrase ‘‘ sharp color transition in the end reaction”’ is here used with the restricted, definite mean- ing given to it in the explanatory observations below. Any compound that yields a solution at the end of the titration that has a pronounced color other than pink is likely to be a species of Genus IV. Observations on Generic Test III.—Never titrate hot solutions nor substitute some other indicator for phenolphthalein. Never omit to reduce the substance to a uniformly fine powder before beginning a titration, unless it is known in advance that it dissolves quickly in cold water. All but the weakest and most insoluble acids may, with a little patience, be success- fully titrated without the use of alcohol if this injunction is observed and the suspended powder is persistently stirred. Even terephthalic acid, which is said to require 67,000 parts of cold water for solution, gives little trouble. But if an acid is at once almost absolutely insoluble and very weak, like stearic and other higher solid fatty acids, an aqueous suspension will not neutralize the alkali, and the use of alcohol becomes indispensable. The sharpness of the color change at the end of a titration is usually more striking in aqueous than in aicoholic solutions. The end reaction in Generic Test III may be defined as beng sharp in the sense intended, when a single drop of decinormal alkali, added at the rvment when the solution is exactly neutral but still colorless, suffices to develop a full strong pink color which is not greatly intensified if the quantity of jree alkali 7g vncreased. Some phenols, $-diketones, and similar compounds, consume more than 2 cc. of the alkali before the appearance of a pink color, but they may be distinguished from the species of Genus III by the lack of sharpness in their ‘‘@nd reactions.” That is to say, an excess of a single drop of the alkali, added at the end of the titration of such a substance, produces only an almost imperceptible pinkish coloration, that then gradually increases in intensity when more alkali is added. There is no abrupt transition such as is observed in titrating a true acid whose salts are not hydrolyzed in solution. The quantity of alkali consumed in titrating from colorlessness to a full pink, has been found to diminish as the strength of the acid (as indicated by its ‘‘affinity constant’’) increases. The limits vary from a fraction of a drop to several cubic centimeters. Presence of carbonate in the alkali, or of carbon dioxide in the water, increases the transition interval, and is very detrimental to sharpness whenever the impurity is at all considerable. A decinormal alkali prepared from the purest commercial caustie soda and ordinary distilled water will, however, be found sufficiently pure for practical use. A blank titration of two or three drops of acetic acid will quickly determine the condition of any doubtful alkali solution. Within quite wide limits, the abruptness of the color change in an end reaction is independent of the quantity of substance dissolved. An acid GENUS III. ACIDS. 37 containing an appreciable quantity of a phenol as an impurity will titrate like a phenol, the pink color appearing gradually after the acid has been neutralized. Aromatic oxyacids (e.g. salicylic acid) titrate as sharply as other acids of the same strength that do not contain phenolic hydroxyl. Polybasic acids with several carboxyl groups also titrate sharply, the end reaction first appearing when ‘all the carboxylic hydrogens have been replaced. Although a small bottle of approximately decinormal alkali, and a glass tube medicine-dropper with a rubber nipple, are all the apparatus that is absolutely necessary for the performance of Test III as a generic reaction, it is strongly recom- mended that the alkali should be carefully standardized, and used from a burette mounted in the manner to be described in Test 301. Accurate neutralization equivalents of an unknown acid may then be quickly determined while making the generic test, without involving any additional manipulations, and will be found nearly or quite as useful as melting-point or boiling-point data in completing the identification. The time limit stated in the direction to ‘‘ Titrate to a pink color that does not disappear after stirring for one minute,” is imposed for several reasons. The first of these is, that nearly insoluble acids, towards the end of a titration when the quantity in suspension has become small, neutralize the dilute alkali very slowly. Yet, if the stirring were to be continued for a much longer period, the color would eventually fade away through absorption of carbonic acid from the air; or, in the case of many esters, from the gradual neutralization of alkali by saponification. A few esters like methyl formate, dimethyl oxalate, and some esters of hydroxyacids, do neutralize decinormal alkali within the time limit selected, and are, in consequence, described with the acids; but this behavior is very excep- tional, as has been found by a large number of ester titrations. Isolated cases may, however, occur in the tables, in which esters or lactones that should have been placed in this genus have been wrongly assigned other positions through this cause. In titrating acid anhydrides a very characteristic, and at first sight surprising phenomenon, will often be noticed. The solution, instead of becoming pink when the neutral point is passed and alkali is present in excess, remains colorless; but after standing for some time gradually becomes pink. The explanation seems to be that the anhydride attacks the hydroxyl groups of the indicator, as in the Schotten-Baumann Reaction, so that the power to form colored alkali salts is lost. The colorless reaction product is, however, gradually saponified by the excess of alkali present after the titration, and the colored salt of the indicator is again formed. Confirmation of this explanation is found in the fact that direct titrations of acid anhydrides may be successfully made by testing the neutrality of the solution from time to time with fresh pieces of phenolphthalein paper. The indicator under these conditions is always present in the free state, and so performs its proper function. General Physical and Chemical Characteristics of the Acids.—The odors of the liquid acids vary greatly. The sharp penetrating quality, so familiar in the odor of acetic acid, is perhaps the most characteristic element that can be traced in any considerable number of species; but even this property is not common to all species. 38 GENUS III, ACIDS. The solid acids are in a majority of cases odorless or nearly so, though there are many ex- ceptions to the rule. A sour taste and the power to redden blue litmus are properties common to all acids that are sensibly soluble in water. The power of acids, when dis- solved in water or alcohol, to instantly and completely neutralize alkalies, is their most striking chemical characteristic, and has been discussed in the preceding paragraphs. The melting-points, boiling-points, and neutralization equivalents of the tables always have reference to the dry acids when these can be obtained jree from water of crystallization by drying in an oven at 100°-110°. For a few species which can not be easily freed from water of crystallization, the data relate to the air-dried acid. In these exceptional cases the hydrated condition of the acid is always made evident in the tables by the context. The number of acid species that occur com- bined with water of crystallization which may be expelled below 110° is large. Genus III has a Division A of solid, and a Division B of liquid, species. Of these divisions A is much the larger. Each division comprises two sections, 1 and 2, of which 1 contains “‘soluble acids,’’ i.e. such as are soluble in less than fifty parts of cold water, and 2 the ‘“‘difficultly soluble acids.’’ Where serious doubts have arisen as to the sectional position of an acid it has been mentioned in two sections. The solubilities of the acids have, however, been more carefully studied than those of any other equally important group of compounds. To find the section in which an unknown acid is to be sought, it is always necessary to at least roughly determine its solubility. This may be rapidly accom- plished as follows: Weigh out 0.2 grm. of the acid—in the form of an impalpable powder, if it is a solid, in a five-inch test-tube. Add cold water in small measured portions from a graduate or pipette, shaking thoroughly and persistently after each addi- tion. If complete solution is effected by 1 cc., the substance will be described * as ‘‘very soluble,” or ‘“‘v. s.”; if by 1-4 cc., as “ easily Soluble” Gre eee if by 4-10 cc., as “soluble,” or ‘“s.”; if by more than 10 cc., but less than about 30 cc., as ‘‘difficultly soluble,” or ‘“d. s.’”’ Greater degrees of insolu- bility are expressed by the terms ‘‘ very difficultly soluble,” or ‘‘ vy. d. s.,” and “ in- soluble,’ or “i.” If the supply of the acid is very limited, it is possible to make the solubility determination in a smaller test-tube, using only half the quantities of substance and solvent that have been recommended. * It is impossible to be entirely consistent in the use of this approximate solubility ter- minology, because many of the solubility data incorporated in the tables are merely literal quotations from authorities who have given no numerical values, and who have probably attached a different and less definite meaning to the terms of this solubility scale. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I}. GENUS III, ACIDS. DIVISION A, SECTION 1,—SOLID ACIDS “SOLUBLE” IN COLD WATER. Melting-point (Oley 15 15-5 17 18 27 29-30 31 32-3 33 35°5 40-2 Neut. Equiv. 86 86 86 90 112 158 118 130 116 102 144 104 166 100 100 156 SOLID ACIDS.—Colorless and generally Soluble (see note, p. 38) in 50 parts of cold water. Methacrylic Ac.—Cf. Div. B, Sec. 1, b. p. 162°-3°. t Isocrotonic Ac.—Odor like butyric ac._—Cf. Div. B, Sec. 1, b. p. 169°. Trimethylenecarbonic Ac., C,H,;.CO,H. — B. p. 182°-2-5°. G, _ 1-0879?°/,.— ‘Somewhat”’ s. aq. { i-Lactic Ac., Me.CHOH.CO,H.—B. p. (12 mm.) 119°.—Ordinarily a hygroscopic syrup containing some anhydride, and hence giv- ing too high a neut. eq.— Misc. w. aq., alc., or eth.— Heated in test- tube decomposes, gives off white vapors and leaves a viscous residue. Gives a-hydroxyacid Test 302 /—Warm sol. quickly decol- orizes neutral permanganate w. effervescence.—} Heat nearly to dryness 1 cc. lactic acid in a large test-tube over a moderate flame, using an inverted closed capillary to prevent bumping. Conduct the vapors through a glass tube abt. 25 cm. long into 2 cc. aq. in a test-tube surrounded by cold water. Test this sol. (no odor of acetaldehyde) by Test 111 for acetaldehyde.— Neutral salts all s. aq.—{d. and 1. lactic acids are likewise soluble acids giving the same reactions]. Propylacetylenecarbonic Ac., Pr.C:C.CO,H.—Violet color w. FeCl, —AgA ppt. Octanon(7)-oic Ac., Me.CO.C;H,,.CO,H.—Tbl. e. s. aq.—AgA, tbl. e. s. h. aq. a-Oxyvalerianic Ac., Me.(CH,),.CHOH.CO,H.—Hygroscop. ndl.; v. s. aq., ale., or eth. Gives Test 302! Gives anhydride easily.— AgA, scales, d. s.c. aq.; CaA,, ndl., s. in 28 pt. aq. at 15°; ZnA,+ 2 aq. s., in 136 pt. aq. at 15°. : G-Propionylpropionic Ac., Et.CO.(CH,),.CO,H.—V. s. aq., alc., or eth. Violet color w. FeCl,—AgA ppt. { Levuiinic Ac., Me.CO.(CH,),.CO,H.—B. p. 245°-6°.—Deliquescent ; usually met with in liq. state. E. s.aq., ale., or eth. Easily oxid. by CrO, mixture—Gives iodoform by Test 801 immediately _in the cold. In CHCl, sol. 4Br gives stable C;H,Br,03, which cryst. fr. aq. w. m. p. 114°-15°.—Ca and Ba saltse.s.aq.; AgA characteristic lfts., s. in 150 pt. aq. at 17°. Trimethylacetic Ac., Me,.C.CO,H.—B. p. 163-7° (th. i.).—S. in 45 pt. aq.—Ag, Zn, and Pb salts all ppts. fr. moderately conc. sols, w-Acetylvalerianic Ac., Me.CO.(CH,),CO,H.—B. p. 250°-53° at 280 mm.—Cryst. e. s. aq., alc., oreth. AgA ppt. lft. fr. h. aq. + a-Oxybutyric Ac., Me.CH,.CHOH.CO,H.—B. p. 255°-60° d. Salts generally deliq. and v. s.—Gives a-hydroxyacid Test 302! o-Oxyphenylglycollic Ac., HO.C,H,.CO.CO,H.—Nadl. fr. bz.; s. aq. (2); e. s. alc. or eth.—Dist. gives CO, and salicylic ac. (Test 319). a-Ethylacrylic Ac., CH,: CEt.CO,H.—B, p. 180°.—AgA, lft., s. h- aq.—Unsaturated (Test 304). Angelic Ac.—Cf. Div. A, Sec. 2.—B. p. 185° (th. @.). Diallyloxalic Ac.—Cf. Div. A, Sec. 2. 39 40 GENUS III, DIV. A, SECT. 1. (ORDER I, SUBORDER I.) Moelting-point Neut, |SOLID ACIDS.—Colorless and generally Soluble (see note, p. 38) in Choy Equiv. 50 parts of cold water. 54 118 | + Dimethyl Oxalate, C,0,Me,.—B. p. 163-3° (cor.). Monoclin. tbl. Titrates like a monobasic ac.—Add several vols. strong NH,OH to conc. aq. sol.; a heavy cryst. ppt. of i. oxamide immediately forms. 55-6 192 | d-Phenyllevulinic Ac., Ph.CH,.CO.C,H,.CO,H.—Silky ndl.; s. aq.; e. s. alc.—BaA,+14 aq. e.s. aq.; AgA curdy ppt., lifts. fr. h. aq. 57-8 130 | Paraconic Ac., C,H,0,.CO,H.—Deliq. mass. Heated gives citraconic anhydride. 60-2 132 | a-Oxycaproic Ac., Me.(CH,),,CHOH.CO,H.—Gives Test 302. On long heating at 100° partly sbl. and is slowly changed to a syrupy anhydride i. aqg.—Warmed w. CrO, mixture gives valerianic alde- hyde and acid (odor). 64-5 100 | + Tiglic Ac., Me.CH:CMe.CO,H.—Pr or tbl. rather d.s.c¢. aq.; e.s. h. aq.—B. p. 198-5° (th. i.)—Peculiar sharp ‘‘spicy’”’ odor.— Gives Test 304 (w. KMn0O, instantly—w. Br, only upon heat- ing).—CaA,+3 aq., s. c. aq. and, unlike the angelate, more s. h. than c.; mod.s. ale. (unlike angelate).—AgaA cryst. scales fr. h. aq. 64-5 144 | 2-Methylhexanol(4)-oic(6) Ac., C;H,,0;.—Lustrous Ift., e. s. ¢. aq. or eth.— Aga scales, e. s. h. aq. 65-6 150 | Benzoylformic Ac., Ph.cO.CO,H.—Heated gives benzoic ac. (Test 312), CO,, and benzaldehyde (odor).—V. s. aq.—Ba, Pb, and Ag salts d. s. ppts. The acid ppts. oily fr. salts and solidifies on standing in desiccator. It gives the ketone reactions. Warmed w. conc. H,SO,, it gives benzoic Ac. and CO,.—Cf. Ber. 12, 1505, for additional specific reactions. 66-8 118 | a-Methyl-a-oxybutyric Ac., Et.CH(MeOH).CO,H.—Cryst. sbl. at 90° in ndl. V. s. aq., ale., or eth. Gives Test 302.—BaA, v e.s. aq.; AgA s. aq. 69-5-70 50 | @-Dimethylacrylic Ac., Me,.C:CH.CO,H.—B. p. 195°.—Sbl. in ndl. —PbA,+ H,0 Ift., e. s. aq.—Unsaturated. 70 114 | 2, 3-Dimethyl-buten(2)-oic(1) Ac., C,H,,0O,.—Ndl. fr. aq.; 100 pt. aq. dissolve 5.15 pt. at 19°-—BaA,+34 aq., powder, e. s. aq. Turns yellow in air. Unsat. 72 43 | + a-Crotonic Ac., HCMe:HC.CO,H.—B. p. 185° e.—S. in 12 pt. aq. at 15°.—Ba and Ca salts e. s. aq.; AgA curdy ppt.—Reduction of boiling aq. sol. by Na amalgam gives butyric ac. easily.—Gives Test 304! 73 132 | [—], 2-Methyl-pentanol(4)-oic(5) Ac., C,H,,0,—Ndl. sbl. at 100°. At 225° gives svrupy anhydride.—V. s, aq., ale., or eth.—Zn salt, scales, s. in 300 pt. aq. at 16°, or 204 pt. at 100°.—Gives Test 302. 74 144 | Mesitonic Ac., Me,.C(CO,H).CH,.CO.Me.—Small pr. fr. aq.—S. aq.; v. s. ale. or eth.—Dist. gives an anhydride w. m. p. 24° and b. p. 167°.— Salts vs s. aq. 74-5 138 ap-Dioxybutyric Ac., C,H,0,+aq.—Long deliq. pr.; v. s. aq. and alc.; i. eth. Effloresces over H,SO,. Gives Test 302. 74-5 120 | $-Methylisoglyceric Ac., Me.(CHOH),.CO,H.—Pr.; e s. aq. or alc.; d.s.eth. Cryst. w. 1 aq. Effloresces over H,SO,.—AgA, fr. h. aq., v. stable —Gives Test 302. 74-6 87 | (8)-s-Dimethyladipic Ac., CO,H.CHMe.(CH,),.CHMe.CO,H.—B. 321°.—E. s, c. aq., alc., oreth. Heated w. dil. HCl at 200° gives a acid w. m. p. 140°. 76 84 | Tetrolic Ac., MeC: C.CO,H.—B. p. 203°.—Broad tbl., s. aq., eth., or CS,. Sbl.—Gives Test 304. Dec. at 202° to CO, and allylene.— Salts all s. and reduce Au and Hg sols.—Heat w. conc. aq. KOH sol. at 105°, Distil, and test for acetone in the distillate (Test 711). 76 80 | Sec.-Butylmalonic Ac., Bu.CH.(CO,H),.—Cryst. fr. bz. E. s. aq., alc., or eth.—Gives Test 303.—AgA ppt. ee EN eee Melting-point (C.°). 77-8 76-80 78-9 79 after Sbl. at 50° 80 80 82 82-3 84 83-6 87-8 -5 89 90 Neut. Equiv. 73 81 76 104 132 87 166 166 166 108 GENUS III, DIV. A, SECT. 1. 41 (ORDER I, SUBORDER I.) SOLID ACIDS.—Colorless and generally Soluble (see note, p- 38) in 50 parts of cold water. a-Methylglutaric Ac., CO,H.CHMe.(CH,),.CO,H.—Pr. v. s. aq,, alc., oreth. Boiled 20 min. gives oily anhydride, b. p. 272°-75°. [+ or —j Ethoxysuccinic Ac., CO,.H.CH,.CHOEt.CO,H.—Pr. v. s. aq. Opt. active.—CaA (100°) v. s. c. aq. 1 Glycollic Ac., CH,OH.CO,H.—Lft. fr. eth.; deliq. if not absolutely pure. S. aq. and not easily extracted by eth.—Long heating at 100° gives anhydride, C,H,O,, m. p. 128°-30°, i. eth., alc., and c. aq.—Gives Test 302! Solubilities of salts in water:—BaA,, 1:79; CaA,, 1: 82 at 10° (easily supersaturates); PbA,, 1 : 32 at 15°; CuA,, 1: 184; AgA+14 aq., e. s. c. aq., e. dec. by h. ag. a-Oxyisobutyric (Acetonic) Ac., Me,.COH.CO,H.—Hygroscopic pr, v. s. aq., alc., or eth. Gives Test 302.—CaA, v. s. aq.; AgA scalex s. in 14 pt. c. aq.— Fusion w. KOH gives acetone (Test 711). + Citraconic Ac., Me.C(CO,H):HC.CO,H.—Dist. gives anhydride, b. p. 213°-4°. Deliq. 4-sided pr. s. in 0.42 aq. at 15°. Aq. sol. boiled w. HCl gives mesaconic acid, which is also formed on evaporating sol. containing mineral acids.—(NH,),A, boiled w. FeCl, sol. (avoid excess), gives red ppt.—Ba salt, tbl. v. d.s. c. aq.: PbA, ppt. fr. h. sol.; Ag,A ndl. fr. h. aq.—Unsat., but gives Test 901 only w. boiling aq. Br sol. Oxydiethylacetic Ac., Et,.COH.CO,H.—Triclin. cryst. Sbl. fr. 50° V. s. aq., alc., or eth. BaA, v. s. aq., alc., or eth. ZnA,, scales s. in 301 pts. aq. at 16°, less s. hot —Gives Test 302. Pentylmalonic Ac., C,H,,.CH.(CO,H),—Clear pr. Dec. at 140° giv- ing CO, and cnanthic ac. (Test 303).—V. s. aq., alc., or eth. o-Hydrocumaric Ac. (Melilotic Ac.), HO.C,H,.(CH,),.CO,H.—(In Melilotus officinalis). Dist. gives anhydride.—S. in 20 pt. aq. at 20°; e. s. ale., eth., and h. aq.—FeCl, gives transient bluish color in aq. sol.—Fusion w. KOH gives acetic and salicylic ac. (Test 319).—CaA, v. d. s. c. aq.; BaA,+3 ag. e. s.; PbA, cryst. ppt.; AgA curdy ppt. (ndl. fr. h. aq.). m-Methylmandelic Ac., Me.C,H,.CHOH.CO,H.—Lust. pr. fr. bz.; e. s. aq., alc., oreth. Gives Test 302. a-Oxyisovalerianic Ac., Me,.CH.CH,OH.CO,H.—Rhomb. tbl. volatile at 100°. V. ss. aq., ale., or eth.—Oxid. by CrO, mixture.—Dil. H,SO, at 130°-40° gives formic ac. (Test 315) and isobutyric alde- hyde.—Ca, Zn, and Ag salts d. s. c. aq. 2, 2-Dimethylpentanedioic-(1, 5)Ac., C,H,,0,.— Woolly, ndl. fr. cone- HCl, e. s. aq.—M. p. of anhydride 38°; b. p. abt. 265°. 3-Methylpentanedioic(1, 5) Ac., Me.CH.(CH,.CO,H),.—Glassy cryst. e.s.aq., alc.,oreth. Distil. gives anhydride, m. p. 46°; b. p. 283°. —CaA (at 150°) s. aq.; Ag,A ppt. i. aq. i-Ethoxylsuccinic Ac., CO,H.CH,CHOEt.CO,H.—V. s. aq., alc., or eth.—CaA Vv. s. aq. Isopropylmalonic Ac., Me,.CH.CH.(CO,H),.—Dist. gives CO, and iso- | propylacetic ac. (Test 303).—E. s. alc. or eth.—Cryst. fr. bz. w. 2C,H, in long ndl. which effloresce.—Ag,A cryst. powder, i. aq. trans.-Pentamethylenedicarbonic(1, 3) Ac., C,H,.(CO,H),.—Flat. pr. fr. CCl,, s.in 1 pt. c. aq.— Ag, Vv. d. 8. aq., stable. Tigliceric Ac., C,H,(OH),.CO,H.—TDbl. fr. eth.; v. s. aq.; i. CHC];.— CaA,, (at 100°), hard white mass, v. s. aq.; s. abs. alc. [—]}Arabonic Ac., HO.CH,.(CHOH),.CO,H.—Evaporation of aq, sol. gives syrupy anhydride solidifying in dessicator (m. p. 95°-8°— BaA, ppt’d cryst. fr. aq. sol. by ale—Gives Test 302. Methoxylphenylglyoxylic Ac., MeO.C,H,.CO.CO,H.—WNd1l. fr. bz. v. s. alc. or eth. n-Heptylsuccinic Ac., C,,H,,0,—Scales, e. s. aq. or CHCl;—Ag,A i. aq.; CaA+ aq., d. s. white powder. 42 ewes 9 ne Melting-point CO2)s 90 90 91 90-1 92 93 93 93-4-5 95 95 95 96 96 97-5 95-100d. 97-8 98d. 98 99 100 100 GENUS III, DIV. A, SECT. 1, (ORDER I, SUBORDER I.) Neut. [SOLID ACIDS.—Colorless and generally Soluble (see note, p. 38) in Equiv. 178 80 193 160 166 87 80 180 74 19 152 73 68-5 04:5 166 87 73 63 70 80 50 parts of cold water. Monoethyl Tartrate, CO,Et.(CHOH),.CO,H.—Deliq. rhombic pr. s. in aq.—PbaA, lft. d. s. c. aq.; BaA,+2 aq. s. c. aq.—Gives Test 302.—Saponification gives tartaric acid. Terpenylic Ac., C,H,.0,.—Cryst. w. 1 aq. (m. p. 57°).—(An oxidation product of oil of turpentine.)—Cryst. s. aq. or eth.—Sbl. at 130°- 40°. Heat dec. to CO,, etc.—CrO, easily oxid. to acetic acid (cf. Tests 702 and 311), CO,, etc., but may be evaporated w. HNO, (sp. gr. 1-30) without change.—Monobasic to carbonates; dibasic to hot alkalies—BaA d.s. h. aq.; BaA, v. e. s. aq. Propylsuccinic Ac., CO,H.CH,.CHPr.CO,H.—Cryst. fr. aq. 2:83 pt. s. in 100 pt. c. CHCl. Atrolactic Ac., (Me)(Ph)(OH).C.CO,H+ 13H,O.—WNadl. or pr. e. s. ¢. aq.—Ba salt d. s., and Zn salt v. d. s. in c. aq.—Boiled w. conc. HCl gives atropic ac.—Boiling BaO,H, has no action. 2, 2, 4-Trimethyl-pentanol(3)-oic(1) Ac., C,H,,O;—Cryst. s. in 50 pt. c. aq.—Ba and Ca salts e. s. aq. Phenyl-(-lactic Ac., Ph.CHOH.CH,.CO,H.—Pr. v. s. c. aq.—At 180°, or by boiling w. BaO,H, or dil. H,SO, gives cinnamic ac, (Test 313).—BaA,, ZnA,, 14 aq. and AgA, d. s. c. aq. Isoamylmalonic Ac., C;H,,.CH.(CO,H),.—Silky ndl. fr. bz.—E. s, aq., alc., or eth. Loses CO, on fusion (Test 303).—CaA and Ag,A. amorph. ppts. [+ }@-Methyladipic Ac., C,H,,.(CO,H),.—B. p. 210°-2° (15 mm.). V. s. alc.; e. s. lgr—aAg,A ppt. Methyl-f-phenyllactic Ac., Ph.CHOH.CHMe.CO,H.—V. s. alc., eth., or warm aq.—At 280° gives CO, and allylbenzene.—AgaA cryst. ppt. -Oxyglutaric Ac., CO,H.CH,.CHOH.CH,.CO,H.—Nad1l. e. s. aq. or alc. —Boiled w. 60% H,SO, gives glutaric acid. d-Citramalic Ac., C,H,O;.—-Very deliq. cryst. mass. Gives Test 302. Phenoxyacetic Ac., PhO.CH,.CO,H.—B. p. 285° w. sl. dec.—Silky ndl. e. s. aq., alc., or eth.—FeCl, gives yellow ppt.—Cryst. ppt. w. Br aq.—BaA,+3 aq., s. aq.; AgA, d. s. ndl. Propylmalonic Ac., Pr.CH.(CO,H),.—Tbl. fr. bz. which contain n bz. of cryst. (dif. fr. isopropyl comp.).—Gives Test 303. ' + Glutaric Ac., CO,H.(CH,),.CO,H.—Monoclinic pr.; 100 cc. aq. sol. contain 42-9 grms. at 0°; v. s.ale.oreth. Boils w. little dec. at 302°-4°.—CaA. 4 aq. and BaA. 5 aq., v. 8s. aq.; PbA cryst. ppt.; Ag,A ndl. s. h. aq.—Apply Test 316! cis-1, 2, 3-trans-1-Trimethylenetetracarbonic Ac., C;H,O,.—H. s. aq., alc., or eth. Gives Test 303. Phenyl-a-lactic Ac., Ph.CH,.CHOH.CO,H.—Thick pr. fr. aq.—BaaA, e. s.aq. Gives Test 302. Heated above 140° gives formic acid and a-toluic aldehyde. Isoamylmalonic Ac., C,H,,.CH.(CO,H),.—Silky ndl. (fr. bz.+Igr.); v.s.c,aq. Gives Test 303: CaA amorph. ppt. Ethylsuccinic Ac., CO,H.CHEt.CH,.CO,H.—Pr. v. s. aq., alc., eth., or CHCl. Dist. gives liquid anhydride b. p. 243°.—Ba and Zn salts e. s. aq. + Oxalic Ac. (Cryst.), (CO,H),+2H,0.—Monoclinie pr. After fusion subl. at 150°-60°. S. in 10.46 pt. aq. at 14-5°; e.s. c. ale.; s. in 79 pt. abs. eth. at 15°; v. d. s. CHCl,;—Apply Test 317! + Citric Ac. (Cryst.), CO,H.CH,.C(OH)(CO,H).CH,.CO,H + H,O.—Cf. Citric Ac. m. p. 153°. Gives Test 302! Apply Test 314! 3, 3-Dimethylpentanedioic(1, 5) Ac., C;H,,0,—Pearly ndl. fr. bz.; e. s. aq., eth., or h. bz.—Dist. or action of acetyl chloride gives anhydride, m. p. 124°-5°. Melting-point Ci2y, 100 100 100-1 101-2 101-5 102-3 103 103-4 103-4 105 106-7 107 107 110-1 i 111 111-5 112 113-5 113-5 112-15 120 72 80 80 98 72 132 80 80 80 80 87 134 144 166 66 66 72 200 192 GENUS III, DIV. A, SECT. 1. 43 (ORDER I, SUBORDER I.) SOLID ACIDS.—Colorless and generally soluble (see note, p. 38) in 50 parts of cold water. +[+ or —]Malic Ac., CO,H.CH,.CHOH.CO,H.—Deliq. ndl.; cryst. w. difficulty. V.s.aq.; s.ale.oreth. Gives Test 302! Gives with PbAc, a voluminous white ppt. which melts to resinous mass on boiling w. a little aq.—Salts give no ppt. w. BaCl,, White ppt. w. AgNO,. At 175°-200° gives fumaric and maleic acids and maleic arihydride.—Apply color test 314! 2-Methyl-2, 3-propanedioic(1) Ac. , C,H,0,.—_Slowly cryst. syrup; e s. aq.; d.s. eth.—CaA, s. aq. Ethylmaleic Ac., CO,H.EtC:CH.CO,H.—Thick pr. e. s. aq. or eth.— Unsat. (Test 304). Heated gives a liquid anhydride. Na amal- gam reduces to ethylsuccinic acid. s-Methylethylsuccinic Ac. (fumaroid), CO,H.CHMe.CHEt.CO,H.— Ndl. fr. aq.; e.s.c.aq. Heating gives liquid anhydride, b. p. 245°. Butylmalonic Ac. Me.(CH,),.CH.(CO,H),.—Pr. e. s. aq., alc., or eth. Gives Test 303. At 150° gives CO, and caproic acid (disagree- able odor). Pentinoic Ac., C,H,.CO,H.—Monoclinic tbl. fr.eth.; ndl.fr.bz. V.s. aq.—BaA,, scales fr. dil. ale.; v. s. aq—Unsat. (Test 304). Allylmalonic Ac., C,H,.CH.(CO,H),.—E. s. aq. or eth. Adds Br,.— CaA, d. s. aq. ; Bad -taq. pearly Ifts. s. in 1 pt. h. aq.; Ag,A, i. aq. — Gives Tests 303 and 304. a-Hydroxylevulinic Ac., Me.CO.CH,.CHOH.CO,H.—FE. s. aq.; d. s. eth. Reduces Fehling’s sol. At 100° gives an anhydride (ndl. mop. 203° d.): 3-Methyl-3-carboxyl-pentanoic (1) Ac., C,H,,0,—Clear pr. fr. aq.; e. s. aq., alc., or eth. 100 pt. aq. at 15° dissolve 15-4 pt. acid. Heating at 200° gives an anhyd., b. p. 239°-45°. Na ie Ac., (CO,H).(CH,) ,,CO,H.—Tbl. fr. aq. s. in 24 pt. aq. at 20°; e. s. eth.—Sbl. without dec.—BaCl, gives no ppt.; Aga cryst. ppt.; “Cad separates as gran. floc. ppt. when saturated sol. is boiled. Methylpropylmalonic Ac., (Me)(Pr).C.(CO,H),.—E. s. aq., eth., or CHCIl,.—Gives Test 303. Isobutyl Malonic Ac., Me,.CH.CH,.CH.(CO,H),.—E. s. aq. or eth._— CaA and Ag,A, i. ppts.—Gives Test 303. Isobutylsuccinic Ac., C,H,.C,H,.(CO,H),.—Cryst. e. s. aq. or eth_— CaAe.s.; BaAd.s. “The anhydride i is liquid. Angliceric Ac., C,H,.(OH),.CO,H.—Nadl. fr. eth. V.s. aq.; i. CHCl. —Ca salt amorphous, Vv. 8. aq.; 1. abs. ale: ‘Hexahydrosalicylic Ac., o-HO.C,H,,.CO,H. —+sided tbl. or ndl. e. s. aq. or eth. m-Hydrocumaric Ac., HO.C,H,.(CH,),.CO,H.—‘‘ E. s. usual solvents.” Ethylmalonic Ac., Et. CH.(CO,H),.—Cryst. w.1H,O. Pr. v.s. aq. or eth.—Gives Test 303, being completely dec. to CO, and butyric ac. (odor) at 160° \—Na,A gives no ppt w FeCl, (dif. fr. pyro- tartaric ac. below).—CaA less s. h. than c ; BaA+$ aq., fine pr. d. s.aq.; ZnA, 24 aq. characteristic 6-sided tbl. s. in 456 pt. aq. Pyrotartaric Ac., Me.CH(CO,H).CH,.CO,H.—Triclinic pr. e. s. c. aq. oreth. At 200 gives an anhydride. are v e.s.aq.; BaA-2 aq. e. S. aq.; Ag,A, ppt., Vd. 5. fn. ag: Aaah a Aa as eee oto Et 2) Ac., Me.C,H;.(CO,H),.—Silky ndl. fr. bz. S.in 1 pt. c, aq.; e. s. eth. ” Distillation gives valero- lactone.—Gives Test 303 at 140°—Stable towards KMnO,.— CaA +5 aq., glassy pr., e. s. aq.; Ag,A, floc. ppt. (at 70°). Naphthoylformic Ac., C, ,H,.CO.CO,H.—Ndl.,e.s.aq.oreth. Oxid. by, KMn0O, to a-naphthoic ac. Seats S.C. aq.; AgA, amorph. ppt, Ethylbenzoylacetic Ac., Ph.CO.CHEt.CO,H.—E. s. alc. or eth. Boil- ing w. conc. alcoholic potash gives mixture of potassium benzoate. and butyrate ! GENUS III, DIV. A, SECT. 1. (ORDER 1, SUBORDER I.) SOLID ACIDS.—Colorless and generally soluble (see note, p. 38) in fone ase edickencne pee 50 parts of cold water. 114-5d. 91 Dioxytartaric Ac., CO,H.[C(OH),.],.CO,H.—Cryst. mass fr. eth. V.s. aq. Gives Test 303—The aq. sol., when heated, dec. quantita- tively to CO, and tartronic ac.!_ Therefore gives theoretical neut. eq. only at 0°. Salts unstable. 115-16 74 | a-Ethyltartronic Ac., Et.COH.(CO,H),.—Cryst. w. 1 aq. in tbl. w. m. p. 64°-70°.—Ag,A, mic. pr. fr. h. aq. 116 136 | Trioxyisobutyric Ac., (CH,OH),.COH.CO,H.—Pr. fr. alc. v. s. aq.; d. s. ale. or eth.—Gives Test 302.—CaA,+4 aq., s.aq.; PbA,.Aq., d. Sond. 116-5 164 | Hydrocumarilic Ac., C.H,O.CO,H.—Pearly lft. fr. aq.; s aq.; v.e.s. alc. or eth. Dist. w. dec. at abt. 300°.—AgA, v. d. s. h. aq.; BaA,+2 aq., e. 8. aq. 117 80 | Isopropylsuccinic Ac., CO,H.CHPr.CH,.CO,H.—Cryst. crusts e. s. aq., alc., eth., or CHCl,.—On distill. gives liq. anhydride, b. p 245°-50°. —Fuse w. KOH and acidify w. H,SO,. (Odor of butyric ac.). —BaCl, no ppt. Ag salt, d.s. sbi leg 97 | Benzylmalonic Ac., Ph.CH,.CH.(CO,H)..—Triclinic, es. aq. or eth, Test 303 at 180° gives CO, and hydrocinnamic ac 117-8 166 | Tropic Ac., Ph.CH(CH.OH).CO,H. (prepared fr. atropine).—Ndl. or tbl. s. 49 pt. aq. at 14-5°; v.d.s c. bz and CS, Gives Test 302.—CaA,-4 aq., rhombic tbl.—Long boiling w. Ba(OH), gives atropic ac. 118 73 | Methylethylmalonic Ac., (Me)(Et)C.(CO,H),.—Pr. e. s. aq. or eth.— Ag,A, d. s. eryst. powder.—Gives Test 303. 118 152 + Mandelic Ac., Ph.CcHOH.CO,H.—Rhombic cryst., 16 pt. s in 100 pt. aq. at 20°; s. eth—Gives Test 302 !—Dist. or boiled w aq. and MnO, gives odor of bitter almonds!—AgaA cryst. ppt., tbl. fr. h. aq.; BaA,, s. 12 pt aq. at 24°. 119 74 Citramalic Ac. (racemic), CO,H.CH,.C(OH,Me).CO,H.—Glassy deliq. cryst. v. s. aq —At 200° gives citraconic anhydride.—Gives Test 302.—CaCl, added to NH, salt gives floc. ppt. in cone. sol.—Scaly fr h. dil. sol. 119-20 68 | Mesoxalic Ac., (HO)..C.(CO,H),.—Deliq. ndl., vs. aq.; s. eth.—Re- duces ammon. AgNO, sol. when warmed.—Ba, Ca, Pb, and Ag salts v. d. s. ¢ aq.—Ag,A dec. by boiling w. aq., oxalic ac. being among the products. 120d. 85 | 4’-Tetrahydrophthalic Ac., C,H,,0, (dried i. v.)—Lfts fr. aq.; e. s. aq.—Oxid. by alk. KMnO, to adipic ac —At 100° gives anhy- dride, m. p. 74°.—BaA+aq,., gran. ppt.—Gives Test 304. 120-1 94 | 2, 3, 3-ITrimethylpentanediol(2, 4)-dioic(1, 5) Ac. (racemic), C,H,,0,. —(An oxid product of camphoric acid.) Lust. lfts.,e s aq., ale., or eth.—Heated to 220° dee to water, isobutyric ac. (odor and Test 311!), CO, ete —Ag,A ppt. 123 74 | §-Methylmalic Ac., CO,H.CHMe.CHOH.CO,H.—Pr. fr. acetic eth., v. s. aq. or ale —Gives Test 302 —Heat gives citraconic anhy- dride, etc —BaA +24 aq. Ift ds. aq. 123 166 | [—}Tropic Ac., Ph.CH(CH,OH).CO,H.—Cryst. somewhat s. aq.—M. p. of quinine salt 178°. 121-5 80 Diethylmalonic Ac., Et,.C.(CO,H),—Pr, v s. aq. or eth.—Gives Test 303 at 170°-80°, forming CO, and diethylacetic acid.—Zn salt cryst. ppt.—CaCl, precipitates conc. sol. of NH, salt. 124 80 | Methylisopropylmalonic Ac., (Me)(Pr).C.(CO,H),—S. aq.—Gives Test 303.—CaA, v.d.s aq.: Ag,A ppt. 127-8 166 | [+] Tropic Ac., Ph.CH(CH,OH)CO,H.—Pr. fr. eth. S.h.aq. M.p. of quinine salt 186°-7°. Lesss. dil. ale than salt of [—] tropic ac. 128 80 | s-Dimethylglutaric. Ac. (malenoid), CO,H.C,H,,.CO,H.—Triclinic cryst.—100 pt. aq. at 17° dissolve 4.1 pt.—Acetylchloride gives anhydride in the cold, b. p. 272°. Melting-point (C.°). 128c. 129 129 129 129 129-31 130 131 131 132 132 132 133 133 132-4c. 135d. Neut. Equiv. 90 87 152 73 166 81 58 194 72 73 52 65 57 92 112 59 GENUSVIUIS DIVs AS SECTS 1: 45 (ORDER I, SUBORDER I.) SOLID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in 50 parts of cold water. [+ or —}Trioxyglutaric Ac., CO,H.(CHOH),;.CO,H.—Cryst. fr. ace- tone; v.s. aq. or alc.—Ag,A ppt., m. p. w. dec. 173°.—Gives Test 302. s-Diethylsuccinic Ac., CO,H.EtCH.CHEt.CO,H.—Warty masses; v. e. s. h. aq. or eth.—ZnA more s. c. than h.—At 180° gives anhydride. m-Oxyphenylacetic Ac., HO.C,H,.CH,.CO,H.—V.s. aq. oreth. Gives transient violet color w. FeCl. s-Dimethylsuccinic Ac. (malenoid), (MeCH),.(CO,H),.—Pr. s. in 3-3 pt. aq. at 14°—W. Conc. HCl at 180° gives much of the malenoid R641... Dp. 209. Phloretic Ac., p-HO.C,H,.CH(Me)(CO,H).—S. c. aq. or eth. Gives green color w. FeCl, !—Pb salt bulky ppt. $£-Dimethylmalic Ac., CO,H.CHOH.CMe,.CO,H.—Cryst. fr. acetic eth, E. s. aq.; s. eth.—Ag,A, ndl.d.s.h.aq. Gives Test 302! +-Maleic Ac., CO,H.CH:CH.CO,H.—Monoclinic pr. s. in 2 pt. aq. at 10°. Gives Test 901 w. h. bromine water, but does not add Br easily in CCl, sol.—Heating in vacuo above 100° gives solid anhy- dride, m. p. 56°—7°.—At 200° in tube gives fumaric acid (d.s. aq., sbl. at 200°).—Aq. sol. gives ppt. w. BaO,H,; PbAc, gives ppt. No ppt. w. CaCl,.—t} Place 0-1 grm. acid w. 0-2 cc. aniline in a test-tube w. 10 em. glass tube as return condenser. Heat 1 hr. at 190°-200°. Cryst. fr. 15 cc. boiling ale. Cool, filter, wash w. 2 ce. cold ale. and recrystallize fr. 10 cc. boiling ale. Dry at 100°- 110°. Gives phenylaspartic-anil. white cryst., m. p. 209°-10°. Phenyl-(-oxyvalerianic Ac., Ph.C,H,.CHOH.CH,.CO,H.—H. s. aq.; d. s. c. eth.—Dec. on dist.—BaA,+aq,., lfts. d.s. aq.; AgA curdy ppt. trans-Tetramethylenedicarbonic(1, 2) Ac., C,H,.(CO,H),.— Lust. ndl. fr. HCl. Goes easily into anhydride, m. p. 75°. s-Methylethylmalic Ac., CO,H.CHEt. (Me)C(OH).CO,H.—Pr. e. s. aq. Dec. on dist. Gives Test 302. + Malonic Ac., CH,.(CO,H),.—Cryst. s. in less than 1 pt. aq.; s. eth.— Test. 303 gives CO, and acetic ac.!—Fuming nitric acid causes evolution of CO,.—tT Boil 1-2 cgrm. in a test-tube w. 3 cc. acetic anhydride for 3 minutes; then dilute w. 3 cc. acetic ac. A yel- lowish-red sol. w. yellowish-green fluorescence will be obtained.— Ag,A stable cryst. ppt.; CaA+2H,0, alm. i. c. aq. Glutaconic Ac., CO,H.CH,.HC:HC.CO,H.—Pr. e. s. aq. or eth.— _ YZmnA less s. h. than c.—Ag,A d. s. h. aq.—Long boiling w. x’s acetyl chloride gives anhydride, m. p. 87°.—Reduction w. Na amalgam gives glutaric ac. i-Malic Ac., C,H,O,.—Cryst. Not deliq.—Reactions as for [+ ac.] bGtar. p.t00e:) Diallylmalonic Ac., (C;H,),.C.(CO,H),.—Pr. e. s. aq. or eth. Gives Test 303 and 304.—CaA (at 100°) e. s. aq.; Ag,Ad. s. c. aq. Pyromucic Ac., C,H,0.CO,H.—Sbl. fr. 100° in ndl.—S. in 28 pt. aq. at 15°. V.s. h. aq.; e. s. alc. or eth.—Pine splinter, soaked in conc. HCl and held in vapor evolved on heating dry NH, salt in test-tube, becomes deep red !—Sol. in conc. H,SO, warmed w. trace of isatin becomes violet-blue.—Aq. sol. gives reddish-yellow ppt. w. FeCl,.—CaA, and BaA, cryst. and s. aq. or ale.—PbA,+ aq. d. s. c. aq.— Aga lft. Isosuccinic Ac., Me.CH.(CO,H),.—Pr. v. s. aq.; 100 cc. aq. sol. at 0° contains 44.3 grm.—Test 303 gives CO, and propionic ac. (Test 311) Ca, Ba, Pb, and Ag salts v. d. s.; Pb salt s. in x’s of pre- cipitant. 46 GENUS III, DIV. A, SECT. 1. (ORDER I, SUBORDER I.) Melting-point Neut. |SOLID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in (C.), Equiv. 50 parts of cold water. 135d. 73(?) | | Acetonedicarbonic Ac., CO.(CH,.CO,H),.—Ndl. fr. acetic eth. which effloresce in the air.—V. s. aq. or alc.; d. s. eth.—Aq. sol.+ FeCl, gives violet color! Gives Test 303!—-Distil a neutral aqueous solution of the sodium salt and apply tests for acetone (Test 711) to distillate ! 130-8 72 Cis-1, 2-Tetramethylenedicarbonic Ac., C,H,.(CO,H),.—Feathery cryst. v. s. aq., alc. or eth.—Heated above 300° gives anhydride, m. p. 76°-8°.—Oxid. by KMn0O, to oxalic ac.—BaA separates as 6-sided tbl. on boiling a sol. in ammonia w. BaCl, sol. 137 72 | Methylglutaconic Ac., Me.CH.(CO,H).CH:CH.CO,H.—E. s. aq,, alc., or eth.— Unsaturated. 137 152 o-Oxyphenylacetic Ac., HO.C,H,.CH,.CO,H.—Ndl. fr. eth.; s. aq.— Dist. gives anhydride, m. p. 49°; b. p. 236°-8°.—Aq. sol. colored violet by FeCl, ! 138-9 210 Veratrinketonic Ac., (MeO),.C,H,.C,0,H (dried).—E. s. aq., alc., or eth.—KOH fusion gives protocatechuic ac.—Pb salt d. s. ppt. 138-9 72 Cis-Tetramethylenedicarbonic(1, 3) Ac., C,H,.(CO,H),.—Pr. v. s. c- aq.—BaA-+2 aq. s. in 150 pt. c. aq., less s. in h. aq. 139 87 Dimethylethylsuccinic Ac., CO,H.CHEt.CMe,.CO,H.—S. in 27 pt. c. aq.; e.s. alc. or eth.—B. p. 235°-40°. 139 Anhydrocamphoric Ac., C,H,,0;.—Sbl. undec.—H. s. aq., alc., or eth Can be recryst. fr. aq. 139-40 io a-Dimethylsuccinic Ac., CO,H.CMe,.CH,.CO,H.—Thick glassy pr. fr. bz.—100 pt. aq. at 14° dissolve 7-52 pt.; e.'s. ale. or eth.—At 165°-70° gives anhydride, m. p. 29°.—Ca salt separates from ammon. sol. by CaCl, only when warmed. 139 101 Tetrahydroxyterephthalic Ac., (OH),.C,.(CO,H),.—E. s. aq. or ale.; i. eth. No color w. FeCl,.—BaaA e. s. aq. 139 182 | Hydrocaffeic Ac., (OH),.C,H,.(CH,)..CO,H.—6-sided tbl. fr. aq. E. s. aq. Aq. sol. gives intense green color w. FeCl,! Reduces Fehling’s sol. and AgNO, easily. 140 74 Ethylenemalonic Ac., C,H,.C.(CO,H),+aq.—Ndl. fr. eth., v. s. aq. or eth.; s. CHCl,;.—Gives Test 303 and 304.—(NH,),A+ BaCl, gives ppt. almost 1. c. aq. 140 79 | Cis-Pentamethylenedicarbonic(1, 2) Ac., C,H,.(CO,H),.—Ndl. At 160° gives anhydride (tbl. fr. Ac., m. p. 140°). abt. 140d. 67 | Isomalic Ac., Me.COH.(CO,H),.—Cryst., e. s. aq., ale., or eth.—Opt. i.—At abt. 160° gives Test 303 yielding CO, and lactic acid.— BaA+2 aq., d. s. h. aq. 140- 80 | s-Dimethylglutaric Ac. (fumaroid), C,H,,O,.—Pr.—100 pt. aq. at 17° dis. 4.4 pt.—CaA, floc. ppt. 141d. 63-3 | 2, 3-Dicarboxyl-pentanoic(1) Ac., C;H,,0,.— Cryst. fr. acetone, v. s. aq., alc., or eth.—Heated loses CO,.—Ba,gA,, 1. aq. or ale. 140-3 84 Mesotartaric Ac., (HO),.C,H,.(CO,H),.—(Cryst. w. 1 aq.)—Tbl. s. in less than 1 pt. ec. aq—KHA much more s. than acid tartrate or racemate.—Does not ppt. CaSO, sol. (dif. fr. racemic ac.). Gives Test 302.—Opt. i—For microchemical tests cf. R. 17.69. 143-4s.d. 182 | Phenylglyceric Ac., Ph.(CHOH),.CO,H.—V. s. aq. or alc.; d.s. abs. eth.—Gives Test 302, decomposing at 160° to CO, and a-toluylic aldehyde.—CaA,-4 aq. d. s. c. aq. 145-Gd. 64 | Glutinic Ac., CO,H.C: C CH,.CO,H.—H. s, aq., alc., or eth.; i. bz. —Gives Test 303 and 304.—PbA ppt. Melting-point (ORS 145 147 148 148 abt. 150d. 150-3 151 GENUS III, DIV. A, SECT. 1. 47 (ORDER I, SUBORDER I.) Neut. [SOLID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in Equiv. 4- 226 168 152 81 90 64 50 parts of cold water. Galactosecarbonic Ac., HO.CH,.(CHOH) ,.CO,H.—Nadl., s. aq.—Fusion gives an anhydride.—Gives Test 302. Homogentisic Ac., (HO),.C,H,.CH,.CO,H.—V. s. aq., ale., or eth._— Fusion gives anhydride of m. p. 191°.—Gives transient-blue color w. dil. FeCl,—KOH fusion gives hydroquinone, etc.—Cryst. effloresce over H,SQ,. p-Oxyphenylacetic Ac., HO.C,H,.CH,.CO,H.—Flat ndl.,s. c. aq.; v.e. s. h. aq.; s. ale. or eth.—Sol. gives pale-violet color w. FeCl,, changing quickly to a dirty grayish green. Dist. w. CaO gives CO, and p-cresol. (From urine.) Diglycollic Ac., CO,H.CH,.0.CH,.CO,H + Aq.—Rhomb. pr., e. s. aq. or ale.—Dist. w. dec. giving glycollic ac., trioxymethylene, CO and CO,.—BaA, i: aq.; Ag,A, gray ppt.; CuA blue ppt. I-Camphoronic Ac., C,H,,0,.—Cryst. s. in 17 pt. c. aq.; v.s.ale.; e.s. eth.—CO, and isobutyric ac. are among products of slow dist. cis-1, 2, 3-Trimethylenetricarbonic Ac., C,H,.(CO,H), (dried at 120°). —E. s. aq. or ale.—Ca salt less s. h. than c.; Ag,A amorphous ppt. a-Oxyadipic Ac., CO,H.C,H,.CHOH.CO,H.—Sbl. undec. E. s. aq. alc.; or eth. Trimethylsuccinic Ac., CO,H.CMe,CHMe.CO,H.—E. s. aq. or bz.— ZnA, mic. pr. e. s. c. aq., but ppt’d by boiling the sol.—Prepare the anilic ac., m. p. 134°, and the anil. m. p. 129°. i-Trioxyglutaric Ac., CO.H.(CHOH),.CO,H.—Thbl. fr. acetone. aq. orh. ale. Gives Tests 101 and 302. Hexamethylenetricarbonic (1, 4, 4) Ac., C)H,,0,.—S. aq.; d.s. eth.— Dec. at 200°. Gives Test 303. Phenylmalonic Ac., Ph.CH.(CO,H),.—Pr., e. s. aq., ale., or eth.—CaA eryst. ppt.; Ag,A curdy ppt.—Fusion gives CO, and phenylacetic ac. (Test 303). + Citric Ac., CO,H.CH,.C(OH)(CO,H).CH,.CO,H.—Cryst. w. 1 aq. in rhombic pr. (Dry at 130° form. p.) S. in 0-75 pt. c. aq.; v.s. alc.: 100 pt. c. eth. dissolve 2-26 pt.—Gives Test 302.—Hot conc. H,SO, gives yellow color, but does not char.—CaCl, gives a white eryst. ppt. with neutral alkali citrates when the sol. is boiled for a few min.,—otherwise only after some hours; an alkali citrate sol. after being made strongly alkaline w. NaOH gives an amorphous ppt. immediately.—Ca,A, is soluble in HCl, in Ac, in citric ac., in NH,Cl, and in alkaline citrates—_{Neutral alkali tartrates and oxalates give an immediate ppt. w. CaCl,; calcium oxalate is insoluble in acetic acid. Malic ac. and neutral malates give no ppt. w. CaCl, unless alc. is also added. A cone. sol. of citric ac., or of an alkali citrate acidified w. acetic ac., gives no ppt. when treated w. a 5% potassium acetate sol. and alc. (dif. fr. tartrate) ].—Gives color reac. 314! (rac.)-Trioxyglutaric Ac., CO,H.(CHOH),;.CO,H.—Cryst. fr. acetone Vos ag. oh. ale: 1, 1-Tetramethylenedicarbonic Ac., C,H,.(CO,H),.—Pr. fr. eth. E.s. aq.; s. eth.—Gives Test 303 at 210°——Ba, Pb, and Ag salts are ppts. [+ or —] Talomucic Ac., C,H, ,0,.—Mic. lft. fr. acetone; e. s. c. aq. or h. ale.—CaA (at 105°), d. s. h. aq. Ethenyltricarbonic Ac., (CO,H),.CH.CH,.CO,H.—Pr. e. s. aq., alc., or eth. Test 303 gives CO, and succinic ac. (Test 320!). Ca,A, and Zn,A, are more s. inc. than in h. aq.; Ag,A is an amorphous ppt. Diacetylsuccinic Ac., CO,H.CH(MeCO).CH(MeCO).CO,H.—NadL. s. aq. or ale.; d. s. eth.—Heated w. HCl gives carbopyrotritaric ac. Tartronic Ac.—See m. p. 185°-7°. Vere, 48 GENUS lil, DIV. A, SECT: 1. (ORDER I, SUBORDER I.) Melting-point CORE 161d. 160-1 161-6c. 162d. 166 166-7 166-7 166-7 167d. 167-5 168-70 169 170 169-71 172d. 175 Neut. Equiv. 65 132 fe) 58-7 72 72°7 ays) 164 75 — 188 72 51-5 65 SOLID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in 50 parts of cold water. + Itaconic Ac., CH,:C(CO,H).CH,.CO,H.—Rhombic octahedra, s. aq. (1 <.2°at 207)s sales d: 8. eth.—Gives Test 304. —Gives red- brown ppt. on boiling | w. x’s FeCl,.—CaA-aq. s. in 45 pt. aq. ab 18°; Ag,A v. d. s. h. aq. _"“Warmed w. acetylchloride gives anhy- dride, m. p. 68°. Saccharine.—Cf. Genus V, Div. A. + Quinic Ac., (OH),.C,H,.CO,H.—Monoclinic pr. s. 2-5 pt. aq. at 9°; less s. ale.; alm. i. eth. —Gives Test 302.—Dry distillation gives phenol, salicylic ac. (Test 319), and benzoic ac. (Test 312).— + Gives pungent odor of quinone on boiling in test-tube w. dil. H,SO, and MnO,!—Br substitutes—I and KOH give iodoform (Test 801).—Ca and Pb salts e. s. ¢. aq.—Occurs in cinchona bark, coffee-beans, etc. Teraconic Ac., Me,.C:C(CO,H).CH,.CO,H.—E. s. c. aq., ale., or eth. —Dist. gives aq. and an anhyd. w. b. p. 270°-80°.—CaCl, gives pulv. ppt. (best on warming). Tricarballylic Ac., CO,H.CH.(CH,.CO,H),.—HE. s. aq. or ale.; d.s. eth- —Sbl. w. dec Cd ein d. s. aq.; Pb,A, pulv. ppt.—FeCls gives floc. ppt. Acetoxyl-a-propionic Ac., Me.CH(C,H,0,).CO,H.—Ndl. v. s. aq. or ale. After long keeping becomes i. in ale. and does not melt at 300°. Dae v. s. aq.—Boiled w. NaOH gives acetic and lactic ac. salts. Methylitaconic Ac., Me.CH:C(CO,H).CH,.CO,H.—Pr. s. aq. or eth. —Ba salt cryst. ppt.—Gives Test 304. Isocamphoronic Ac., C,H,,0,.—Pr. s. c. aq.; e. 8. ale., or eth.— Sbl.— Ag, A. —NH, OH and BaCl, give no ppt. Dicarboxyglutaric Ac., (CO,H),.CH.CH,.CH.(CO,H),.—V. s. aq., alc.; d.s. eth.—Test 303 gives CO, and glutaric ac. (Test 316). Ca, Ba, and Pb salts form ppts. Prehnitylic Ac., Me,.C,H,.CO,H.—Glassy pr. fr. ale. ‘‘Somewhat”’ s. in aq. { d-Tartaric Ac., CO,H.(CHOH),.CO,H.—Monoclinic eryst.—100 pt. aq. dissolve 139 pt. at 20°.—HE. s. alc., v. d. s. eth.—Solutions [+]. Applv Tests 362 and 314! CaCl, gives volum. ppt. from sol. of neutral K or Na salts, but not from solution of the free acid. The ppt. is sol. in mineral and acetic acids, in cold N aes and in an excess of alkaline tartrate. .From rather dil. sol. appears slowly and in ecryst. form. —KC,H,O, gives a ppt. ia tartaric acil sols. (facilitated by diluting with an equal vol. of alcohol). Neutral salts must first be acidified with acetic ac.! —TIf to an aq. sol. of the acid or a soluble tartrate, 1 drop FeSO, sol., a few drops H,O, sol. and an x’s NaOH be added, a fine deep violet color is immediately produced, which in cone. sols. is so deep as to be nearly black. (Cf. Allen, I, 515.) This color is not given by citric, malic, succinic, or oxalic acids. Naphthol (8)-carbonic Ac., HO. Coie. CO »H.—HE. s. aq., ale., or eth.— CaA, sol. gives w. F eC, a violet ppt. trans-Tetramethylenedicarbonic(1, 3) Ac., C,H,.(CO,H),..—Sbl. in fine ndl.—sS. in 26 pt. aq. at 20°; ‘d.s.eth.—Does not add Br.—Gives an anhyd. w. difficulty, m. p. 50°. { s-Ethanetetracarbonic Ac., C,H,.(CO,A),.—E. s. aq., alc., or eth. © —Gives Test 303, vielding CO, and succinic ac. (Test 320!). Aq. sol. gives ppt. w. BaCl,. Oxalacetic Ac., CO,H.CO.CH,.CO,H.—E. s. aq., alc., or eth.—Gives Test 303. ’ Phenylhydrazine hydrochloride gives 1-phenylpyra- zolon (5) carbonic (3) ac. Trimethylenedicarbonic (1, 2) Ac. (fumaroid), Cs H,.(CO,H),.—Glassy thls. in. 5 pte: aq.Ag.A d. s. h. aq.— B. p. (30 mm.) abt. 210°. GENUS III, DIV. A, SECT. 1. 49 (ORDER I, SUBORDER I.) Melting-point Neut. [SOLID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in (C.°). Equiv. 50 parts of cold water. —_——__— 176 79 =| Cis-3, 3-Dimethyltrimethylenedicarbonic(1,2) Ac., C,;H,,0,—\Tbl. rather d. s. c. aq.—Above m. p. gives anhyd., m. p. 56°. Very stable towards KMnO, and Br. 175d. 226 | d-Mannoheptonic Ac., C,H,,0,.—S. in 25 pt. c. aq.—Opt. [—]— Cad, s. h. aq.; BaA, d. s. ec. aqg.—Gives Test 302. 175-8 Glucuronic Anhyd., C,H,O,.—V. s. aq.; 1. ale-—Reduces Fehling’s sol.—Ac. syrupy and e. s. alc. 177 78 | Diacetylenedicarbonic Ac., CO,H.C : C.C : C.CO,H+aq.—Tbl. fr. ale.—eth. S. aq.; e. s. ale. or eth._—Turns purplish in light. —Ammon. Cu,Cl, gives a red ppt. at 30°. 178d. 67 | Methyltartronic Ac., Me.COH.(CO,H),.—Rhombic cryst., s. aq.— NH, salt ppt’d by boiling BaCl,.—Gives Test 303. 178-9 57 | Acetylenedicarbonic Ac., CO,H.C : C.CO,H.—(Cryst. w. 2 aq.— Cryst. effloresce in air; lose aq. of cryst. over H,SO,).—V. s. aq., alc., or eth.—Gives Test 304 easily. Is reduced to succinic ac. ' (Test 320) by Na amalgam.—Ag. salt v. unstable. BaA-+agq,., Ci denC. ac. 180 80 | s-Methylethylsuccinic Ac. (fumaroid), CO,H.CHEt.CHMe.CO,H.— Ndl., 3 pt. s. in 100 pt. aq. at 17°; e. s. eth.; d. s. CHCl;:— A 5% sol. of Na,A gives w. c. CaCl, no ppt., but w. h. CaCl, cubical cryst., CaA, which disappear again on ‘cooling. 181d. 91 | Oxyphthalic Ac., C,H, (OH)(CO »H).(4 : 1 :2).—Gives anhyd. on melt- ing.—Rosettes Ss. in 32 pt. aq. at 10°; s. eth.—Aq. sol. reddish yel- low w. FeCl,.—Fuse for a short time w. some resorcine at 200°: Fusion s. in aq. w. greenish fluorescence; KOH turns to dark yellowish red. 183 152 Oxytoluic Ac., C,H;.(OH)(Me)(CO,H)(6: 1: 2).—Ndl. s. ¢. aq.; v. s. eth. — FeCl, gives light-brown ppt. a Views: aC. 184d. 58 { 1,1,2-Trimethylenetricarbonic Ac., C,H;.(CO,H);—Pr. fr. aq.— Gives Test 303. 185 59 | +Succinic Ac., CO,H.CH,.CH,.CO,H.—Monoclinic pr., s. in 14-57 pt. aq. at 20° , or in Q- 826 pt. at 100° + seale-: dos, eth: 51. CHC, or CS, —Distils at 235° giving anhydride! Burns w. blue smokeless flame.—CaCl, gives white cryst. ppt. only in cone. sols.*of alkaline salts. Ppt. s. in aq., Ac, HCl, or hot NH,Cl sol.; 1 -hydroxy acid, gives a somewhat similar coloration in Test 302.—Apply Test 320! 185 105 | Isosaccharic Ac., C,H,,0,—Rhombic cryst., e. s. aq. or alc.; d.s. eth.—Aq. sol. shows birotation.—Dec. on dist. —Ag,A, cryst. ppt. which gives silver mirror on warming w. ammonia. 185-7d. (?) 60 | Tartronic Ac., HO.CH.(CO,H),..—(Cryst. w. 4 aq.)—Pr. fr. eth., e. s. aq. or alc.; d. s. eth. when not anhyd.—Sbl. at 110°-120°. —Gives Test 303, yielding glycolid (ay Dz "990°, —BaA (at me ; floc. ppt. changing to lft. v.d.s. h. aq.; Ag,A cryst. ppt. d.s h. aq. 186-8d. 61-5 | Cyclopentane-tetracarbonic(1, 1, 3, 3) Ac., C,H,,0,.— Hygroscopic cryst. mass. Gives Test 303. 189d. 58-5 | (@)-3, 4-Dicarboxyl-hexanedioic(1,6) Ac., C,H,,O,.— Silky ndl. fr. aq.— 100 pt. aq. dis. 27-4 pt. at 19°. — In “melting gives an anhyd.—Ag,A, amorph. ppt. 189-5 45 + Oxalic Ac. (Anhydrous), CO,H.CO,H.—Octahedra. Takes on water quickly.—S. aq.—For reactions see the hydrated acid on p. 42 of this section ! 191d. 58 + Aconitic Ac., CO,H.CH,.C(CO,H) :CH.CO,H.—Lft. mod. s. ¢. aq v.s. alc.; e. Ss, eth. (dif. fr. citric ac.) —Sol. boiled w. x's Ca(OH), sol, “gives no ppt. (dif. fr. citric ac.)—BaA,, s. in 24 pts. aq.; Ba,A, is ppt.; Zn,A,, i. aq.; Ag,A, floc. ppt. fr. (NH,),A and AgNO,.—Gives Test 304 (and 901 slowly, hot).—Reduced by Na amalgam to tricarballylic ac. 50 GENUS III, DIV. A, SECT. 1. (ORDER I, SUBORDER I.) Melting-point Neut. |SOLID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in COR). Equiv. 192-3d. 66 195 87 198-203d. 58 199d. 154 199-200d. re 199-200 154 199-200 76-7 201 abt. 200 202 65 204 190 205-6 84 208 152 209 73 d.210 213 79 216d. 70 218-20d. 65 50 parts of cold water. Dimethylmalonic Ac., (CO,H),.C.Me,.—4-sided pr. s. in 10 pt. ¢. aq.; e. s. eth.—Sbl. in ndl. at abt. 120°.—Gives Test 303, yielding CO, and isobutyric ac. (cf. Test 311). Tetramethylsuccinic Ac.—(Cf. Div. A, Sec. 2.) Tetramethylenetetracarbonic(1, 1, 2, 2) Ac., C,H,.(CO,H),.—V.e.s. aq., alc., or eth. Gives Test 303. Protocatechuic Ac., (OH),.C,H,.CO,H.(3 : 4: 1).—(Loses water of eryst. at 100°.)—S. aq.; v.s. alc.; mod. s. eth.—Aqueous sol. + FeCl, becomes blue-green; on adding Na,CO, changes to dark red !—PbAc gives ppt. s. in dil. Ac—Reduces ammon, AgNO,, but not Fehling’s sol.—On distil., or NaOH fusion, gives pyro- catechin and CO, (cf. Test 416). Camphenic Ac., C,,H,,0,.—E. s. aq. or eth.—Ba salt, v. e. s. aq.; Pb, A, (at 100°). 2, 5-Dioxybenzoic Ac., (HO),.C,H;.CO,H.—Nadl. or-pr., e. s. aq., alc., or eth.—FeCl, gives deep-blue coloration! On heating w. FeCl, sol. gives CO, and odor of quinone.—BaA,, v. s. aq.; PbA,, v. d. s. aq.—Reduces ammon,. AgNO, and Fehling’s sol. when warmed. —On distil. dec. to CO, and hydroquinone. Camphoic Ac., C,)H,,0,.—Cryst. v. s. aq., ale., or eth.—Gives off CO, at 300°.—Pb,A, (at 100°) ppt.; BaA cryst., e. s. aq. Camphanic Ac., C,H,,0,.CO,H.—Sbl. fr. 110°.—S. aq.; e.s. alc. or eth, + Tannic Ac., C,,H,,0,.—Cf. III, A, 1, m. p. 210°. Mesaconic Ac., Me(CO,H)C:CH.(CO,H).—Ndl. fr. aq. or ale. S. in 37 pt. aq. at 18°; v.s. hot.—Sbl. undec.! Does not give Test 304 easily. Warmed w. acetyl chloride gives citraconic anhyd.—NH, salt gives brown floc. ppt. w. FeCl; (i. h. or in x’s of reagent).— Ca and Ba salts mod. s. aq.—PbA and Ag,A ppts. 2, 3-Dioxybenzoic Ac., C,H,(OH),.CO,H.2 aq.—S. aq.—Gives blue color w. FeCl,, changing to violet w. Na,CO,.—Ba and Pb salts v. d. s. aq.—Distil. gives CO, and pyrocatechin. (Cf. Test 416.) t+ Racemic Ac., CO,H.(CHOH),.CO,H.—Triclinie cryst. containing 1 mol. H,O which effloresce in the air !—Hydrated ae. s. in 4-84 pt. aq. at 20°, or in 48 pt. c. ale-—Gives Tests 302 and 314! Ppts. CaSO, sol. (unlike tartaric ac.); ppt. s. in dil. HCl and reppt’d at once by NH,OH (dif. fr. tartaric)—BaA, 23 aq. alm. i. c. aq.— Ag,A less s. than tartrate. 5-Oxy-3-toluic Ac., Me.C,H,OH.CO,H.—Tbl. fr. h. ag. ‘‘Mod. s. ¢. aq.”’—Sbl.—PbA, eryst. ppt.; CaA,.2 aq., pr. e. s. aq.—Dist. w. CaO gives CO, and m-cresol. s-Dimethylsuccinic Ac. (fumaroid), (CHMe),.(CO,H),.—Pr. fr. aq.; i. CHC],—Acety] chloride gives anhyd. w. m. p. 43°. + Gallotannic Ac., C,,H,,0, (?).—A light buff-colored powder or scales. Taste very astringent!—S. c. aq.; less s. alc.; i. abs. eth.—1 drop FeCl, (10% sol.) +20 cc. aqueous tannin sol. (1 : 5000) gives a color that is deep blue by transmitted light! Gelatine sol. gives immediate white ppt. !—(The last two reactions distinguish from gallic ac.) Alkaline sol. quickly absorbs O and becomes brown! At 210° gives CO,, pyrogallol, etc.—The salts are amorphous.— Reduces AgNO, sol. on boiling. trans-3, 3-Dimethyltrimethylenedicarbonic(1, 2) Ac., C,H,,O,.—Pr.e. s. h. aq.; d. s. eth.; alm. i. CHCl,—Stable. Heating alone gives no anhyd. a-Trimellitic Ac., C,H;,.(CO,H),(1, 2, 4).—S. h. aq. or eth.—Gives an anhyd. on fusion.—Distil and test distillate for phthalic anhyd. by Test 318-1 !—Ba,A,. d. s. aq.—Ag,A, ppt. d. s. aq. I, I, 3, 3-Hexamethylenetetracarbonic Ac., C,,H,,0,.—Pr., s. c. aq.; e. s. h. ale.; d.s. eth.—Ag,A gelat. ppt.—Dec. on melting to CO, and dicarbonic acids. Melting-point (0.2). 220 232 236 (s. h.) 237d. 238d. 264d. 286-8 345-50 Neut. Equiv. 58 181 58:5 63-5 63-5 63-5 57 70 GENUS= Tie DIV A kG Ls 1, 51 (ORDER I, SUBORDER I.) SOLID ACIDS.—Colorless and generally soluble (cf. note, p. 38) in 50 parts of cold water. cis-trans-s-1, 2, 3-Trimethylenetricarbonic Ac., C,;H;.(CO,H);.—S. aq. or alc.—Ba,A,+aq. ppt.; Ag,A ppt. 3, 5-Dioxybenzoic Ac., (HO),.C,H;.CO,H.13 aq.—Pr. mod. s. ¢. aq.3 e. s. alc. or eth.—Gives no color w. FeCl, and no ppt. w. PbAc.— Fusion w. § pts. NaOH gives resorcine (Test 418).—Gives deep- red color on heating at 14C° w. 4 pts. conc. H,SO,; ppt’d green by aq. a-3, 4-Dicarboxyl-hexanedioic(1, 6) Ac., C,H,,O,.—Lft. fr. aq.—100 pt. aq. dissolve 11-8 pt. at 19°; v.s. alc.; d.s. eth. v-Benzenetetracarbonic Ac., C,H,.(CO,H),.—Cryst. w. 2 aq., which it loses above 100°. E.s. aq.—Aq. sol. not easily extracted by eth. —In melting gives an anhyd.—Crystals resemble prehnite.— Pb,A, i. aq.; Me,A, m. p. 104°-8°; Me,A, m. p. 176°-7°.—Aq. sol. of acid gives a cryst. ppt. BaA,-+ H,O when warmed w. BaCl, sol. (Dif.ir. 1, 2,3, 5 acid:) Q-I, 2, 3, 5-Benzenetetracarbonic Ac., C,H,.(CO.H),.— E. s. aq.— Conc. HCl ppt’s fr. aq. sol. in short ndl. On melting forms an ‘ anhydride.—Gives floc. ppt. w. PbAc,; floc. pp. w. CaAc, on heat- ing; floc. ppt. w. BaO,H,, but none w. BaCl,. s-Benzenetetracarbonic Ac., (Pyromellitic Ac.), C,H,.(CO,H),—In melting gives an anhydride.—Triclinic tbl., 100 pt. aq. dissolve 14-2 pt. at 16°; e. s. ale.—Sbl. giving anhyd. m. p. 286°.—Ca, Pb, and Ag salts are ppts.—Me,A, m. p. 138°. Mellitic Ac., C,.(CO,H),.—Fine silky ndl., v. e. s. aq.; e. 8. ale. (s)-1, 3, 5-Irimesic Ac., C,H,.(CO,H),.—Pr. fr _aq.—‘‘ Moderately” s. ¢. aq.; v. 8. ale.—Sbl. below 300° —Ba,A,-aq., lustrous ndl., alm. i.c.aq.; v.d.s.h.aq.; Zn;A, pr. alm.i.c.aq.; Ag;A, volum. ppt.—Me,A, m. p. 143°. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I}. GENUS IIL, ACIDS. DIVISION A, SECTION 2,—SOLID ACIDS NOT SOLUBLE IN COLD WATER. Melting-point Neut. [SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) (C.°). Equiv. in 50 parts of cold water. 14 282 | { Oleic Ac., C,,H,,0,.—B. p. 232° (20 mm.).—G. 0-89081!"8/,.—Gives Tests 304 and 901! Absorbs O from the air.—Fused in a test- tube w. x’s of moist KOH in a bath the temperature of which is gradually raised from 300°-320°, is converted almost quanti- tatively into potassium palmitate, acetate, and H.—Dilute one volume of the nitrosyl-sulphuric ac. reagent described on p. 13 with one vol. of aq., and shake the mixture in a test-tube with an equal volume of the oily acid, keeping it well cooled with run- ning tap-water. Set the tube aside in a beaker containing cold water for 15 minutes. A solid mass of elaidic ac. (m. p. after purification 51°—2°) soon separates. 16-7, 298 | Ricinoleic Ac., C,,H,,0;—B. p. 250° (15 mm.).—Gives Tests 304 and 901.—Treatment w. nitrosyl-sulphuric acid, as described under oleic ac , gives ricinelaidic ac., m. p. 50°.—Polymerizes easily. 19-4 166 | Ethylethersalicylic Ac., EtO.C,H,.CO,H.—D. s. c., e. s. h. aq.— BaA, Vv. s. aq. 21-3 181 | Umbellulic Ac., C,,H,.0,.—Cryst.—B. p. 275°-80° c.—(An ac. fr. fat of Californian Laurel.) 24-4 114 | 2-Methylpenten(2)-oic(1) Ac., C,H,,0,—B. p. 213° c.—V. d.s. aq.; e. s. eth.—Gives Test 304.—Is volat. w. steam.—AgA, ndl. or tire pad. 94-5 184 | t Undecylenic Ac., Me.C,H,.C,H,,.CO,H.— B. p. 165° (15 mm.).— (From distil. of castor-oil i. v.)—G. 0-9072 *4/,.—BaA,. ndl. or lft. s. in 1073 pt. aq. at 15-5°.—Fuming HNO, oxid. to sebacic ac.— Gives Tests 304 and 901! 26 344 | Anacardic Ac., C,.H,.0,,—(From Anacardium occidentale.) I. aq.; e.s. ale or eth.—AgA (at 100°) ppt. fr. alc. sol. by AgNOs. 26-7 256 | Diheptylacetic Ac., CH(C,H,,),.COOH.—Cryst., alm. i. aq.; Vv. €. s. alc., eth., or bz.—BaAy, fine ndl. fr. alc.; i. aq. 28-5 186 Undecylic Ac., C,,H,,0,.—Scaly cryst. mass.—B, p.212-5° (100 mm.). —Feeble odor like caproic ac.—RaA,, v. d.s.; Aga, 1. aq. 29 Triethyl Methanetricarbonate, HC.(CO,Et);.—B. p. 253°.—Ndl. or pr.—‘‘Is saponified at 0° by KOH to alcohol, CO,, and malonie ac.” ! §. in NaCoO, sol. 30 Acetylperoxide, (Me.CO),.0,.—Flat cryst. w. odor like ozone. ‘Somewhat’? s. aq.—Extremely explosive-——NaOH gives Ac, and sodium peroxide. 30 128 | Hexahydrobenzoic Ac., C,H,,.CO,H.—B. p. 233°.—D. s. aq.; V. Ss. ale. or eth.—ZnA, much more s, in c. than in h. aq.—Volat. w. steam. 31 176 | Cinnamenylpropionic Ac., Ph.CH,.CH:CH.CH,.CO,H. — Tbl. fr. lgr. —Gives Test 304.—BaA,, d. s. aq.; AgA ppt. 31-3 172 | + Capric Ac., Me.(CH,),.CO,.H.—B. p. 268-4° c.—Feeble odor like perspiration.—Alm. i. ¢. aq.; Vv. d. s. h. aq.—Alkali salts alone soluble.—BaA,, lft. fr. h. aq.—G. 0-93 at 37°. (igre a enn 52 Melting-point COs 33 33 33:4 45-5 46-7 Neut. Equiv. GENUS Ill; DIV. A, SECT. 2. | 53 (ORDER I, SUBORDER 1.) SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. 254 114 338 136 270 127 164 214 114 164 113 166 200 240 282 100 Hypogeic Ac., C,,H,,0,—Ndl. e. s. ale—B. p. 236° (15 mm.).— Oxidizes in air.—Nitrous acid (cf. oleic ac.) gives gaidic ac., m. p. 39°. Gives Test 304. Hexen-2-oic-(1) Ac., C,H,,0O,.—Ndl. d. s. ag.—Adds Br, in CS, sol. (Test 304).—Baa,+ 14 aq,, lft.; e. s. ale.; AgA, ndl. fr. aq. t Erucic Ac., C,,H,,.CO,H.—Long ndl. fr. ale. B.p. 264° (15 mm.), Gives Test 304 !—Heated to fusion w. dil. HNO, and treated w. NaNO, gives geomet. isomer, brassidic ac., which after cryst. fr. alc. melts at 60°.—PbA,, e. s. h. eth. or h. bz. p-Methylenedihydrobenzoic Ac., CH,:C,H,.CO,H.—Ndl. fr. lgr. S.h. aq.; e. Ss. ale. oreth. Gives Test 304.—AgaA silky ndl. Oxyhypogeic Ac., C,,H;,,0,;—White mass.—Boiling alkalies give dioxypalmitic Ac. o-Toluic Anhyd., (Me.C,H,.CO),..0.—R. p. a. 325°.—Cryst. fr. eth. or bz.—Test 307 gives ac. w. m. p. 102°, v. d. s. c. aq.! a-Methylhydrocinnamic Ac., Ph.CH,.CHMe.CO,H.—B. p. 272°, Lft. v. d. s. c. aq.— Ag, cryst. ppt. Tridecylic Ac., Me.(CH,),,.CO,H. a-Ethylcrotonic Ac.—C,H,,0,.—Cryst.—Sbl.—D. s. aq.—Fusion w. KOH gives acetic and butyric acids. (Test 311.) Ethylphenylacetic Ac., Ph.CHEt.CO,H. 7 Benzoic Anhyd., (C;H,O),.0.—B. p. 360° c.—Rhomb. pr. i. and very slowly attacked by c. aq.; s. ale. or eth. For behavior on titration cf. p. 37. Test 307 gives ac. (cf. Test 312) w. m. p. 121°, nearly i. c. aq.! o-Oxyphenylgiyoxylic Ac., HO.C,H,.CO.CO,H.—Ndl. Dec. on dist. to CO, and salicylic ac. (Test 319). t Lauric Ac., C,,H,;.CO,H.—Ndl. fr. ale-—Dec. by dist. under normal pressure.— Non-alkali salts all v. d. s. h. aq.—BaA,, pearly lft. Cimicic Ac., C,,H,,O,.—Pr. fr. eth—BaA,. amorph. ppt.—Unsat. (Test 304). Isooleic Ac., C,;H;,.CH:HC.CO,H.—Rhomb. plates fr. eth—E. s. alc.; less s. eth.—ZnA, cryst. fr. h. alc. (sep. fr. oleate). PbA, less Ss. in eth. than Pb oleate-——Occurs in some commercial ‘“stearic ac.” Angelic Ac., Me.CH.MeC.CO,H.—B. p. 185° (th. i.). Long-con- tinued boiling gives isomeric tiglic ac., m. p. 64-5°.—Pr. d. s. ¢. aq ; e. 8s. h. aq.—Spicyv odor.—CaA,+2 aq. alm. i. alc.; s. ¢. aq.; much less s. at 60°-70°.—BaA, +43 aq., e. s. aqg.— PbA, d. s. aqg.— Fusion w. KOH gives acetic and propionic acids (Test 311). Paraffinic Ac., C,,H,,0,.—Lft. fr. ale-—(Fr. action of fuming HNO, on paraffin.) Diisoamylacetic Ac., (C;H,,),..CH.CO,H.—Ndl. i. aq.; e. s. eth., alc. or bz. m-Ethylbenzoic Ac., Et.C,H,.CO,H.—Ndl. fr. h. aq., alm. i. ce. aq.— CaA, e. s. aq. or ale.—Test 905-1 gives isophthalic ac. Palmitolic Ac., C,,H,.0,.—B. p. 240° (15 mm.). Silky ndl.; i. aq.; v. s. ale. or eth_—Fuming HNO, oxid. violently.—BaA,, cryst. fr. h. alc.; i. aq.—AgaA, ppt., blackens in light.—Gives Test 304. Benzylpropionic Ac., Ph.(CH,),.CO,H.—Flat lft. fr. h. aq.; e. s. ale. or eth.—B. p. abt. 290°.—-CaA,, v. s. aq.; BaA,, Ift., s. aq. Stearolic Ac., C,.H,,0,.—Long pr. fr. ale-—D. s. c. ale.; e. s. h.— Distils w. little dec.—Gives Test 304.—Oxid. by fuming HNO,,. —BaA,, ppt. fr. aq.; s. h. ale. ; Diallyloxalic Ac., HO.C(C,H,),.CO,H.—Ndl. ‘‘rather d.” s. aq.; e. S. ale. or eth.—Gives Test 304.—Dec. on distil—Ca and Ba salts, e. S. C. aq. = —_————— eS 54 Melting-point Neut. (G2). Equiv. 48-7 150 50 298 50 310 Sy 242 51 244 51 164 51 296 OL 258 51-5 282 52 178 53 168 53-8 228 54-6 338 54-5 270 56-7 49 56-7 57 OF 148 57-5 336 58 164 58-9 178 59-5 182 59-9 270 60 or 65 146 60 338 61 150 62-6c 256 GENUS, DIV, A, SECT, 2. (ORDER I, SUBORDER I.) SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. Hydrocinnamic Ac., Ph.CH,.CH,.CO,H.—B. p. 279-8° (th. i.).— Ndl. fr. ale. or h. aq.; s. in 168 pt. aq. at 20°.—BaA,, mod. s. ndl. —Boiling with CrO, mixture (cf. Test 702) gives benzoic ac, (cf. Test 312). Ricinelaidic Ac., C,,H,,0,.—Ndl.—Oxid. by HNO, gives cenanthic ac. Eikosenic Ac., C,,»H;,,0,.—B. p. 267° (15 mm.) (th. i.).—Gives Test 304.—BaA,. Cryst. fr. ale. Pentadecylic Ac., C,;H ,0,.—Dec. on distil—Pearly scales. Oxymyristic Ac., C,,H,,0,.—Pearly lft., e. s. ale-—Dec. on distil._— Ca and Ba salts, ppts., d. s. h. aq. o-Isopropylbenzoic Ac., Pr.C,H,.CO,H.—Pr. s. h. aq.—Ba salt vy. s, aq.—lest 905 gives phthalic ac. (cf. Test 318-1). Ricinostearolic Ac., C,,H;,.0;—Ndl. fr. alc.—I. aq.; e. s. alc. or eth. Gives Test 304. Volatile w. very slight dec.—BaA, lft. fr. alc.; i, eth—AgaA gran. ppt.; i. eth. Oxypentadecylic Ac., C,,H.,0,.—Ndl. fr. dil. ale. (From convolvulin.) + Elaidic Ac., HC. (C,,Hus) : HC.CH,.CO,H.—Lft. fr. ale-—Solidifies at 44°_45°, on) p. 234° (15 mm.). Bai, PbA, are ppts.—(Geom. isomer of oleic ac.) 1-Methoethylphenethanoic(4) Ac., Me,.CH.C,H,.CH,.CO,H.—Ndl. fr. h. aq.—V. s. ale. or eth.—CaA, heated w. CaO gives cymene. {-Campholenic Ac., C,,H,,0,.—B. p. 247°.—Gives Test 304.—I. aq.; v. s. ale. or bz. BE Cy es ndl.,e. s. alc.; d.s. aq. { Myristic Ac., C,,H,,0,.—Lft. a SG, Ate or eth.—B. p. 196-5° (15 mm,).—BaA, cryst. powder; v. d.s. alc. or aq.; Pb, amorph, powder. Isoerucic Ac., C,.H,,0,.—Tbl. fr. alc.; rather d. s. ale. or eth.—Adds Br, in glacial Ac. sol. (Test 304.) Daturic Ac., C,;H,,0,.—Small ndl. fr. ale.; i. aq.i— PbA,, m. p. 104°-5°. Maleic Annede C,H,O;.—Cryst. melt eee h. aq., gradually giving maleic ac.—Ac. obtained by Test 307, v. s. aq., m. p. 130°. Glutaric Anhyd., C,H,O,.—B. p. 287° c.—Ndl. d. s. h. eth—Acid obtained by Test 307, s. aq.; m. p. 97-5°. Isocinnamic Ac., HCPh : HC.CO,H.—Monoclinic pr. fr. lgr.—v. s. ale., eth., or Igr. —Gives Test 304.—On continued boiling gives cinnamic ac. (Test 313) and styrene.—CaA,, s. in 8 pt. aq. Behenolic Ac., C,.H,,0,.—Ndl. e. s. abs. ale.—Gives Test 304.—Zn. dust and acetic ac. reduces to brassidic ac.—BaA, ppt. i. aq. and alc. o-Propylbenzoic Ac., Pr.C,H,.CO,H.—Lft. fr. dil. ale—Test 905 gives phthalic ac. 0-Phenylvalerianic Ac., Ph.(CH,),.CO,H.—Lft. fr. h. aq., e. s. ale.-— Ba salt d. s. aq. Undecolic Ac., C,,H,,0,.—Lft. e. s. ale——BaA, v. d. s. c. aq.—B. p. 177° (15 mm.). Gives Test 304. Margaric Ac., C,,H,,0,.—Cryst. Pecan aiiistts Ac., Me.(CH,),.CHOH.CO,H.—D. s. c. aq.—Sbl. Brassidic Ac., C,.H,,0,.—Lft. fr. ale —B. p. 160° (0 mm.) —V. d.s. ec. alc.—Less s. in alc. or eth. than erucic ac.—PbaA, v. d. s. h. eth.— JKOH fusion gives arachidic ac., m. p. 77°—Gives Test 304. m-Tolyacetic Ac., Me.C,.H,.CH, .CO,H.—Ndl. e. s. h. aq.—AgA, ndl. fr. hag. —Amide, ity 0 141° t Palmitic Ac., Me.(CH,),,.CO,H.—Ndl. or greasy feeling scales, s. in 10-7 pt. ale. at 20°; e.s. h. pipe) p. 339°-56° d.—G_ 0-8527 epee —Nearly odorless and tasteless. N early or quite neutral to in- dicators excepl in alc. sol. ng ee ee Melting-point (C.°); 64 64-5 65 66-5 67 68 68 68 69 69-5 69-3c. 71-2 77 Neut. Equiv. 330 100 162 308 160 284 144 180 166 142 162 180 296 208 178 214 136 312 GENUS III, DIV. A, SECT. 2. 55 (ORDER I, SUBORDER I.) SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. Dioxyricinoleic Ac., C,,H;,0;—I. aq.; v. e. s. ale. or eth.—Gives ee UUEEEEEEEEEE EEE 00 OO Test 304. Tiglic Ac., Me.CH:CMe.CO,H.—Gives Test 304; and 901 (slowly hot).—Cf. Div. A, Sec. 1. (a?)-Phenylcrotonic Ac., Ph.CH,.CH : CH.CO,H.—Nadl. fr. h. aq., e. s. ale., eth., and bz.—Gives Test 304.—CaA,+3H.0 silky ndl. Nondecylic Ac., C,,H,,0..—CaA,, cryst. ppt. Palmitoxylic Ac., C,,H,,0,—I. aq.; e. s. abs. alc. or eth_—AgaA gran. ppt. fr. alc. Itaconic Anhyd., C;H,O,.— Dist. in vacuo gives citraconic anhyd., m. p. 7.°—Rhomb. pr. tr. CHCl,; v. d.s. eth.—Unites rather easily w. aq to form its acid (cf. Test 307). o-Ethylbenzoic Ac., Et.C,H,.CO,H.—Lustrous flat ndl.—Test 905 gives phthalic ac. (cf. Test 318-1). Allocinnamic Ac., HCPh : HC.CO,H.—Pr. or tbl. fr. lgr.—Aniline salt ppt’d fr. bz. solution by aniline, m. p. 83° (Dif. fr. hydrocinnamic ac.)—Less s. c. lgr. than isocinnamic ac —Gives Test 304. Eikosinic Ac., C,,H;,0,—1I. aq.—B p. 270° (15 mm.). a-Oxycaprylic Ac., Me.(CH,) ,., CHOH.CO,H.—Large plates, v. d.s.aq.; e. s ale. or eth.—CrO, mixture oxid. to cenanthol and cenanthic ac.—Salts generally d. s. + Stearic Ac., Me.(CH,),,.CO,H.—Odorless, tasteless Ift.—Distils w. dec. at abt. 360°.—I. aq.; s. 40 pt. c. alc.; e. s. ¢ eth., bz., CS, or CHCl,.—Does not dissolve on shaking w ec. Na,CO, or deci- normal KOH.—CaCl, and BaCl, give gelat. ppt. w solutions of alkali salts. Monoethyl Fumarate, CO,H.C,H,.CO,Et.—D s. aq.; e s. alc. or eth. Gives Test 304.—Saponify and identify the fumarie ac. 3-Methtoethylphenol(2)-methanoic(1) Ac., C,,H,,0,—Ndl. fr. aq.— V.d.s.aq.; e s. ale. or eth.—Volat. w. steam.—Aq. sol. intense violet-blue w. FeCl, !—AgA mic. ndl. d. s. aq. Methoxyphenylacetic Ac., Ph.CH(OMe).CO,H.—Tbl. fr. lgr D.s. aq. orc. lgr.; e. s. alc. or eth.—CaA,, ppt., rather d. s. c. aq. Carnaubic Ac., C,,H,,0,.—(Combined in Carnauba wax.)—E. s. alc. or eth.—PbA, (103°), ppt. m. p. 110°-1°; i. eth. y-Ethoxy-4’-tetrahydrobenzoic Ac., EtO.C,H,.CO,H.—E s ale.— Gives Test 304.—AgA, ppt. a-Benzalpropionic Ac., Ph.CH : CMe.CO,H.—B. p. 288° Cryst.e s. ale., eth., or bz.—Gives Test 304—BaA,, d.s.c aq Phenyl-1’-cxybutyric Ac., Ph.CHOH.(CE,),.CO,H.— Pr. fr. c CHCl. —S. h. aq.; v.e.s. ale, eth., or CHCl;—Aq.+ HCl at 80° gives anhvd., m. p. 37°.— BaA,, v s aq.; AgA, ppt.,i aq. Dioctylmalonic Ac., C,,H,,0,—Cryst. fr bz—CaA, d.s. aq.—Gives Test 303. a-Hydropiperic Ac., C,,H,,0,. —Ndl.fr h.aq.—V.d.s ¢ aq.-e s ale or eth.—KMn0O, oxid. to piperonal (odor like heliotrope'), ete. Gives Test 304 —AgaA cryst. ppt 1-Methyl-3-propylbenzoic(4) Ac., (Me)(Pr).C,H;.CO.H.—Ndl fr. aqg.— Volat. w steam.—Ba and Ca salts v s aq. or ale, Lanolic Ac., C,.H,,0,.—Cryst powder.—I. aq. or lgr —BaA,+aq. ppt. { Phenylacetic Ac., Ph.CH,.CO,H.—B. p 265-5° ¢ —Thin Ift e s. h. aq.; d.s c aq.; v s. alc. or eth—BaA,+3H,0, e.s. aq. or alc. BaCl, gives no ppt Warming w dil. H,SO, and MnO, gives benzaldehyde (bitter almond odor, Test 113). Arachidic Ac., C,,H,,0,.—Lustrous lft., s in 222 pt 90% alc. at 20°. (Less s. than stearic ac.)—Salts resemble stearates.—Occurs in peanut-oil, etc. Melting-point (Ccy 77-8 78 78 78-80 80 80-1 87-8 88-9 88-9 89 90 382 Neut. Equiv. 396 312 176 194 368 162 272 106 300 340 300 314 176 218 312 162 204 56 240 64 272 178 150 282 452 ee ee ee GENUS III, DIV. A, SECT. 2. (ORDER I, SUBORDER I.) SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. Hyenic Ac., C,,H,,O,.—Cryst. grains. Cerotic Ac., C,,H,,0,.—(In beeswax.)—Tasteless and usually granular. —Alm. i. c. alc. (dif. fr. stearic and palmitic ac.).—Stellate mic. ndl. fr. h. ale-—S. bz. or eth.—Does not dissolve in h. dil. NaOH. Ricinstearoxylic Ac., C,,H;,0,.—Ndl. e. s. ale. or eth.—Gives Test 304.—BaA,, volum. ppt.; AgA, gran. ppt. Pinoylformic Ac., C,,H,,O,.—Lft. fr. h, aq.; v. s. h. aq.; e. s. eth.— Gives soluble KHSO, compound. y-Methylhydrinden-{-Carbonic Ac., C,,H,,0..—B. p. 300°-30°.—S. h. aq.; e. s. ale—BaA,+4 aq., ndl., v. s. aq. o-Ethylethermelilotic Ac., o-EtO.C,H,.C,H,.CO,H.—Silky ndl. fr. aq.; v.d.s.c., d.s. h. aq.; e. s. alc. or eth.—Ba salt, e. s. aq. turns red at 100°. Lignoceric Ac., C,,H,,0,.—D. s. c. ale.; e. s. eth., bz., or CS,.—Pearly lustre, a-Benzalpropionic Ac., Ph.CH : CMe.CO,H.—Repeated recryst. gives ac., m, p. 74°. Gives Test 304. Mono-methyl Phthalate, C,H,0,. Examine saponification products. a-Oxypalmitic Ac., C,,H».CHOH.CO,H.—Sceales fr. alc.; e. s. ale. Monoethyl1 Carbopyrotritarate, C,H,0,.Et. —D. s. h. aq.—Lft. e. s. eth.; e. s. alc. Distil. undec.—AgaA ppt. f-Oxystearic Ac., C,,H;,0;.—6-sided tbl. fr. ale. S. in 10-4 pt. ale. at 20°. Behenic Ac., C,,H,,0,.—Solidifies at 78°. a-Oxystearic Ac., C,,H;,0;.—6-sided tbl. fr. eth. §S. in 172 pt. ale. at 20°. Ketostearic Ac., C,,H;,,0,.—Silky cryst. fr. dil. ale—AgA, cryst. ppt. Ac.-Tetrahydro-a-Naphthoic Ac., C,,H,,.CO,H.—Pr. fr. acetic ether. S, in 1052 pt. c. aq.; v. s. ale—KMnO,+ Na,CO,; sol. decolorizes after 2 min.—AgaA ppt. Dioxyundecylic Ac., C,,H,,.0,—Ndl. fr. aq.; e. s. h. aq. orale.; d.s. eth. Stearoxylic Ac., C,,H;,0,—Lft. d.s. ¢. alc.; e. s. h. ale-—BaA, semi- solid ppt., i. ale.; AgA cryst. powder. $-Benzalpropionic Ac., Ph.CH : CH.CH;.CO,H.—B. p. 302° (long-con- tinued boiling gives H,O and a-naphthol, Test 402).—Ndl. fr. h. aq.; d.s. h.aq.; e. 8. alc., eth., or CS,.—-CaA, v. s. aq. Monomethyl Camphorate, CO,H.C,H,,.CO,.M .—Long ndl. fr. h. aq.; e. s. alc. oreth.— Saponify and test distillate for methyl alcohol by Test 819. re Glutaconic Anhyd., C,H,O,.—Nadl. fr. eth., s. in Na,CO, w. efferves- cence, giving sodium glutaconate (m. p. of acid 138°). Dibenzylacetic Ac., (Ph.CH,),.CH.CO,H.—Pr. fr. lgr.; i. aq.; s. eth.— BaA, ndl. d. s. h. aq.—Heated w. CaO gives dibenzylmethane. s-Dimethylsuccinic Anhyd. (a), C,H,O;.—RB. p. 235°.—S. h. aq. giving s.fumaroid acid, m. p. 124°, and a little less s.-anti acid, m. p. 195°, Lanopalmitic Ac., C,,H,,0;—(In combination in wool grease.)—I. in aqueous KOH, s. in ale. (a) o-Methoxycinnamic Ac., MeO.C,H,.CH:CH.CO,H. —E. s. ale.— Heat gives isomeric () ac., m. p. 182°-3°.—Gives Test 304. o-Tolylacetic Ac., Me.C,H,.CH,.CO,H.—Silky ndl., e. s. h. aq—Amide m. p. 161°.—Oxid. to phthalic ac. by KMnO, (cf. Tests 905-1 and 318). . Dibenzylacetoacetic Ac., C,,H,,.0;. Melissic Ac., C3 >H,.0,.—Silky scales (fr. beeswax).—E. s. CHCl,, CS,, and h. ale.; alm. i. c. ale. or eth.—PbA,, amorph. ppt.; may be ervst. fr. toluene. Ee GENUS III, DIV. A, SECT. 2. 57 (ORDER I, SUBORDER I.) Melting-point .C.°). 91 91 95-7 95-5 96 96-5 96-7 97-9 97 98 98-9 99 Neut. quiv. 150 174 328 178 180 466 226 250 176 boty. 164 240 07 468 356 150 166 154 206 372 184 162 164 176 316 SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. p-Tolylacetic Ac., Me.C,H,.CH,.CO,H.—B. p. 266°.—Ndl., d. s. c. aq.; e. s. h—AgaA ndl., e. s. h. aq.—Amide, Ift. fr. h. aq.; m. p. 184°! a-Dihydronaphthoic Ac. (labile), C,,H,,O,.—Tbl. fr. lgr.; s, in 552 pt. c. aq.; e. Ss. ale. or eth.—Gives Test 304.—Boiling w. dil. NaOH gives stable form, m. p. 125°, Fikosanol(2)-oic Ac., C,,H,,0;.—Silky lft. fr. bz.+lgr.; e. s. ale— BaA, (at 100°) floc. ppt. Tolylisobutyric Ac., C,H,.CH,.CHMe.CO,H.—wNadl. fr. lgr.—AgA, ppt v. d. s. aq. Methylethermelilotic Ac., o-MeO.C,H,.C,H,.CO,H.—Pr. fr. h. lgr.— Dee act: Coceric Ac., C;,H,.03;,—Cryst. powd. fr. h. alec. o-Benzoylbenzoic Ac., Ph.CO.C,H,.CO,H.—Triclin. ndl. (+aq.) fr. h. aq.—Ignited w. Zn dust gives anthracene (Test 912).—Oxime melts at 162°. Alantolic Ac., HO.C,,H,,..CO,H.—Ndl. d. s. c. aq.; e. s. alc. or eth.— Loses aq. on fusion giving anhyd., helenine, m. p. 76°. $-Tetrahydronaphthoic Ac., C,,H,,.CO,H.—Nadl. fr. dil. ale.; 1.¢. aq.— Adds Br, in the cold, but is not immediately oxid. by Na,CO,+ KMn Q,. 4-Methoethylphenol(2)-methanoic(1) Ac., Me,.CH.C,H,OH.CO,H.— Lft. fr. aq., v. d. s. c. aq.; s. h. aq.; v.s. alc. or eth.—Red-violet color w. FeCl,.—Distil. gives CO, and m-propylphenol.—BadA, asad, p-Toluylcarbonic Ac., Me.C,H,.CO.CO,H.—I. c. aq.; e. s. ale. or eth.— Unstable.—Conc. H,SO,+bz gives deep-red sol. changing to blue- violet; red ppt. on dilution.—Oxid. by KMnQ,. Benzyl-o-tolylacetic Ac., (C;H,),.CH.CO,H.—Large cryst. fr. ale. 3, 6-Dimethylphthalic(1, 2) Ac., Me,.C,H,.(CO,H),.— Pr. e. s. eth. or ale. ‘‘ Moderately” s. aq. Oxymelissic Ac., Cs).H,.0;.—Fine ndl. fr. bz. a-Oxybehenic Ac., C,.H,,0;.—E. s. high-boiling petroleum ether. ac 3-Dimethylbenzoic(2) Ac., Me,.C,H;.CO,H.—Nadl. fr. h. aq. Alorcinic Ac., C,H, ,0;.+H,O (air-dried).—Ndl. d. s. c. aq.; e. s. ale. or eth. Alkaline sol. becomes cherry-red on standing in air! Reduces Fehling’s sol.—Fusion w. 3 pt. KOH gives orcine. Dried over H,SO, melts at 115°. Methyluvinic Ac., C;H,O.CO,H.—Ndl. d. s. aq.; e. s. alc. or eth.— CaA,+4 aq., pearly lft. i. ale-—Boiled w. conc. KOH gives potas- sium acetate (Test 311). Benzyllevulinic Ac., C,,H,,0;—B. p. 230°-35° (40 mm.). Ndl. fr. dil. alc., v. d. s. aq.—Dec. on dist.—H,SQ, sol. yellow, but after 1 or 2 days blue-green.—Dibrom. derivative fr. Br in Ac., m. p. ibe ad: Isodioxybehenic Ac., C,,H,,0,.—Tbl. fr. alc., d. s. c. alc. or eth— AgA ppt. [—] Pinonic Ac., C,,H,,0;—B. p. (12 mm.), 178°-80°. Methylethersalicylic Ac., o-MeO.C,H,.CO,H.—TDbl. or pr. s. in 200 pt. aq. at 30°.—Baa,, v. e. s. aq.—Deec. a. 200° to CO, and anisol. s-Dimethylphenylacetic Ac., Me,.C,H;.CH,.CO,H.—B. p. 274°.—Mod. s. h. aq.—CaA,+3 aq., e. 8. aq. Benzoylacrylic Ac., C;H,0.C,H,.CO,H.—Ndl. fr. toluene, d. s. c. aq.; e. s. ale. or eth.—On warming w. alkali gives acetophenone (Test 712).—Heated above m. p. becomes ruby-red.—Gives Test 304. Dioxystearic Ac., C,,H;,0, (from elaidic Ac.).—Alkaline perman- ganate gives azelaic, pelargonic and oxalic acids. 58 GENUS IIL) DIVA “SHOT (ORDER I, SUBORDER I.) Mettioe noi Neut. {SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) re, Equiv. in 50 parts of cold water. 100-5 208 | Acetylphenyl-{-lactic Ac., Ph.CH.(MeCO,).CH,.CO,H.—Pearly scales. —Dec. at 200° to acetic and cinnamic ac. (Test 313). 102 164 | o-Tolylpropionic Ac., Me.C,H,.C,H,.CO,H.—S. h. aq.—H,SO, gives o-methylhydrindon. 102 136 | o-Toluic Ac., Me.C,H,.CO,H.—B. p. 259° (th. i.).—Ndl., mod. s. h. aq.; v. s. ale.—Test 905-1 or 3 gives phthalic ac. (Test 318).—BaA e, s. aq.—Amide melts at 138°. 102 164 1, 3-Dimethylphenethanoic(4) Ac., Me,.C,H;.CH,.CO,H.—B. p. 265°. —Ndl. e. s. alc. or eth. AgA + Aq. e. s. h. aq. 102-2-5 194 | Meconin, C,,H,,O, (anhydride of meconic ac.).—Sbl.—Ndl. s. in 700 pt. c. aq. or 22 pt. h. aq.—Contact w. alkalies gives salts of meconic ac. (free ac. unknown); is not soluble in ammonia.—Found in mother liquors from opium alkaloids.—Heated w. dil. H,SO, and MnO, gives opianic ac. 103 192 | (a), o-Ethoxycinnamic Ac., EtO.C,H,.CH:CH.CO,H.—Tbl. v. d. s. d. s.h.aq.; e.s. ale. or eth.— BaA, + 2 aq. e. s. aq.—Heat gives oh, f-ac., m. p. 135°.—Gives Test 304. 103-4 184 | i-Pinonic Ac., C,,H,,0,—Lft. fr.aq. ‘‘ Rather’ d.s. c. aq.; e.s. alc. or eth.—M. p. of oxime 150°. 103-4d. 164 Benzoylacetic Ac., Ph.CO.CH,.CO,H.—D. s. aq.; v. s. ale. or eth.— Ale. sol., colored violet by FeCl, !—Boiled w. KOH sol. gives ben- zoic ac. (Test 312), and acetophenone. Melts w. dec. to CO, and acetophenone (Test 712)! Attacked by Br or alk. permanganate. 104 176 | Phenylangelic Ac., Ph.CH:CEt.CO,H.—Ndl. v. d. s. e. aq.—CrO; mixt. oxid. to benzaldehyde and benzoic ac.! Gives Test 304. 104 176 | Phenylpenten(4)-oic Ac., Ph.C,H,.CH:CH.CO.H.—Tbl. fr. eth., d. s. aq.; e. s. eth.—Gives Test 304.—CaA+3H,0O, ndl. d. s. aq. 104—5d. Lanoceric Ac., C3,H,.0,.—Mice. lft. fr. ale.; d.s.eth. (In combination in wool fat). 105 174 | @-Dihydronaphthoic Ac., C,,H,,O,.—Pr. s. in 1734 pt. aq. at 14°.— Oxid. by KMnO, to phthalic ac. In C8, sol. changed by Br to bromanhydride m. p. 140° d. 105 170 | Campholic Ac., C,,H,,0,.—B. p. 260°.—Lft. fr. eth.-ale.; alm. i. aq- Volat. w. steam.—Ppt’d fr. sol. of alkali salts by CO,.—Fuming HNO, gives camphoric and camphoronic acids.—CaA,+H,0, cryst. ppt. 106 94 | + Azelaic Ac., CO,H.(CH,);.CO,H.—B. p. a. 360° (sl. d.).—Lft. e. s- h. aq.; s. in 700 pt. aq. at 15°.—5S. in 37 pt. c. eth_—CaA, v. d. s. gran. ppt. appearing when the ammoniacal sol. of the acid is boiled w. CaCl,! ZnA, v. d. s. eryst. ppt.—Does not give Test 304. 106 168 I, 3, 3-lrimethylcyclohexene(1)carbonic(2) Ac., C,,H,,0,.—B. p. 138° (11 mm.).—Ndl. fr. h. aq.—Unsat. 106-7 148 | + Atropic Ac., CH,:CPh.CO,H.—B. p. 267° d.—Monoclin. tbl. s. in 692 pt. aq. at 19°; s. CS,—Oxid. by CrO, to benzoic ac. (cf. Tests 702 and 312)!—NaA sol. gives no ppt. w. MnCl,. (dif. fr. cin- namic #¢c.).—CaA,+5H,0O s. in 43 pt. aq. at 18°.—Gives Test 304! 106-7 152 | m-Methoxybenzoic Ac., MeO.C,H,.CO,H.—Ndl. sbl. undec.—E. s. alc., eth., or h. aq.—Dist. of Cad, gives phenol (Test 414). 107-8 212 | m-Benzylbenzoic Ac., Ph.CH,.C,H,.CO,H.—Nadl. fr. aq.; d.s. c. aq.; e. s. ale. or eth.—CrO, mixt. oxid. to m-benzoylbenzoic ac.— BaA,+4H,0, s. aq.; AgA, ppt., d.s, h. aq. 108 228 | Phenylethermandelic Ac., Ph.HC(OPh).CO,H.—Ndl. fr. h. aq., v. d. s. c. aq.—Oxid. by h. dil. HNO, to benzaldehyde and picric acid. | 108-5 168 | + Dehydracetic Ac. (Methylacetopyronon), C,H.O,.—B. p. 269-9° ¢.— | S. in 100 pt. aq. at 6°; e. s. h. aq., ale. or eth.—1 drop 10% FeCl, gives yellow or orange (YO-OY) ppt. in aqueous solution !—Sol. in NaOH pale yellow.—Boil w. conc. NaOH and test distillate for acetone (Test 711).—Evaporation of the sol. in v. conc. ammonia gives an amide, m. p. abt. 200°. es Melting-point (G.°). 108-9 109 109-5 110 110-11 110-5 112 112 112-3 112-3 112-5d. 113 114 115 115 115 115 115 116 116-5 ws 118 GENUS @ le Dive Ames ECT, 2: 59 (ORDER I, SUBORDER I.) Neut. [SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) Equiv. 126 268 160 106 198 136 122° 194 150 166 192 214 212 164 288 162 178 226 178 164 180 in 50 parts of cold water. 2, 5-Methylpyromucic Ac., C,H,O(Me).CO,H.—Ndl. d. s.c.aq.; v.s. h. aq.; e. s. eth.—Sbl easily.—BaA,, octahedra, v. s. c. agq— Warmed w. conc. H,SO,-+ trace of isatin gives chrome-green color! Dibenzoylacetic Ac., (Ph.CO)..CH.CO,H.—D. s. aq.; e. s. eth.—Ale. sol. gives reddish color w. FeCl,. Boiled w. dil. H,SO, gives benzoic acid and acetophenone (Tests 312 and 712). Methylphenylpropiolic Ac., Me.C,H,.C : C.CO,H.—Gives Test 304.—Ag salt explosive ppt. Ethyl Isocarbopyrotritarate, C,,H,,.O,.—Ndl. fr. h. aq.; v.d.s. c. aq.; e. s. alc. or eth.; e. s. NaOH, Na,CO, or ammonia, but reppt’d by CO,.—Ale. sol. blue w. FeCl,! Reduces Ag or Cu salts in the cold. o-Phenylbenzoic Ac., Ph.C,H,.CO,H.—B. p. 343°.—Ndl. d.s. h.aq.; e. s. h. ale-—UaA,+2H,0, d. s. aq.; ignited w. CaO gives diphenyl, etc.—Fuming HNO, at 0° gives nitro deriv., s. alc., m. p. 221°. m-Toluic Ac., Me.C,H,.CO,H.—B. p. 263°.—Pr. fr. h. aq. s. in 60 pt. aq. at 100°, e. s. alc. or eth.—Oxid. by CrO, ‘mixt. to isophthalic ac. (Tests 905-2 and 318). Brassylic Ac., CO,H.(CH,),,.CO,H.—100 pt.'aq. at 24° dissolve 0.74 pt.; e. s. alc. or eth—CaA+H,O, pulv. ppt. Benzoyllactic Ac., Me.CH(C,H,0,).CO,H.—Cryst. s. alc. or eth., and in 400 pt. c. aq.—Boiled w. dil. HCl gives benzoic ac. (Test 312) and lactic ac. p-Ethylbenzoic Ac., Et.C,H,.CO,H.—Lft. s. h. aq.; e. s. alc. or eth.— BaA,+2H,0, s. in 45 pt. c. aq.—Oxid. to terephthalic ac. (Test 905 and 318). Phenoxypropionic Ac., Me.CH(OPh).CO,H.—V. d.s. c. aq.; e. s. h. aq: e. s. eth.—CaA,+2H,0, v. d.s. ale.; AgA, small ndl. blackened by light. Ethylbenzoylacetic Ac., Ph.CO.CHEt.CO,H.—Nadl. fr. dil. alc.; e.s. ale: or eth.—Boiling w. conc. alc. KOH gives benzoic ac. (Test 312) and butyric ac !—Oxime m. p. 89°-90°. Phenylethersalicylic Ac., o-PhO.C,H,.CO,H.—B. p. 355° d.—Lft. fr. dil. ale.; v.s. alc. oreth. NH,A, m. p. 180°. o-Benzylbenzoic Ac., Ph.CH,.C,H,.CO,H.—Sbl. in ndl.—D. s. ¢. aq.; e. s. eth.Warmed w. conc. H,SO, gives anthranol.—BaA,+ 54H,0, s. aq. o-Acetophenonecarbonic Ac., Me.CO.C,H,.CO,H.—Cryst. s. cone. H,SO,. Sweet taste.—With alc. NH, at 100° gives comp., m. p. 204°. Sol. in conc. H,SO, on standing forms isomethylenephtalid, m. p. es Dioxypalmitic Ac., C,,H;,0,.—Lft. s. alc. or eth. m-Methylcinnamic Ac., Me.C,H,.CH:CH.CO,H.—Silky ndl. fr. h. aq.; e. s. eth. or bz.—FeCl, gives egg-yellow ppt. w. NH, salt.—Gives Test 304. m-Methoxycinnamic Ac., MeO.C,H,.CH: CH.CO,H.—S. h. aq.; e.s. eth. —Gives Test 304. p-Phenyltolylacetic Ac., C/H;.CHPh.CO,H.—Lft. fr. aq.; v. d.s. ¢. aq.; s. h. aq.; e. s. ale. or eth.—Oxid. by CrO; to p-phenyltolylketone, ete.—CaA,+H,0, d.s. h. aq. f-Benzoylpropionic Ac., Ph.CO.(CH,),.CO,H.—E. s. aq. at 70° Heated above m. p. turns orange-yellow. PbA,+2H,0O, ndl., d.s. c., e. Ss. h. aq. Cuminic Ac., p-Me,.CH.C,H,.CO,H.—Triclin. cryst. v. d.s.c. aq.; e. 8. eth.—BaA,, lft. s. in 100 pt. aq. at 20°.—Oxid. gives terephthalic ac. (cf. Tests 905-1 and 318). Pyromeconic Ac., C;H,0;.—Cf. Phenols. FeCl; gives cherry-red color! Salicylic Ac. Acetate, o-C,H,0,.C,H,.CO,H.—Fine ndl. fr. h. aq. FeCl, gives violet color w. aq. sol. !—Saponification by hot alkalies gives acetic and salicylic acids! (cf. Tests V, 311 and 319). 60 GENUS III, DIV. A, SECT. 2. (ORDER I, SUBORDER I.) Melting-point Neut. |SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) cCGeS) %) Equiv. in 50 parts of cold water. 119-6 261 t+ Succinic Anhyd., C,H,O,.0.—(For behavior on titration ef. remark on page 37.—Long ndl. fr. alc.; v. d. s. eth.—Test 307 gives ac. s. aq., m. p. 185° (Test 320). 120 152 o-Oxymethylbenzoic Ac., HO.CH,.C,H,.CO,H.—Nadl. s. in 0-428 pt. aq. at 20°; s. eth.—In melting or on prolonged standing w. aq. gives phthalid, m. p. 73°.—Salts all soluble. abt. 120 Fellic Ac., C,,;H,,0,—(In human gall.)—Ndl. fr. dil. ale.; i. aq.; s. ale. or eth.—Taste bitter.—Opt. act.—BaA,+4H,0, s. in abt. 800 pt. c. or h. aq.—Color reac. w. sugar and H,SO, (cf. H. 11. 274). d.120 264 | Santonic Ac., C,,H,,0,—\Cryst. gradually turn yellow.—D. s. c. aq.; e. s. alc.; d. s. eth.—Fusion on boiling w. aq. gives aq. and san- tonin. Opt. active.—Pb.A, (at 100°) ppt. 120 or 127 192 | p-Toluyl-@-Propionic Ac., C;H,.CO.C,H,.CO,H.—Tbl. fr. Igr., e. s. h. aq., alc., or eth.—Turns red above m. p.—AgaA ndl. 121 -2c. 122 | + Benzoic Ac., Ph.CO,H.—B. p. 249-2° c.—Monoclin. lft. or ndl.— Sbl. easily, vapor producing coughing.—S. in 344-8 pt. aq. at 20°, or in 17 pt. at 100°; at 15° s. in 2-14 pt. abs. alc., or in 3-19 pt. eth.— Apply Test 312! ey, 216 | Diisoamyloxalic Ac., (C;H,,),.COH.CO,H.—Silky fibres, s. eth.—Sbl.— BaA,, d. 8. c. aq. 122 164 Cetylmalonic Ac., Me.(CH,),,.CH.(CO.H),.—Rhomb. tbl. d. s. c. ale.: e. s. eth.-alc.—BaA cryst. ppt.; Ag,A powd. ppt.—Gives Test 302. 123 194 | o-Thymotic Ac., HO.C,H,(Me)(Pr).CO,H.—V. d.s. h. aq.; e. s. eth.— Blue color w. FeCl. ! 123 139 | n-Dodecanedicarbonic Ac., CO,H.(CH,),..CO,.H.—Lft. mod. s. c. alc. or eth. 124-5 324 | Lichen-stearic Ac., C,,H;,0,.CO,H.—Pearly plates, i. aq.; e. s. h. bz. or CHCl,.--Not attacked by Br or permanganate.—NH,A, pr. fr. h. aq. (m. p. 106°). 125 161 | m-Tolylpropionic Ac., Me.C,H,.C,H,.CO,H.—Ndl. fr. h. aq—Oxid. by Test 905-1 gives isophthalic Ac. (Test 318-2). 125 204 Benzallevulinic Ac., Ph.CH:C(CO.Me).CH,.CO,H.—Cryst. fr. CHCl. S. in conc. H,SO, w. red color !—After boiling w. conc. KOH gives iodoform reac. w. I. (Test 801). 125 179 | a-Dihydronaphthoic Ac., C,,H,,0,.—S. in 3215 pt. c. aq.—Br addition- | product m. p. 152°. 125-7 Fluorescine, C,,H,,0,.CO,H.—Ndl. s. Ac. or eth—Gentle oxid. gives | fluorescein ! ; 126 150 1, 3-Dimethylbenzoic(4) Ac., Me,.C,H,.CO,H.—Sbl.—B. p. 268°.—D. s. h. aq.; e. s. h. ale—CaA,+2H,0, and BaA,+2H,0, e. s. aq. 127 164 I, 2, 4-Trimethylbenzoic (6) Ac., Me,.C,H,.CO.H.—Thbl., fr. lgr., v. d. s. c. aq.; s. h. aq.; v.s. ale. or eth.—Volat. w. steam. Distils un- decomposed.—Ignited w. CaO gives pseudocumene. 127 178 | m-Isobutylbenzoic Ac., C,H,.C,H,.CO,H.—Nadl. fr. lgr —Amide, ndl. fr. adi, My plod 127 180 mmnepere es Ac., C,H,0,.C,H,.CO,H.—Cryst. s. h. aq.; e. s. alc, or eth. 127-8 166 | [+] Tropic Ac., Ph.CH(CH,OH).CO,H.—Hard pr. fr. eth. 128 144 | Lactide, C,H,O,.—B. p. 255°.—Monoclin. tbl. fr. h. abs. ale., alm, i. ¢. aq.; ve d. s. ale.-—Boil w. aq., and apply Test 302 for lactic ace. to the cold solution.—Dry NH, gas gives lactamide, s. aq., and alo. o Mop4y 128 158 | Oxyroccellic Ac., C,,H;,0,.—Lft. of greasy feel, e. s. eth. or CHCl,.— At 160° gives anhyd. m. p. 82°.—Ag,A floc. ppt. Melting-point (.°); 128 128-9 128-9d. 128-9 128-30 128-5 130 130-5 130-40d. 131 133-3 :-5 133-4 133-5 134-5 135 135 Neut. Equiv. 74 166 196 170 101 a eee GENU See Diy swe CG dee 2: 61 (ORDER I, SUBORDER 1.) SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) in 50 parts of cold water. } Phthalic Anhyd., o-C,H,.(CO),.0.—B. p. 284-5c., subliming in fine long ndl.—Alm. i. ¢. aq.; s. h. aq. or c. ale-—Mix a few mgrms. w. an equal quantity of either phenol or resorcin; barely moisten w. conc. H,SO, and fuse according to Test 402. The fused mass dis- solves in dil. alkalies, in the first case with the deep red color of phenolphthalein, or, in the second case, with the strong green fluorescence characteristic of fluorescein. p-Hydrocumaric Ac., HO.C,H,.(CH,)..CO,H.—Monoclin. cryst., e. s. h. aq., alc., or eth.—Cold sat. aq. sol. becomes blue-gray w. 1 drop FeCl, sol—Reacts like tyrosin w. HgN,O,.—No ppt. w. PU.Ac, or w. BaCl, —-ZnA,+2H,O, s 130 pt. c. aq. Camphocarbonic Ac., C,,H,,0,.—D.s. aq.; e.s.eth. Fusion gives cam- phor and CO, (Test 715)! FeCl, gradually added to alc. sol. gives first a dark blue and finally a dark green !—Easily oxid.—Br sub- stitutes easily, giving ac. m. p. 109°. Pinonic Ac., C,H,,0,.—Cryst. fr. CHCl,; d.s.c. aq.; v.d.s, lgr.—B. p. (17 mm.), 187°-93°. Glycollic Anhyd., C,H,0,.— Powder i. c. aq., ale., or eth.; s. h. aq. giving glycollic ac.—Heated above m. p. gives glycollide (m. p. 220°). {-Methoxyisocrotonic Ac., Me.C(OMe):CH.CO,H.—S alc. or eth. Gives Test 304. Hydrindoncarbonic Ac., C,H,.C,H;.CO,H.—Ndl. s. in 120 pt. aq. at 100°.—BaA, v- s. aq.—Oxid by alk. KMnO,.—Br substitutes cold. Cinnamic Anhyd., (C,H,0O),0.—I. aq.; v. d. s.c. ale.—Cryst. powd. Test 307 gives acid of Test 313. Acetophenoneacetacetic Ac., (C,H,0)(C,H,O).CH.CO,H.—Heai gives acetophenoneacetone and CQ). a-Naphthylacetic’ Ac., C,,H,.CH,.CO,H.—E. s. h. aq.; e. s. eth.— Ignition w. CaO gives a-methylnaphthalin. 1, 4-Dimethylbenzoic(2) Ac., Me,.C,H;.CO,H. — B. p. 268° (th. 1.) — Ndl. v. d. s. h. aq.; v. s. ale-—CaA,+2H,O, mod. s. aq.—Amide, nal. dis. bh. ag.sm. p. 186°. a-Ethylnaphthoic Ac., Et.C,,H,.CO,H. Roccellic Ac., C,,H;,0,—(In certain alge.)—Cryst., i. h. aq.; e.s. ale. or eth.; s. Na,CO;—Swells up in cone, KOH, dissolving after dilution w. aq.—Ag,A, i. aq ; CaA, 1. aq. {+ Cinnamic Ac., Ph.CH:CH.CO,H.—B. p. 300° without dec., but does not sublime.—Monoclin. pr. fr. ale-—Odor faintly aromatic.— S in 1000 pt. aq. at 20°; in 4.3 pt. alc. at 20°; v.s eth.; s. CHCL,; d. s. CS, —Warmed w. CrO, mixt oxid. easily giving strong odor of benzaldehyde.—Identify by Test 313! Sebacic Ac., CO,H.(CH,),.CO,H.—B. p 243-5° (15 mm.).—Thin Ift. s. in 1000 pt. aq. at 17°, or in 50 pt. at 100°; e. s. alc. or eth.—Stable toward CrO, mixture —CaA, ppt —Ignition w. BaO gives octane. Oxid. w. dil. HNO, gives adipic, glutaric, and succinic acids. 6-Naphthoic Anhyd., (C,,H,O),0.—D. s. c. eth.; s. h. eth. or h. bz. Obtain acid of m. p. 184° c- by Test 307. Cis- (iso) Campholitic Ac., C,H,,0,.—B. p. 255°-6°.—Pr. fr. dil. ale.— Odor camphor-like —S. 5000 pt. c aq.; e. s. ale.—Unsat.— CaA, + 34H,O, ndl.,e.s.aq.; ZnA,,s. eth.; i aq. Sorbic Ac., Me.CH: CH.CH:CH.CO,H.—B. p. w. dec. 228°.—Long ndl. fr h. aq.; e. s. ale. or eth.—BaA,, silvery scales scarcely more s. in h. than in c. aq.—Gives Test 304. (@)o-Ethoxycinnamic Ac., C,,H,,0;.—Ndl. fr. h. aq.—CaA,+2H,0, v. d. s. c. aq.—Gives Test 304. Methylatropic Ac., Me.CH:CPh.CO,H.—Gives Test 304. 2 GENUS III, DIV. A, SECT. 2; (ORDER I, SUBORDER I.) Melting-point Neut. |SOLID ACIDS.—Colorless and generally not soluble (cf. note, p. 38) (9%: Equiv. in 50 parts of cold water. 135 140 2, 5-Dimethylfurfuranecarbonic (Uvic) Ac., (Me,).C,HO.CO,H.—Ndl. s.400 pt. h. aq.; e. s. ale. or eth—Warmed w. 2 drops fuming HNO, and then treated w. 6 drops conc. H,SO, gives cherry-red color.— Br substitutes very easily.—With aq. at 160° gives acetyl- acetone.—BaA,+4H,0O, ndl. d. s. c. aq.; ZnA,+8H,O (charac. cryst. aggregates) more s. c. than h. 136-7 146 | } Phenylpropiolic Ac., Ph.C:C.CO,H.—V. long hair-like ndl. fr. h. aq.—kKE. s. alc. or eth.—Melts under h. aq. at 80°.—Boiled w. Zn dust in glacial Ac. gives cinnamic ac. (Test 313).—Reduced by Na amalgam to hydrocinnamic ac.—Salts unstable in h. sol.—Gives Test 30+. 136-5 316 | Dioxystearic Ac. (from oleic ac.), C,,H,,0,—Lft. e. s. h. ale—BaA,, gran. ppt., 1. aq. or alc. 137 166 | m-Ethoxybenzoic Ac., EtO.C,H,.CO,H.—Ndl. d. s. h. aq.; s. ale. or eth.— BaA,, e. s. h. aq. 137-5 121 | @-Ethoxyisocrotonic Ac., MeC(OEt):CH.CO,H.—Pr. s. alc. or eth.— Boiled w. dil. H,SO, gives acetone (Test 711). 139 234 | p-Octylbenzoic Ac., C.H,,.C,H,.CO,H.—Lft. fr. h. ale.; v.d.s. h. aq.— Ag.A bulky ppt. 140 164 | p-Propylbenzoic Ac., Pr.C,H,.CO,H.—Lft. fr. h. aq. e. s. ale. or eth.— Oxid. by KMnO, to terephthalic ac. (Tests 925 and 318). 140 87 | Suberic Ac., CO,H.(CH,),.CO,H.—B. p. abt. 300° without dec.—Ndl. or tbl. v. d. s. eth.; alm. i. CHClI,; s. in 704 pt. aq. at 15-5°.— CaA+H,0O, s. in 161 pts. aq. at 14°.—BaA, s. c. aq., less s. h. aq. Ignition w. BaO gives hexane. 140-1 87 | a, s-Dimethyladipic Ac., CO,H.CHMe.(CH,),.CHMe.CO,H.—B. p. 321°. —D. s. eth. . 141 332 | Trioxystearic Ac., C,,H;.(OH),.CO,H.—Ndl. fr. h. aq. d. s. eth. 141 138 | Furfuracrylic Ac., C,H,0O.CH:HC.CO,H.—B. p. 255°-65° d.—Thin ndl. s. 500 pt. c. aq.; e. s. eth. or alc-—S. in cone. HCl w. green color !—Ba salt v. s. aq. or alc.—Gives Test 304. 141-3 316 | Dioxystearic Ac., C,,H;,0, (fr. Castor-oil).—I. eth.; d. s. c. ale-—HI reduction gives stearic ac. 141-3 180 | 4-Methoethylphenol(3)carbonic(1) Ac., C,,H,,0,—Boils w. decomp. —Ndl. fr. aq., v. d. s. c. aq.; s. h. aq.; v. s. alc. or eth.—Not ppt’d in dil. sol. by Pb.Ac,; BaA,, e. s. aq.—Long fusion w. KOH gives m-oxybenzoi¢e ac. 142d. 160 | Agaricic Ac., C,,H,,0,—Silvery lft. fr. 30% ale. (Cryst. w. 1H,O which is lost at 100°; loses more aq. in melting.)—Gelatinizes w. boiling aq., dissolves, and cryst. out on cooling.—D. s. alc. or eth.— (Obtained fr. Polyporus officinalis.).—BaA, amorph. ppt.; Ag,A (at 90°) gelat. ppt. 142-3 87 + Hydrochelidonic Ac., CO.(CH,.CH,.CO,H),.—Rhomb. tbl. d. s. aq. or eth.; i. bz.; s. ale-—Above m. p. gives anhydride (lft. fr. dil. alc., m. p. 75°). Oxid. by HNO, or alk. KMnOQO, to oxalic and succinic ac. (Test 320).—BaA+2H,0, e. s. lit.; ZnA+2H,0, charac, 6-sided 1. lft. 142-4d. 204 Benzoyltetramethylenecarbonic Ac., C,,H,,0,.—Pr. fr. eth. v. d. s. c. aq.; e. s. ale. or eth.—AgaA cryst. ppt. 144 150 1, 2-Dimethylbenzoic(3) Ac., Me,.C,H;.CO,H.—Glassy pr. fr. ale. — V. d. s. h. aq.—CaA,+H,O, mod. s. c. aq.; ignited w. CaO gives o-xylene Test 921. 144d. 90 perpen Cl 3) D * oe and with the color standard (cf. p. 232), observing the ms color from above. After a few seconds the color of the tartaric-acid a aa Ph )) faueieerce LO TS Se TS solution will be a clear yellow (Y-YT1). If the hue of the solution of the unknown acid is nearly the same, ——— while the intensity of its color equals or exceeds that =S: of the standard, the substance is very likely to be an : a-hydroxy-acid. If, on the other hand, the color is distinctly paler than the standard (i.e. lighter than YT1), or is a tint of yellow-orange or orange-yellow, the test has little significance. STS This test can be used only with cold solutions; for heat alone develops a yellowish coloration in ferric- chloride solutions of the concentration employed. Nearly all hydroxyl derivatives, when in sufficiently concentrated solution, will give a slight coloration with dilute neutral ferric chloride. The test is therefore valuable only when made comparatively. While it is not impossible that the hydroxyl group may produce identical color-effects in the case of some acids in which it does not occupy the alpha position with reference to carboxyl, in absence of any direct evidence that such acids exist, it may be assumed that the phenomena of this test are characteristic of the a-hydroxy-acids. Yellow colors approaching Tint 2 are likely to be given by almost any soluble acid. The colors given by the polybasic and keto-acids are much the most intense. Oxalic acid gives YT2-1— GYT2-1. Succinic and glutaric acids give slightly brownish colors, OYT1-2. Malonic acid gives no color. Pyruvic acid gives a Y-YO, and might almost be mistaken for an a-hydroxy-acid. Acetic acid and its homologues give a color that is YT2 or paler. 303. Acids Losing Carbon Dioxide at 200°. Place 0.1 grm. of the acid in a piece of glass tubing 8 cm. long and 5 mm. in internal diameter, sealed at one end. Connect the open end by a bit of rubber tubing with a narrow —_ Yn | | i HH | i Mn [| iN } i | | | | | ih I i RAH | My | || I i | | i || i fl Hl | | ii! |,| | | | i i i li | | | NUMBERED SEMI-SPECIFIC TESTS FOR ACIDS. 79 gas delivery-tube that leads into a three-inch test-tube (‘‘weighing-tube”’) containing clear baryta solution. Immerse the tube holding the acid for half its length in a bath of melted paraffin, or the sulphuric-acid mixture of page 219, contained in a small beaker. The bath must have been previously heated to 200° and be held constant at this temperature during the experiment. Continue the heating for two minutes. Acids that lose one or more molecules of carbon dioxide below 200° will give a heavy precipitate of barium carbonate. This test is given by all acids having two or more carboxyl groups attached to the same carbon atom. Other acids, excepting only a few of unusual instability, do not give it. It is not given, for example, by oxalic, tartaric, citric, lactic, salicylic, tannic, or gallic acids, although none of these compounds are particularly stable substances. Whenever the reac- tion does take place with a polybasic acid, one product is an acid of lower basicity. Thus, malonic acid gives carbon dioxide and acetic acid: CH2.(CO.H),=CO,+CH;.CO.H. By repeating the experiment on a somewhat larger scale, and continuing the heating as long as carbonic acid is given off, the organic acid formed may generally be isolated and identified. 304. Unsaturated Acids. Dissolve 0.1 grm. of the acid in 3 ec. of sodium-carbonate solution (the ordinary laboratory reagent, about 1:10). Then add, drop by drop, a one-per-cent solution of potassium permanganate. If the purple color of more than 1 cc. of the permanganate is instantly destroyed, and a brown precipitate of oxides of manganese appears, the acid may be unsaturated. The essential phenomena in this test are very uniform, and easily observed. Several cubic centimeters of the permanganate are usually reduced, and the reaction is practically instantaneous. It is unsafe, however, to draw the conclusion that every acid which shows this behavior must be unsaturated. Formic acid, and most phenol acids like oxybenzoic acid and gallic acid, behave like the unsaturated compounds; but saturated acids are, as a rule, very slowly attacked, if at all. As a confirmatory test for unsaturation in acids, Test 901 is often very useful. But as the addition of bromine at the multiple bonding, on which this reaction depends, takes place very slowly in the case of some of the double-bonded dibasic acids, the results (e.g. with fumaric acid) are occasionally a little difficult to interpret. Other cases in which unsaturated acids do’not add bromine easily are discussed by Bauer (Ber. 37, 3317), and Sudborough and Thomas (Soe. 97, 715). 305. Use of Esters with Characteristic Odors. The odors of many volatile esters are highly characteristic, though an adequate verbal description of their peculiarities can seldom be given. Ethyl cinnamate and ethyl ben- zoate may both be said to have an agreeable, sweet, aromatic odor; yet no one who is in the least familiar with these compounds would be in any danger of mistaking one for the other. The following procedure is occasionally referred to in the tables as a simple means for distinguishing between acids by differences in the odors of their esters. It is most satis- factory when it can be followed by a duplicate comparative experiment in which the organic acid used is known. The result requires confirmation by other more exact methods. To a few centigrams of the dry acid in a test-tube, add 0.5 ce. of a mixture of one part of concentrated sulphuric acid and two parts of methyl or ethyl alcohol. Heat the mixture several minutes at about 100°, keeping the tube loosely stoppered and the upper portion cool. Pour off into 3-5 ec. of cold water in a watch-glass. Warm gently and note the odor. An odor is much more easily observed in the open watch-glass than in a test-tube, and the dilution with water removes the sharp smell of sulphurous acid or alcohol that might otherwise mask the more delicate odor of the ester. 80 NUMBERED SPECIFIC TESTS FOR ACIDS. 306. Precipitation of Metallic Salts. The statement in the description of any acid, that its calcium salt is insoluble in water, does not justify the unqualified conclusion that it will appear as a precipitate when an aqueous solution of the acid is mixed with one of calcium chloride; for the salt will often be held in solution by the hydrochloric acid, which is the second product of the reaction. But a precipitate may usually be expected, whenever the neutral sodium salt of an organic acid is mixed with an equivalent quantity of any other neutral metallic salt which by a metathesis could yield a compound described in the tables as “‘ insoluble.” In attempting to prepare an insoluble salt of an acid for analytical purposes, it is therefore a good general rule to start from an exactly neutral solution of its sodium salt, rather than from the free acid itself. To obtain such a solution quickly, a small quantity of the acid may be dissolved or suspended in about twenty parts of water, a trace of phe- nolphthalein added, and caustic-soda solution then dropped in until the first appearance of a pink color; or, when the acid is difficult to obtain in quantity, the solution left over from the determination of neutralization equivalent in Test 301 may be used, after being somewhat concentrated by evaporation. When engaged in experiments of this kind, it is well to remember that some precipitates which, when once separated from solution, are very insoluble, do not appear immediately upon mixing the reagents; also, that some of the most characteristic salts of certain acids with the alkali earths, manganese, and zinc are more soluble in cold than in hot water, and hence do not begin to precipitate until the solutions containing them are heated or boiled. 307. Acid Anhydrides of Genus III. All these anhydrides are soluble in dilute aqueous alkali to salts of the corresponding acids, though in many cases solution proceeds slowly. A general method for the identifi- cation of such compounds is, therefore, to exactly neutralize and dissolve them, while sus- pended in water, by the addition of an equivalent quantity of caustic-soda solution; to decompose the soluble sodium salts with an exactly equivalent quantity of normal sulphuric or hydrochloric acid; and then, finally, to isolate and examine the liberated organic acid. A second important method is conversion into anilides or p-toluides. The anhydride is treated—heating above 100° for some minutes is occasionally necessary—with some- what more than an ‘‘equivalent’”’ weight of aniline or p-toluidine. The reaction product is crushed; washed with a little cold dilute acid, to remove the excess of base; and then purified by crystallization from hot water, dilute alcohol, or ligroin. The anilides and toluides are distinguished for the ease with which they can be crystallized and purified. The melting-points for a very large number have been determined and will be given a place in Vol. II of this work. 311. Acetic, Propionic, Butyric, and Isobutyric Acids. Whenever these acids have to be identified 7n an aqueous solution—and this is the problem which in actual practice will have to be solved more frequently than any other— the first step should always be to exactly neutralize with caustic soda, and then evaporate to dryness on a water-bath. The dry residue of sodium salt, from which it is not necessary that the water of crystallization should be removed, is then ready for use in the following tests. In very careful work, the result from the “ Preliminary Test 1” should be accepted as final only when it is negative. If, on the contrary, it points to the probable presence of one of these acids, Test 2, which is trustworthy and specific, should be applied. 1. [Preliminary Test.]|—Place 0.05 grm. of the dry salt in a three-inch test-tube. Add 0.1 cc. of concentrated sulphuric acid, and warm over a very small flame until the odor NUMBERED SPECIFIC TESTS FOR ACIDS. 81 of the vapors of the liberated organic acid can be easily recognized at the mouth of the tube. After noting whether the odor is simply sharp like acetic or propionic acid, or sharp and rancid like the butyric acids, cool; add 0.1-0.2 cc. of strong ethyl alcohol, and warm until vapors again begin to come off freely. Then pour into a watch-glass containing 5 ce. of cold water and carefully observe the odor of the ester that has been formed. (Cf. Test 305.) This is sensibly different for the different acids; but the differences are not great and the odors may all be described as ethereal and fruity. That given by acetic acid, and closely resembled by the ester from propionic acid, is often spoken of as “refresh- ing and agreeable.” The test is rather delicate, and, if made comparatively, may suggest which of the four acids is present. More than this should not be expected from it. 2. [Identification as Toluides.]—Mix in a dry six-inch test-tube 1.0-1.2 grms. of para- toluidine, and 0.3-0.4 cc. of concentrated hydrochloric acid. Add 0.4 grm. of the powdered sodium salt of the fatty acid. Rest the lower end of the test-tube in a circular hole 1 em. in diameter cut, by a cork-borer, in a piece of thick asbestos-paper or thin asbestos felt, to screen the side walls from overheating; and support the tube in a vertical position by a clamp on a lamp-stand. Boil gently over a very small gas-flame for one hour. During the first fifteen minutes steam should be allowed to escape slowly. After about twenty minutes, the water having all been removed by evaporation, the vapors of the condensing toluidine should be seen wetting the glass in a ring showing a clearly outlined upper margin and extending half way up the tube. Regulate the heat so that this appearance will continue unchanged to the end of the hour. [The following treatment of the fused mixture is designed to separate the acid-toluide, the desired product of the reaction (RCO.NH.C,H,), from the excess of toluidine, and from a dark oily resinous substance, by which it is always accompanied. MResinous residues filtered off in the course of this treatment should never be thrown away until it is found that the yield of acid-toluide will be sufficient for the purpose of identification; for unless properly extracted, small quantities of the resin will hold back the greater part of the toluide. The sep- aration depends on the solubility of the toluides and the insolubility of the resin in boiling weter, and on the volatility of toluidine with steam. If the directions given are carefully followed, the yield of pure acid-toluide will be entirely satisfactory, although never large.] Boil the cooled reaction product with 5 cc. of strong alcohol until nothing but white sodium chloride remains undissolved. Pour the solution, with stirring, into 50 ce. of hot water in a small beaker, and boil down quickly to 10-12 ce. Filter the boiling hot solution through a very small wet filter supported in a funnel that has been warmed by rapid rota- tion in a flame. Wash the filter with 2 cc. of boiling water. Unless the resin left on the filter forms only an exceedingly thin film, boil out filter and resin with 5 cc. of water, and filter hot into the first filtrate. Boil down the combined filtrates to a volume of about 10 ec. Cool well with running water; shake vigorously and filter. Dissolve the pre- cipitate in 5 cc. of boiling water; or, if it will not dissolve in this volume of water, increase the quantity by successive additions of 1 cc. until all does dissolve. Filter hot through a very small wet filter in a hot funnel 2.5 cm. in diameter. Wash with 2 cc. of hot water. Cool well in running water. Shake and filter. This precipitate should be white and free fromresin. If yellowish, another crystallization from 5 cc. of boiling water followed by hot filtration will be necessary. Dry the precipitate at 100°, if the odor of the acid was not rancid,—otherwise at a lower temperature,—and determine its melting-point. Acetic Acid (properties tabulated on p. 73) gives acet-p-toluide, melting-point 146°-7° (uncor.). The corrected melting-point of the pure compound is 148.2°. Propionic Acid (properties tabulated on p. 73) gives propion-p-toluide, melting- point 123.5°-124.5° (uncor.). Isobutyric Acid (properties tabulated on p. 73) gives isobutyr-p-toluide, melting point 104°-5° (uncor.). 82 NUMBERED SPECIFIC TESTS FOR ACIDS. n-Butyric Acid (properties tabulated on p. 73) gives butyr-p-toluide, melting-point 72.5°-73.5° (uncor.). By diminishing the quantities of reagents and solvents used, heating for two hours instead of one, and working very carefully, Test 2 may be carried out with one quarter of the weight of sodium salt recommended; but the yield is then so small that failures will sometimes occur. The quantity of hydrochloric acid used in a test ought never to exceed greatly the quantity theoretically required to combine with the sodium of the organic salt, toluidine hydrochloride reacting upon the toluides at high temperatures. Hence, if the quantity of salt taken for any experiment is less than has been directed, the hydrochloric acid must be diminished proportionally. A moderate excess of para-toluidine will, however, do no harm, and the quantity should under no circumstances be reduced to less than 0.5 grm. Test 2 may be used for the identification of acids containing slight admixtures of homo: logues. In the case of acetic acid it is still applicable when the impurity is quite con- siderable, if the first crop of impure acet-toluide crystals is recrystallized from hot ben- zene. The benzene gives at the same time a good separation both from the resin and from homologues. The other toluides are too soluble in benzene to be crystallized from it with advantage, but they may be recrystallized from a few cubic centimeters of hot petroelum ether, in which the resin will remain dissolved on cooling. Whenever it is desired to separate the acids under consideration from a dilute aqueous solution containing salts, neutral compounds of any description, or non-volatile acids, proceed as follows: Distil over into a dish containing 3 cc. of normal caustic-soda solution, or 0.12 to 0.14 grm. of solid caustic soda dissolved in a little water, the solution being colored by the addition of a little phenolphthalein. As soon as enough acid has distilled over to discharge the pink color, evaporate to dryness, scrape together the residue of dry sodium salt, and use the whole of it for Test 2. 312. Benzoic Acid. (Properties tabulated on p. 60.) 1. To 0.1 grm. of the acid in a dry test-tube add 0.17—-0.20 grm. of phosphorus pen- tachloride, and warm, stirring with a glass rod until a clear solution is obtained. Cool, and add, drop by drop, cooling, 1 cc. of cold water to destroy the excess of chlorides of phosphorus. Then add slowly 0.4-0.5 cc. of aniline. Dissolve the reaction product in 2 to 5 cc. boiling dilute alcohol (1:1). Cool. Filter off the white crystalline precipitate; dry at 100°, and determine the melting-point. The benzanilide obtained from benzoic acid in this test is in the form of pearly-white scales melting at 159.5°-160.5° (uncor.). 2. Heat in a six-inch test-tube for one-half hour 0.1 grm. of the acid, 0.5-0.7 grm. of para-toluidine, and two or three drops of concentrated hydrochloric acid. The tube must be supported by a clamp, and its bottom made to rest in a circular hole 1 em. in diameter, cut by a cork-borer in a piece of thick asbestos-paper which has been laid upon the small iron ring of a lamp-stand. Heat with a very small flame whose height is so regu- lated that the vapor of the boiling toluidine shall condense upon the walls of the tube for a distance of two to three inches from the lower end. Dissolve the reaction product in 10 cc. of dilute alcohol (1:1). Filter hot. Cool and filter. Wash the crystalline precipi- tate with 5 cc. of cold water. Repeat the crystallization with the same quantity of solvent, and wash as before with 5 cc. of water. Dry at 100°-105° and determine the melting-point. p-Benztoluide, the product in this test, crystallizes in white or slightly yellowish plates melting at 155.5°-156.5° (uncor.). 313. Cinnamic Acid. (Properties tabulated on p. 61.) 1. Stir 0.05 grm. of the acid into 3 ce. of a cold ten-per-cent solution of potassium NUMBERED SPECIFIC TESTS FOR ACIDS. | 83 permanganate on a watch-glass or in a small round-bottomed glass dish. A strong odor of bitter almonds (benzaldehyde) will immediately develop. 2. Stir 0.1 grm. of the powdered acid into 3 cc. of fuming nitric acid (sp. gr. 1.48- 1.60), contained in a small round-bottomed dish. The substance will at first dissolve, but within two or three minutes a considerable light-colored precipitate will separate. Allow to stand for 7-10 minutes. Then mix with 30 ce. of cold water and stir for a minute. Filter off the bulky precipitate of nitro acids and wash with 10 cc. of cold water. Transfer the precipitate to a test-tube and boil with 5 cc. of strong alcohol. Cool well. Shake, and allow to stand a few minutes to insure complete precipitation. Filter, and wash with 5 cc. of cold alcohol. Boil up the precipitate in a test-tube with 5 cc. of ether. Cool. Shake and filter. Wash the rather scanty precipitate with 5 cc. of cold ether. Dry at 100°, and make a melting-point determination. ' The final product in this test is para-nitrocinnamic acid. It is more or less distinctly crystalline, nearly white, and melts to a dark-brown liquid at 286°-287° (uncor.), after turning brown and beginning to soften at about 265°-270°. [Ortho-nitrocinnamic acid, and possibly a little nitrobenzoic acid, are also formed during the nitration, but they are completely removed by the treatment with alcohol and ether.] 314. Color Reactions for Citric, Malic, and Tartaric Acids. To 0.05 grm. of the finely powdered acid in a small porcelain evaporating-dish add 10-15 drops of a freshly prepared solution of 0.1 grm. £-naphthol in 5 cc. of pure concen- trated sulphuric acid. Place the dish on a boiling water-bath and remove it at intervals of thirty seconds to one minute for the observation of the color changes which follow one another in quite rapid succession. When the maximum color intensity has been reached, dilute cautiously with four to five volumes of water and again note all the changes that occur. Citric Acid (cf. p. 47) gives at first a pale greenish blue, soon turning to blue-green (BG), and finally, rather slowly on continued heating, to an wmpure green of very slight antensity and permanence. The color after dilution with water is similar in quality to that from tartaric acid, only very much paler. Tartaric Acid (cf. p. 48), after exhibiting a momentary pale blue-green color changes very rapidly to pure intense green (G), which is rather persistent, even when heated on the water-bath. The dilution with water causes a change to a very distinct orange-yellow (YO-OY). Malic Acid (cf. p. 43) at first gives a momentary greenish yellow (GY-Y) that changes rapidly to an intense yellow (Y) which is quite permanent. Dilution gives a yellow- orange (YO), which is distinctly more intense than the corresponding color from the two other acids. These tests were first described by Pinerua (Compt. rend. 124, 291). While not con- elusive unless supported by other specific tests, they are useful reactions. They are most satisfactory when used as “comparative tests.” 315. Formic Acid. (Properties tabulated on p. 73.) Formic acid has a very sharp penetrating odor much like that of acetic acid, but more irritating. Like other acids of its series, aqueous solutions of its neutral sodium salt show reddish or orange colorations w:th ferric chloride. Unlike its homologues it reduces alkaline permanganate in the cold in Test 304. 1. To 5 cc. of a 1-3 per cent aqueous solution of the acid, add one gram, or an excess; of powdered mercuric oxide. Warm to a temperature of 40°-50°. Close the mouth of the tube with the thumb and shake vigorously for about one minute. Filter off the 84 NUMBERED SPECIFIC TESTS FOR ACIDS. undissolved oxide, and boil the clear filtrate for at least half a minute. A dark gray pre- cipitate of finely divided mercury will appear suddenly within a few seconds after boiling begins. HgO+CH,O,=Hg+CO,+H,0. 2. Place at least two drops of strong acid, or 0.1 grm. of the dry sodium salt in a small “weighing-tube” (a narrow three-inch test-tube). Add five drops of concentrated sul- phuric acid and heat over a very small flame until a brisk effervescence begins. Ignite the escaping gas. [H,CO,=H,0+CO.] The carbon monoxide will burn at the mouth of the tube with a pale-blue flame for some seconds, if the heating is continued. 316. Glutaric Acid. (Properties tabulated on p. 42.) In a dry test-tube fitted with a cork stopper and a 25 cm. length of glass tubing, to act as a return condenser, heat 0.1 grm. of the acid with 0.4—0.6 cc. of aniline at 175°- 190° for one hour. Boil with 10 ce. dilute alcohol (1:1). Cool and filter. Wash with 2 cc. cold dilute alcohol (1:1). Crystallize from 5 cc. boiling strong alcohol. Cool, shaking if no precipitate appears at once. Filter. Wash with 1 cc. cold strong alcohol. Recrystallize from 4 cc. boiling strong alcohol. Filter. Wash with 1 ce. cold alcohol. Dry at 100°, and determine the melting-point. The product, glutarantlide, crystallizes in white needles and melts at 221°-222°, It begins to sublime slightly at 214°-218°. 317. Oxalic Acid. (Properties tabulated on p. 42.) 1. Dissolve a few centigrams of the acid in water. Add ammonia in excess, and then a few drops of calcium-chloride solution. A white pulverulent precipitate of calcium oxalate will at once make its appearance. The precipitate is insoluble in ammonia or acetic acid, but dissolves readily in dilute hydrochloric acid. 2. In a dry three-inch test-tube (small “weighing-tube”) place 0.1 grm. of the acid and five drops of concentrated sulphuric acid. Heat over a very small flame so as to obtain a brisk effervescence. Ignite the gas that issues from the tube—(a mixture of carbon monoxide and dioxide). The carbon monoxide will burn with a pale-blue flame for several seconds, if the application of heat is continued. 3. Heat in a six-inch test-tube for fifteen minutes 0.1 grm. of the acid and 0.5-0.7 grm, of para-toluidine. The bottom of the test-tube should be made to rest in a circular hole 1 cm. in diameter cut by a cork-borer through a piece of heavy asbestos-paper. The tube should be supported in an upright position by a clamp, and the asbestos-screen rested upon the small iron ring of a lamp-stand. Heat with a very small flame protected from drafts, and so regulated that the toluidine vapors shall be seen to condense and flow back along the walls of the lower third or half of the tube. Boil out the reaction product with 10 cc. of dilute alcohol (1:1). Cool and filter. Wash the residue of oxaltoluide on the filter with 5 cc. of cold water. Transfer to a test-tube and boil up with 10 ce. of strong alcohol. Cool and filter. Wash with 2 cc. of strong alcohol. Dry at 100°-110°, and determine the melting-point. | Oxal-para-toluide crystallizes in white plates melting at 266.5°-267.5° (uncor.). 318. The Phthalic Acids. The different behavior of these isomers towards heat is an important distinguishing characteristic. Phthalic acid melts with loss of water at 184°, giving a sublimate of thin flat needles of its anhydride. Isophthalic acid also melts and then sublimes; but this occurs above 300°, and the sublimate is the unchanged acid. Terephthalic acid sublimes unchanged above 300°, but without previously melting. Phthalic Acid. (Properties tabulated on p. 67.) _ 1. Mix 0.05 grm. of the powdered acid with an equal quantity of resorcin. Place in a dry test-tube and moisten with one drop of concentrated sulphuric acid. Stand the — a ee oe ee NUMBERED SPECIFIC TESTS FOR ACIDS. 85 test-tube in a small beaker containing a liquid bath (cf. p. 152), that is, at a temperature of 160°, and heat for three minutes. Cool. Treat the fused mass with 2 cc. dilute sodium- hydroxide solution. Pour off into 500 cc. of cold water. The water will show a very intense yellow-green fluorescence due to fluorescein (cf. Test 402). The isomers of phthalic acid do not give this reaction, though similar colorations are given by some other dibasic acids, like succinic and glutaric. The test is extremely delicate. 2. Heat in a six-inch test-tube for fifteen minutes 0.1 grm. of the acid and 0.4-0.6 ce. of aniline. The tube must be supported by a clamp, and its lower end rest in a circular hole 1 cm. in diameter cut by a cork-borer through a square piece of thick asbestos-paper that is supported on the iron ring of a lamp-stand. Heat with a very small flame whose height is so regulated that the boiling aniline vapor shall be seen to condense upon the walls of the tube for a distance of two or three inches from its bottom. Boil the reaction product with 10 cc. dilute alcohol (1:1). Cool and filter. Wash the precipitate with 5 cc. of cold water. Recrystallize from 10 ce. of boiling strong alcohol. Cool and filter. Dry at 100°, and determine the melting-point. o-Phthalanil, the product in this test, crystallizes in white plates which melt at 204°-205°, Isophthalic Acid. (Properties tabulated on p. 72.) Mix in a dry test-tube 0.1 grm. of the acid and 0.3 grm. of phosphorus pentachloride. Heat cautiously over a very small flame until the mixture fuses to a clear liquid. Cool. Dissolve in 2 cc. of pure methyl alcohol. Precipitate out the dimethyl isophthalate formed, by adding 5 cc. of cold water, cool- ing and shaking. Filter. Wash the flocculent crystalline precipitate with 2 cc. of cold water. Recrystallize from 4 cc. of boiling dilute methyl alcohol (1:1). Cool well. Shake. Filter, and wash with 2 cc. of cold water. Press the precipitate between dry filter-paper. Dry at a temperature not exceeding 50°, and determine the melting-point. Dimethyl isophthalate melts at 64° (uncor.). It is very much more soluble in dilute methyl alcohol than the corresponding terephthalate. Terephthalic Acid. (Properties tabulated on p. 72.) Follow the direction given in the test for isophthalic acid, as far as the close of the first paragraph. Then precipitate the dimethyl ester from the methyl-alcohol solution by the addition of 10 cc. of cold water. Filter, and wash the precipitate with 5 ce. of water. Recrystallize from a boiling mixture of 4cc. strong methyl alcohol and 1 cc. of water. Filter off the heavy precipitate of thin, white, lustrous crystals that separates when the solution cools, and wash with 3 ce. of dilute methyl alcohol (1 : 1).—[Dimethyl terephthalate melts at 140°. This test might be successfully condueted, if it were necessary, with much smaller quantities of acid and reagents than are here recommended.] 319. Salicylic Acid. (Properties tabulated on p. 64.) (1) Prepare the methyl ester from methyl alcohol and 0.05 grm. of the acid or one of its salts by the method of Test 305. Methyl salicylate has the agreeable odor of oil of wintergreen. There are a few rare phenol-acids that are said to have a somewhat similar odor; but it is one that is not given by the isomers of salicylic acid, or by any acid of commercial importance. (2) Dissolve 0.1 grm. of the acid in 5 ce. of boiling water. Add 1 ce. of nitric acid (sp. gr. 1.2) and boil gently for five minutes. Pour into 20 cc. of cold water. Filter off the precipitate. Wash with 2 cc. of cold water. Recrystallize twice—the first time from 5 cc. of boiling water; the second time from 3 cc. Dry, and determine the melting-point. 5-Nitrosalicylic acid, the product in this test, crystallizes in white needles which begin to sinter together at 220°-222°, and then melt sharply to a brown liquid at 226°- 227° (uncor.). | 86 NUMBERED SPECIFIC TESTS FOR ACIDS, [The purple coloration (RV-VR), which will be observed in a 1 : 10000 aqueous solu- tion of the acid while applying Generic Test IV with ferric chloride, is a simple and favorite reaction. It is said to be sufficiently delicate to show the presence of the acid in solutions containing only one part in 500,000 parts of water. It is also given by neutral solutions of salicylates of the alkalies, but is prevented by the presence of free acids, alkalies, or salts of strongly alkaline reaction, like the alkaline carbonates or borax. The isomers of salicylic acid do not give it. Calcium and barium chlorides do not give a precipitate in neutral solutions of sodium salicylate, even after dilution with an equal volume of alcohol, or after adding ammonia and warming. Sharply ignited above its melting-point, salicylic acid emits a faint odor of phenol.] 320. Succinic Acid. (Properties tabulated on p. 49.) Place in a dry test-tube 0.1 grm. of the acid and 0.5 grm. of para-toluidine. Immerse the lower part of the tube in a small beaker containing one of the liquid baths mentioned on page 152. Insert a cork stopper fitted with a 25 cm. length of glass tubing to serve as a return cooler, and heat for one half hour at 200°-220°. After the tube has been removed from the bath and allowed to partially cool, add 10 ce. of dilute alcohol (1 : 1), and boil. Cool well and filter off the crystalline precipitate of succintoluide. Wash with 2 cc. cold dilute alcohol (1:1). Crystallize from 5 cc. of boiling strong alcohol. Filter. Wash the crystals with 1 cc. cold strong alcohol. Dry at 100°, and take the melting-point. The succintoluide thus obtained forms white needles melting at 254.5°-255.5° (uncor.). CHAPTER VI. GENUS IV. PHENOLIC COMPOUNDS OF SUBORDER I, ORDER I. (Colorless Compounds of Carbon, Hydrogen, and Oxygen.) To this genus belong all the true phenols of the suborder not included in the fore- going genera, and many non-aromatic “enols.”’ GENERIC TEST IV. APPLY PROCEDURE 1 OF THIS TEST FIRST TO EVERY COMPOUND, SOLID OR LIQUID. APPLY PROCEDURE 2 TO EVERY SOLID COMPOUND THAT FAILS TO GIVE A COLORATION IN PROCEDURE 1; BUT NOT TO LIQUIDS. COMPOUNDS THAT SHOW A PHENOLIC BEHAVIOR IN THE FIRST PART OF THE TEST ARE CLASSI- FIED AS PHENOLS IRRESPECTIVE OF THEIR BEHAVIOR IN PROCEDURE 2. PROCEDURE 1. (The Test with Ferric Chloride.) Dissolve about 0.05 grm. of the substance in 1 cc. of cold water; or, if this should be found impossible prepare a hot saturated aqueous solution; cool; filter, and use 1 cc. of the cold saturated filtrate. To this solution, in a narrow three- inch test-tube (small weighing-tube), held in front of a sheet of white paper, add three drops of the ferric-chloride reagent described below,* pausing for a few seconds after the addition of each drop to note whether any color change occurs. If no coloration is noticed, repeat the test in the same way as before, except that alcohol is substituted for water as the solvent. If any coloration, transient or permanent, other than a tone of yellow or orange-yellow (Y or OY), is observed, the substance is probably a phenol or an enol. PROCEDURE 2. (The Test with Alkali.) a. Place 0.10 grm. of the finely powdered substance in a narrow three-inch test- tube with 1 cc. of cold water, and ascertain by shaking and stirring whether it will dissolve. If it dissolves completely in the cold, and gave no color with ferric chloride in Procedure 1, it is not a phenol. * The Ferric-chloride Reagent.—Prepare the reagent as required for use by diluting three drops of the 10 per cent stock solution of ferric chloride with 1 cc. of water. 87 88 PHENOLIC COMPOUNDS. b. If the substance did not dissolve appreciably in experiment a, add 1 cc. of a cold aqueous sodium-hydroxide solution (1:10) to the mixture. Shake or stir well for about one minute, and notice whether solution is effected, and whether any strong coloration is produced. If the compound now dissolves completely, or if it dissolves completely after diluting the alkaline mixture with an additional cubic centimeter of cold water, the compound should be sought among the phenols. The appearance of any pronounced coloration in the alkaline solution, also shows the compound to be a phenol, though most of the phenols give colorless solutions in alkali. If a considerable part of the substance, though not all, dissolves in experi- ment a, add a little more of it to the solution, so that an undissolved residue of about 0.10 grm. shall remain. Treat this mixture with sodium hydroxide just as directed in the last paragraph, except that the subsequent dilution with water should be omitted in this case, unless a change in the appearance of the powder should indicate strongly that the formation of a sodium salt insoluble in concentrated alkali has taken place. ‘The phenomena observed are to be interpreted as in the last paragraph. OBSERVATIONS ON GENERIC TEST IV. In ‘‘the test with ferrie chloride” yellow and orange-yellow colorations have to be disregarded, because tones of these hues are produced by many polyatomic alcohols belonging to subsequent genera. A strong yellow also appears whenever alcohol is substituted for water as the solvent. Fortunately the colorations given by phenols, although varying widely in hue, intensity, and permanence, are not very often yellow, or either of the two adjacent hues in the color standard. The colorations characteristic of some phenols appear in extremely dilute solutions, others only in concentrated solutions. Some remain unchanged in quality for many hours; others appear and disappear within a second. A trifling excess of the reagent is sometimes sufficient to destroy the color; in other cases it is beneficial or necessary. It is for this reason, that it is desirable to observe the color after the addition of each drop of the chloride. The ferric-chloride test is applicable to cold solutions only. For further information concerning this reaction see numbered Tests 302 and 401. In ‘‘the test with alkali ”’ several distinct principles are involved. The first and most important of these is, that, with the exception of some polyatomic phenols like resorcin and pyrogallol, the species of this genus as a class are not ‘‘ easily soluble” in cold water, although they do dissolve readily in cold sodium-hydroxide solutions of certain concentrations. For the larger number of species a ‘‘ normal” concentration of the alkali has been found to be the best. But since the sodium salts of some phenols (e.g. sodium-methy] salicylate) are much less soluble in strong caustic soda than in water, they occasionally appear as precipitates even when the alkali used is only normal. It is to provide for this contingency that it is directed to dilute with about one volume of water whenever a precipitate (an insoluble sodium phenolate) is found to form. The use of a weaker alkali at the start is not advisable, because the salts of many phenols are so completely hydrolyzed in solution, unless a considerable excess of alkali is present, that their solubility in decinormal soda may appear to be no greater than in pure water. Finally, it should be men- PHENOLIC COMPOUNDS 89 tioned that a few compounds having phenolic structure will not dissolve unless the alkali is much stronger than normal. But their number is so small that it has been considered better to treat them as exceptions than to complicate the test for the sake of assuring them a position with the other phenols. The production of a colored solution in the test with alkali is not a general reaction of the phenols, but whenever a coloration does appear at this point, or in the titration in Test III, in the examination of an unknown substance, it is a very significant phenomenon, and is alone sufficient to indicate that the body should be sought among the phenols. The colors are sometimes very brilliant, as with the phthaleins, but often yellow, and sometimes dark brown, appearing gradually on stirring. Brown colorations are characteristic of phenols like pyrogallol, whose alkaline solutions are rapidly oxidized by the absorption of atmospheric oxygen. It is necessary to restrict ‘‘the test with alkali” to solid phenols, because it has been found that a considerable number of liquid species in Genus V and VI (e.g. diethyl succinate), which react neutral in Test III with very dilute alkali, are saponified by short shaking with a 1:20 aqueous soda solution. Since the liquid phenols, so far as is certainly known, all give colorations with ferric chloride, this limitation placed on the application of the alkali test is accompanied by no serious disadvantages. General Physical and Chemical Characteristics of the Phenols and Enols. Many of the phenols, like ordinary phenol, eugenol, and methyl salicylate, possess intense and characteristic odors and tastes; but many solid species are odorless and taste- less. All except a few of the simpler phenols, such as ordinary phenol, resorcin, and pyrogallol, are nearly insoluble in cold water, though soluble in solutions of the caustic alkalies. All the water-soluble species either give colorations in the test with ferric chlo- ride, or else solutions in dilute sodium hydroxide that rapidly turn brown through oxida- tion upon exposure to the air. In alkaline solution many phenols reduce potassium per- manganate in the cold in Test 304, and a smaller number, including many of the polyatomic phenols, reduce metallic silver from Tollen’s reagent in Test 101. The phenols are as a rule readily soluble in cold concentrated sulphuric acid, being very easily sulphonated, and are not reprecipitated upon dilution with water. In Test VIII they evolve hydrogen when treated with sodium, and are sometimes acetylated in the treatment with acetic anhydride. The color reactions of the phenols are numerous. Those depending upon: fusion with phthalic anhydride (cf. Test 402), treatment with sulphuric acid containing oxides of nitrogen, or with aromatic diazonium salts, all have analytical application. Colorations obtained with ferric chloride, as in Test IV, have been described for about half the solid species mentioned in this volume, and for nearly every liquid species. These color- ations are ascribed to the formation of unstable iron salts. Some phenols, like e-naphthol, whose dilute aqueous solutions are little or not at all colored by ferric chloride, are oxidized by it, and then separate from the solutions as precipitates of insoluble condensation prod- ucts (like dinaphthol). A portion of the aromatic hydrogen in phenols is very easily substituted by halogens or by nitro groups, poly-halogen, or poly-nitro derivatives being formed. Even very dilute aqueous phenol solutions consequently give precipitates upon treatment with an excess of bromine water (cf. Test 414-3). Test 901 may also be applied when evidence as to ease of substitution by bromine is desired. The nitro derivatives are readily prepared on the small scale, and are very often useful in completing identifications (cf. Tests 414-(2), 415, 418-(2), and 419). A fev’ phenols, like guiacol (cf. p. 91), give characteristic crystalline derivatives with picric acid. 90 PHENOLIC COMPOUNDS. One of the most important reactions of the enols is their behavior upon saponifica- tion. The saponification may be conducted, and the saponification products identified, by the method of Part 2 of Test V, as described on pp. 113 et seg. The following are examples of such reactions: CH,.CO.CH,.CO.CH,, (or, CH,.C(OH): CH.CH,) +KOH=CH,.CO.CH, + CH,.CO,K. (Acetyl acetone) (Acetone) (Potassium acetate) CH,.CO.CH,.CO,Et, (or, CH,.C(OH): CH.CO,Et) + 2KOH=K,CO, + CH,.CO.CH, + EtOH. (Acetoacetic ether) (Acetone) (Alcohol) The names usually applied to the enols in the tables of this volume, and in the illus- trations here given, are those properly belonging to the ketones with the corresponding desmotropic formule. This keto nomenclature, while open to criticism, is used, because, besides being probably the one in more general use at the time of writing, it also more quickly suggests the names of the saponification products that are to be expected. The enols, like the phenols, are soluble in cold dilute alkalies, give colorations with ferric chloride, and are attacked by sodium or bromine. When shaken with a saturated solution of copper acetate in water or dilute alcohol, some enols give precipitates of yore and characteristic blue or green copper salts. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I]. GENUS IV, PHENOLIC COMPOUNDS. DIVISION A,—SOLID PHENOLIC COMPOUNDS. eee eon PHENOLIC COMPOUNDS.—OColorless and Solid. 26 211-5c. J 1, 3-Xylenol(4), Me,.C,H,.0H.—V. d. s. aq.; miscible w. alc. or eth.—In Test 401 w. FeCl,, the 1% alc. sol. gives a GB color, very quickly fading through G to YT2, while the aq. sol. (1:100) gives a BV color, which fades in 2 min, to a white turbidity. 26 228 m-Propylphenol, Pr.C,H,.OH.—V. d. s. aq.—Aq. sol. pale blue w. FeCl,; alc. sol. green. 30 190-8 t o-Cresol, Me.C,H,.OH.—1% aq. sol. w. FeCl, in Test 401 gives a VB color on mixing, changing to Y in 5 min. and later to a turbid brown —The picrate, prepared by mixing a sol. of the cresol in a little 50% alc. with a concentrated solution of picric acid in 50% alc., forms orange-yellow ndl. w. m. p. 88° (m- and p-cresols give no picrates).— Unlike phenol, not dissolved by 5 pt. conc. NH,OH! 31-2 205 + Guiacol, o-MeO.C,H,.OH.—S. in 60 vols. aq. at 15°.—The 1% aq. sol. gives w. FeCl, in Test 401 a ROR color which slowly fades, the sol. becoming turbid. The 1% alec. sol. gives a GB w. FeCl,, which very rapidly fades to a YT2.— The alkaline sol. fr. the fusion w. phthalic anhydride in Test 402 has a VB-BV color, and an absorption spectrum not easily distinguishable from that of thymol (IV, A, m. p 49-6°)—7To a mixture of 0-1 grm. guiacol and 1 ec. aq., add a hot sol. of 0-2 grm. picric acid in 5 cc. aq.; shake well and allow to cool slowly. A brilliant O-YO cryst. ppt. of the picrate compound, w. m. p. 86°, appears within @ minute or two! 35 Diacetylbenzoyl Methane, Ph.CO.CH.(COMe),.—E. s. alc.; s. w. yellow color in Na,CO,;.—Ale. sol. blood-red w. FeCl,.— Cu salt dark blue tbl. w. m. p. 224°-5°, s. CHCl;.—Saponi- fication by Test V-2 gives acetophenone and acetic ac. (Tests 712 and 311). 36 201-8 } p-Cresol, Me.C,H,.OH.—Is not dissolved by 5 pt. cone. on mixing; the sol. then finally becomes turbid. 40-1 250 (560 mm.)| o-Oxybenzophenone, Ph.CO.C,H,.OH.—M. p. oxime 133°-4°, NH,OH.—Aq. sol. (1:100) in Test 401a gives BVT1-BT1-2 42-5 172-3 (12 mm.)| + Phenyl Salicylate (Salol), o-HO.C,H,.CO,Ph.—Odor faintly 414). aromatic.—Alm. 1. h. aq. (dif. fr. phenol); e. s. alc. or eth.— Dil. ale. sol. colored violet-red w. FeCl,.—Saponification by Test V—2 gives salicylic acid and phenol (Tests 319 and 42-5-3 183 + Phenol, C,H;.OH.—S. in 15 pt. aq. at 16°; alm. i. Na,CO,; miscible w. alc. or eth. Is dissolved by less than 5 pt. cone. ammonia (dif. fr. cresols)—An aq. sol. (1:100) w. FeCl, (Test 401) gives a violet color (V), permanent for more than 15 min.—Identify by Test 414! 43 Ethyl Benzoylpyruvate, Ph.CO.CH,.CO.CO,Et.—Dec. on dist.— Pr. fr. lgr., e. s. ale—Alec. sol. blood-red w. FeCl,—Saponifi- cation by Test V—2 gives acetophenone (Test 712), sodium oxalate, and ethyl alcohol. 91 92 GENUS. 1V,, DIV, A. (ORDER I, SUBORDER I.) Melting-point (C.2%, 46 47 49 49 49-6 50 51 51-2 53 57 59-60 60 60-1 61 63-6 65 Boiling-point CORA. 218-5 239d. 211-2 231-8 251-2 253 243 239 330-40d. 260-2 229¢ 225c. PHENOLIC COMPOUNDS.—Colorless and Solid. p-Ethylphenol, Et.C,H,.OH.—V. s. alc. or eth.—Aq. sol. gray- blue w. FeCl, Warmed w. P.O, gives phenol and ethylene. Isohomopyrocatechin, Me.C,H,.(OH),(1, 2, 3).— E. s. aq., alc., or eth.—Aq. sol. gives a transient green w. FeCl,. 1, 3-Xylenol(2), Me,.C,H;.OH.—S. h. aq.—Tribrom-derivative, in opeelio-. Diacetylacetone, CO.(CH,.COMe),.—Decomposes spontaneously, —Lustrous lft. e. s. eth. or h. alc.; sol. in alkalies w. yellow color! Gives dark-red color w. FeCl,.—Gives a leaf-green Cu salt and light-yellow Ba salt i. aq—With NH, gives lutidone. {+ Thymol, Me.C,H;.(Me,CH)(OH)(1, 4, 3).—Strong odor of thyme !—S. at 15° in 1200 pt. aq., or in 900 pt. at 100°.— Gives no color w. FeCl, except in cone. ale. sol. (1:2), when a trace of the very dil. reagent gives a transient green color (G). (Dif. fr. guiacol.)—Test 402 w. phthalic anhyd. is very striking though similar to that given by guiacol, The fused mass, which has a very intense VR-R color, dissolves to an intense blue (B) in dilute NaOH. This sol. shows an absorption band, when viewed through the spectroscope, extending fr. E to the orange. It narrows on cautious dilution until it finally appears as a thick line almost exactly at D!—Identify by Test 419! Paénol, Me.CO.C,H,OH.OMe.—Ndl. es. alc. or eth.; vol. w. st.—Alc. sol. colored dark red-violet by FeCl,.—Oxime, ndl., e. s. ale.; d.s. aq. Homopyrocatechin, Me.C,H;.(OH).(1, 3, 4). — V. s. aq. ale. or eth.— W. FeCl, gives green color, which changes to red- violet w. Na,CO,—Reduces AgNO, or Fehling’s sol. Pyrogalloldimethylether, HO.C,H..(OMe),.—FeCl, gives céru- lignon (s. in conc. H,SO, w. intense corn-flower color).— Conc. HCl at 100° gives pyrogallol. Hydroquinone Methyl Ether, p-HO.C,H,.OMe.—Not vol. w. st.—E. s. c. bz.—Reduces h. ammon. Ag. sol. Iridol, Me.C ,H,.(OMe),(OH)(3, 4, 5, 1).—E. s. alc., eth., or bz. Dioxybenzophenone, (C,H,OH),.CO.—Pale-yellow pr. fr. lgr.; alm. i. aq.; v. 8s. ale. or eth.; s. in K,CO; sol., but ppt’d by CO,.—Dil. alc. sol. colored brown-red by FeCl;—Warming w. conc, H,SO, or boiling w. KOH sol. gives carbonyldi- phenyleneoxide, i. aq.; m. p. 173°-4°. 1,2 (af)-Hydronaphthoquinone, C,)H,.(OH),. — Silvery Ift., s. in NaOH w. yellow color, which changes to an intense green.—Diacetate melts at 105°. Benzoylacetone, Ph.CO.CH,.COMe.—D. s. c. aq.; v.s. ale. or eth.; e. s. NaOH; d. s. Na,CO,; i. NaHCO,.—Intense red color w. FeCl,!—Saponification by Test V-—2 gives acetophenone (Test 712).—Cu salt, pale-green ppt. by CuAc, fr. dil. alc. sol.! Ag salt i. ppt. p-Isopropylphenol, Me,.CH.C,H,.OH.—Aq. sol. becomes pale blue w. FeCl,; alc. sol. green. Dioxytoluene, Me.C,H;.(OH).(1, 2, 6). — E. s. aq. or ale.—W. Ca(OCl), quickly turns to a fuchsine-red color that changes to yellowish brown. t 1, 2-Xylenol(4), Me,.C,H,.0H.—Long ndl. fr. h. aqg.—Odor like phenol. Cold saturated aq. sol. becomes B on mixing with FeCl, (Test 401); the color rapidly fades, however, and is replaced by a white turbidity.—Tribrom-derivative melts at 169°. te ea ee a Melting-point Boiling-point (C.*). (C2), 66 246-7 64 or 68 219-5 67 68-9 219-5c. 71-2 234-5 73-4 | | 74.5 211-5 (th. i.) 15 218¢. 76-5 79 262 79-80 81 81 a. 200 80-5 | - 84 84 abt. 325 86° 86 266 (th. i.) GENUS IV, DIV. A. 93 (ORDER I, SUBORDER I.) a ee PHENOLIC COMPOUNDS.—Colorless and Solid. Hydroquinone Ethyl Ether, p-HO.C,H,.OEt.—Thin lft.e.s. h. aq. oreth:; d.s..c. aq. 1, 3-Xylenol(5), Me,.C,H,.OH.—V. d.s. ec. NaOH.—No color w. FeCl,;.-M. p. of tribrom-derivative 162-5°. m-Oxybenzyl Alc., HO.C,H,.CH,OH.—Cryst., e. s. alc., eth., or h. aqg.; d. s. CHCl,—Aq. sol. gives violet-blue color w. a little FeCl,. Mesitol, Me,.C,H,.OH(1, 3, 5, 2).—V. s. ale. or eth.; i. NH,OH or Na,CO,.—No color w. FeCl. Pseudocumenol, C,H,.(Me;)(OH)(1, 2, 4, 5).—Alm. i. c. aq.; Vv. s. ale. or eth.—No color w. FeCl,.—Very vol. w. st.—Acetic ac. sol. with Br gives Br deriv. m. p. 35°. Coniferyl Alc., MeO.C,H,:(OH)(C,H,.OH).(3, 4, 1).—D.s. h. aq.; e. s. eth.; s. alkalies—Dil. mineral acids change quickly to amorphous isomer, alm. i. eth—Na amalgam reduces to eugenol, Div. B, b. p. 247°.—CrO, mixture oxid. to vanil- line, ete. I, 4-Xylenol(2), Me,.C,H;.0H.—Odor like phenol.—Gives no pronounced color reac. w. FeCl, in aq. or alc. ! 1, 2-Xylenol(3), Me,.C,H,.0H.—Odor like phenol.—Aq. sol. blue w. FeCl, !—M. p. of tribrom-derivative 184° (ndl. fr. alc.). Diethyl Ketipate, EtCO,.CH,.CO.CH,.CO,Et.—Flat pr. fr. ale.— I. c. aq., e. s. eth.—Gives intense-red color w. FeCl, Boil- ing w. dil. H,SO, gives diacetyl !—Substitutes Br, easily.— The free acid is unstable. Pyrogalloldiethylether, HO.C,H;.(OEt),.—V. 8. ¢. bac G dil. ale-—Vol. w. st. Propylpyrogallol, Pr.C,H,.(OH),(1, 3, 4, 5).—V. s. aq., alc. or eth.—Aq. sol. indigo-blue w. FeSQ,. I, 2, 3-Irimethylphenol(5), Me;.C,H,.OH.—No color w. FeCl. Dibenzoylmethane, CH,.(COPh),.—Tbl. fr. methyl alc.; e.s. ale. or eth.; i. Na,CO,; v. e. s. NaOH.—Ale. sol. intense red- violet w. FeCl, !--Monobrom-derivative formed fr. 1-8 grm. Br and 2-24 grm. substance, each dissolved in 3 pt. CHCl, at 0°, (silky ndl.mijp, 93"): (a)-Dibenzoylacetone, (PhCO),.C: COH.Me.—Pr. fr. lgr.; dec. at 270°.—Sol. in Na,CO, w. yellow color.—Ale. sol. blood-red w. FeCl;.—Quite a strong acid.—Heated for 1 hour at 85° gives (@)-dibenzoyl acetone of m. p. 107°-10°, 1. in Na,CO, sol., and giving no color in alc. sol. w. FeCl. Dipyrocatechin,[C,H,.(OH),],..—Ndl.—Sbl.— Unstable.—Aq. sol. pale green w. FeCl,, becoming dark blue w. a little Na,CO3. p-Benzylphenol, Ph.CH,.C,H,.OH.—Cryst. fr. ale_—S. in NaOH, but not in NH,OH.—Dist. w. P,O, gives benzene, anthracene, and phenol. (Tests 913, 912, and 414.)—Dibrom-derivative. fr. excess of Br in CS, sol., m. p. 175°. + Saligenin, o-HO.C,H,.CH,.OH.—Rhombic tbl.—Sbl. fr. 100° —HE. s. c. aqg.; v. 8. h. aq.; v.s. alc. or eth.—Test 401 w. 3 0:5% alc. sol. and FeCl, gives a RV color, soon changing to YOT,.—The powder stirred w. a little conc. H,SO, gives a red color (RT1-VRT1).—Boiled for a short time w. 5 pts. aniline gives oxybenzyl-aniline, m. p. 108°; ndl. fr. ale. I, 2, 3-letramethy!phenol (4), Me,.C,H.OH.—E. s. alc. or eth.— Gives no color w. FeC],. 94 GENUS IV, DIV. A, (ORDER I, SUBORDER I,) Motte pone oars’ ae oh PHENOLIC COMPOUNDS.—Colorless and Solid. 88 } Diethyl Diacetylsuccinate, C,H,O,.Et,.—TDbL, e. s. alc. or eth. —Sat. aq. sol. w. FeCl, gives, in Test 401, a very pale but rather permanent violet-red (VRT2).—T To 5 cgrms. ester in a test-tube add 1 cc. conc. NH,OH, 1 ce. glacial acetic acid and 10 cc. dilute H,SO,. Place a pine splinter in the mixture and boil for 2 min.—The splinter becomes colored deep red (pyrrol reaction) !—Saponification gives acetonyl- acetone, C,H,OH, and COQ,. 89 2-Methylnaphthol(1), Me.C,,H,.OH.—Ndl. fr. aq—Gives white ppt. w. FeCl,; green ppt. w. Ca(OCl),_Ignition w. Zn dust gives -methylnaphthalene. seer | er 92 2-Methylnaphthol(4), Me.C,,H,.OH.—Gives same reactions as preceding, except that Zn dust gives a-methylnaphthalene. 92-3 255 p-Isoamylphenol, C,H,,.C,H,.OH.—Ndl. fr. h. aq. 93 250d. p-Anol, Me.CH: CH.C,H,.0H.—S. in alkalies—Exposure to air or h. dil. acids gives a brown. oil. 94 278-80 { a-Naphthol, C,,H;.OH.—Monoclinic.—Odor phenolic.—D. s. h. aqa@oi-c. aq. ; e. s. alc., eth., bz., or alkalies —Aq. sol. gives scanty white ppt. w. FeCl,. Identify by Test 412! 95 Pyrogallol Ethyl Ether, (OH),.C,H,.OEt.—Ndl. vol. w. st.—S. c.aq.; e. s. h. aq.; v. d.s. c. bz.—Gives blue-violet color w. FesO,. 95 230-1 (th. i.) | Trimethylphenol, C,H,.(Me,)(OH)(1, 2, 4, 6). 95-7 Ethyl Oxalylacetate, CO,H.CO.CH,.CO,Et.—FeCl, + aq. sol. gives deep-red color. 96-7 $-Hydrojuglon, C,H. (OH),.—Silvery 6-sided ndl. fr. ale.—S. 1000 pt. c. aq.; d.s. ale. or eth.; e. s. CHCl, and bz.—Gives an intense-yellow color w. N aOH, changing to red.—Boiled w. FeCl, gives juglon. 98 Benzocotoin, C,;H,,0,.— Pale-yellow ndL., e. s. eth. or dil. NaOH. —FeCl, gives dark-brown’ color.—Ammon. sol. gives amor- phous yellow ppt. w. PbAc,. 99 237 p-tert.-Butylphenol, Me,.C.C,H,.OH.—Ndl. fr. aq.—Heated w. P.O, gives isobutylene and phenol. 99 o-Oxyhydroanthranol, C,,H,.0,.— Yellowish lft. fr. ale.—S. ale. or eth.—The alc. sol. is colored green by FeCl,.—Solutions show a pronounced green-yellow fluorescence. 103 325 sl. d. Methyl Oxynaphthyl Ketone, Me.CO.C,,H,.OH.—6-sided pale- green pr. fr. bz.; i. aq., d. s. alc.; s. alkalies, but ppt’d by CO,.—Oxime, m. p- 168°-9°, 103-4 267-70 1, 2-Dioxytoluene(4), (OH),.C,H;.Me.—HE. s. aq., alc., or eth.; d. s. bz.—Aq. sol. colored green-blue by FeCl,; gives ppts. Ww. Br or PbAc,; gives yellow color w. Ca(OCl), sol.—Phthalic anhyd. fusion (Test 402) gives a fluorescein. 104 240-5 + Pyrocatechin, o-C,H,.(OH),.—Lft. fr. bz.; e. s. aq., ale., or eth.; s. c. bz. (Separation fr. hydroquinone.)—Aq. sol. (1:250) gives w. FeCl, a green (G) color, which, on addition of Na,CO,, changes to R, becoming OR within 15 min. !— Alkaline sol. browns in the air.—PbAc, gives white ppt. (dif. fr. hydroquinone).—Easily reduces sol. of noble metals and Fehling’s sol. on warming.—Apply Test 416! 105 Homosaligenin, Me.C,H;.(CH,OH)(OH)(1, 2, 4).—Lft. s. 15 pt. ec. aq.—Sol. gives deep-blue color w. FeCl,.—Dec. by heat- ing w. dil. HCl to i. homosaliretin, m. p. 200°-5°. 104-6 Dihydroresorcin, C,H,O,.—Pr. e. s. aq. or ale.; v. d. s. abs. eth. —Aq. sol. reacts strongly acid.— Aq. sol gives intense violet color with FeCl,. Reduces Ag sol.—Gives a phenyl- hydrazone w. m. p. 176° ; Melting-point Boiling-point CC). (ay: 105-6 298 106-5-108 287-90 108 108-9 110 110 112 114 255 115 fd: 115 295-300 116 276-5 116 297-8 116 117 227-8 (th. i.) 117 249-50c. 120 120-1 120-1 GENUS IV, DIV. A. 95 (ORDER I, SUBORDER I.) PHENOLIC COMPOUNDS.—Colorless and Solid. Dimethylapionol, C,H,.(OH),(OMe),(1, 2, 3, 4).—S. h. aq., ale., eth., bz., and alkalies. + Orcin, Me.C,H;.(OH).(1, 3, 5).—Cryst. w. 1H,O (m. p. 58°).— Sweet taste.—E. s. aq., alc., or eth.; d.s. CHC],—A 1% aq. sol. gives a VBT1I-BVT1 color w. FeCl, in Test 401, which slowly fades to a light tint of the same hue.—Reduces am- mon. Ag sol.—Sol. in ammonia absorbs O from air, becoming red.—br aq. ppts. tribrom-derivative (ndl. fr. dil. ale., m. p. 98°).—f Bring to a boil a sol. of 5 cgrm. orcin in 5 cc. of a1% NaOH sol. to which 5 drops of CHCl, have been added. An O-OR color is produced. Dilute the solution to 50 cc. and view with a black background. An intense YG fluorescence appears !—The phthalic anhyd. fusion (Test 402) gives a pure OR solution. I, 2, 3-letramethylphenol(5), Me,.C,;H.OH.—Alc, sol. becomes yellow-green w. FeCl). Phloridzin.—Cf. m. p. abt. 170°, at which temp. it remelts after losing aq. Ethyl Isocarbopyrotritarate. — Alc. sol. blue w. FeCl,. — Cf. Genus III (A, 2). p-Oxybenzyl Alc., HO.C,H,.CH,.OH.—Fine ndl., e. s. aq., alc., or eth.—Sol. in conc. H,SO, is red-violet. Phenanthrol, C,,H,.OH.—Lft. w. blue fluorescence.—D. s. aq.; e. s. alc. or eth Pentamethylphloroglucin, C,,H,,0,—E. s. in sol. of NaOH or Na,CO,.—Reduces KMnO, immediately. Abs. methyl alc. sol. with Br gives Br deriv., ndl., m. p. 75°-6°. Vanillyl Alc., C,H,.(Me0O)(OH)(CH,OH),(3:4:1).—Ndl. E. s. ale., eth., or warm aq.—5S. in conc. H,SO, w. red-violet color. —Gentle oxidation w. a little CrO, mixture gives vanilline (odor like vanilla) ! Acetovanillon, MeO.C,H,.OH.COMe.—Pr. s. in 200 pt. c. aq.— Cu salt a yellowish-green ppt.—Oxime melts at 95°. + Resorcin, m-C,H,.(OH),.—Tbl. fr. aq., alc., or eth.—Taste sweet.—V. s. c. aq., alc., or eth.; 1. CHCl, or CS,—A 1% aq. sol. gives a strong clear BV with FeCl, (Test 401), permanent for more than 15 min.—Identify by Test 418! Ethyl p-Oxybenzoate, HO.C,H,.CO,Et.—Saponification by Test V-2 gives p-oxybenzoic ac. and C,H,OH. m-Oxybenzophenone, Ph.CO.C,H,.OH.—Lft. e. s. ale. or eth.— Gives two oximes w. m. p. 76° and 126°; fusion of first gives second. Pyromeconic Ac., C,H,O;.—Sbl. at 100°.—4-sided pr. fr. h. aq. —V.s. ale., CHCl,, and h. aq.—Gives a cherry-red color w. FeCl,.—Boiling w. alkalies gives formic ac. and CO,.—Salts very unstable. I, 2, 4-letramethylphenol(5), Me,.C,H.OH.—Flat pr. fr. ale.— E. vol. w. st. 2, 6-Dioxy-1, 3-xylol, Me,.C,H,.(OH),.—S. aq.; v.s. ale. or eth, —Aq. sol. reddish w. FeCl. I, 3-Trioxynaphthalene, C,,H,.(OH);.—Sbl. in scales.—V. s. eth., CHCI,, or bz. Oxalyldiacetone, C,H,0.CH,.CO.CO.CH,.COMe.—Cryst. d. s. aq.; s alc., eth., or NaOH(Na comp. yellow).—Alec. sol. is col- ored dark brownish-red by FeCl,. saa ne ete et ee ca eee a ric re p-Diphenolethane, Me.CH.(C,H,OH),.—Cryst. fr. bz.; i. lgr.— _ Aq. sol. gives yellow-brown ppt. w. FeCl,.—Gives Ag mirror { @-Naphthol, C,,H,.OH.—D. s. h. aq.; e. s. ale., eth., or bz.— FeCl, gives a white opalescence w. the c. aq. sol.—Identify Sbl. partially. — V. s. Aq. sol. w. FeCl, Sol. in NaOH is blue-green, soon turning brown.—Boiled w. aniline gives compound (lft. fr. Cubebin, CH,.0,.C,H,.C;H,OH.—Nadl., alm. i. aq.; d. s. ale.; s, eth—Conc. H,SO, quickly produces a purple-red color.— Diethyl Succinylosuccinate, C,H,O,.Et,.—Pale-greenish cryst. w. bluish fluorescence fr. eth.; v. d. s. h. aq.—FeCl, colors alc. sol. deep cherry-red.—The sol. in NaOH is deep yellow. Ndl. or tbl.—Sbl.—S. e. aq.; e. s. ale—FeCl, gives cherry-red color w. aq. sol.— Fusion w. KOH gives formic and butyric acids—BaA-+ Methylpyrogallol, CH,.C,H,(OH);.—Sbl. in ndl.—W. FeSO, Diketohydrinden, C,H,:(CO),:CH,.—Cryst. fr. lgr.; v. d.s. ce. aq.; e. s. h. ale. or bz. SS. w. intense yellow color in dil. NaOH or Na,CO,!—Boiled w. aq. or alkali gives an acidic body, m. p. 206°-8°, whose alkaline salts are intensely red- + Pyrogallol, C,H,.(0H),(1, 2, 3).—V. s. ¢. aq.; s. ale. or eth.— Taste bitter (poisonous).—Alkaline sol. absorbs O rapidly. turning brown.—A 1% aq. sol. gives w. FeCl, an OYS! color, changing within 15 min. to OYS2.—V. dil. FeCl; gives bluish color.—Reduces AgNO; sol. in the cold.—Apply Diethyl Hydroquinonedicarbonate, CsH,O;.Et:.—Sbl. in flat greenish lft. w. bluish fluorescence.—D. s. ¢. alc.; sol. fluo- resces blue in reflected light, pale greenish yellow by trans- mitted light.—S. in dil. NaOH w. deep-yellow color.—With p-Benzoylphenyl, C,;H,,»0..—Dist.—Lft. d.s. c.aq., more s. h. aq.; e. s. alc., eth., and Ac.; s. in alkalies, but reppt’d by acids.— Dec. by conc. H4SO; at 200°, giving phenol and benzoic acid. 1, 6-Dioxynaphthalene, C;o>H;.(OH)2.—D. s. ¢. alc.; e. s. eth.— } Furoin, C,H,0.CO.CH(OH).C,H,0.—Nearly colorless (about YT3) eryst., d.c. alc.; 47 aq.—Sol. in ¢) cone] Haat) ae deep blue-green!—FeCl, gives no coloration.—E. s. ec. NaOH to deep bluish-green sol., very deep violet-red by transmitted light; color discharged on dilution, after first changing to green! ‘The violet-red sol. diluted as much as practicable shows heavy absorption bands between D and C in orange, and between D and D4}E!—The m. p. 96 GENUS IV, DIV. A. (ORDER I, SUBORDER I.) Melee Ue Ve reas PHENOLIC COMPOUNDS.—Colorless and Solid. 122 w. h. dil. ammon. AgNO, sol., evolving aldehyde. 122 285-6 by Test 413! 124 2, 5-Dioxytoluene(1), Me.C,H,.(OH),. aq., alc., or eth.; less s. bz.; s. alkalies. gives brownish-red color. aq.) w. m. p. 82°-85°. 125 276-9 m-Xylorcin, C,H,.(Me,)(OH),(1, 3, 4, 6).—Tbl. e. s. aq. or eth. 125 HNO, gives picric and oxalic acids. 126-7 —The alc. sol. shows intense light-blue fluorescence. 128 Ethylsuccinylosuccinic Ac., C,H,O;. 2H,0O, or 4H,0, pale rose-colored crystals. 129 gives same bluish color as pyrogallol. 129-5 9, 10-Dihydroanthrol(2), C,H,:(CH,),:C,H,OH.—E. s. alc. w. blue fluorescence. 129-31 | | violet, and whose Ag salt is dark red! 133 | 293 (sl. d.) 1395955 Test 417! 134 a trace of FeCl; gives a blue-green color. 134-5 FeCl; gives a transient blue color, then a copper-red ppr. 135 of oxime is 160°-1°; of the phenylhydrazone 79°-80°. 135-6 1, 4-Dimethylnaphthol(2), Me,.C,,H,.0OH.—Sbl. fr. 100°.—D, s.aq.; s.alc.; e. s. eth.—Zn dust ignition gives dimethyl- naphthalene.—Acetate, m. p. 77°-78°. i a ee. So Meiting-point Boiling-point yk (C29. 135-6 139 139-5 140 abt. 140 140-5 141-2 142 143 144 145 144-6 GENUS IV, DIV. A. 97 (ORDER I, SUBORDER I.) PHENOLIC COMPOUNDS.—Colorless and Solid. o-Oxystilbene, HO.C,H,.CH:CH.Ph.—Alm. i. h. aq.; d. s. ¢ alc eee alc Butenylonphenol(2), C,,H,,0,—Ndl. d. s. aq.; e. s. ale— Aq. sol. deep blue-violet w. FeCl,.—M. p. of oxime 84°-5°, Oxythymol, Me.C,H,.(Me,.CH)(OH),(1, 4,2,5).—B. p. 290°. —Sbl. undecomposed.—V. dase. 80,7 Ss, Wad) 6. 8. alc: or eth.—Oxid. gives thymoquinone.—Occurs in oil fr. root of Arnica Montana. 1,8-Dioxynaphthalene, C,,H,.(OH),.—D. s. h. aq.;_e. s. eth. or bz..—Dust provokes sneezing.—Aq. sol. w. FeCl, gives flocculent white ppt. which soon becomes dark green.— Kasily oxidized.—Diacetate, silvery lfts. fr. ale. (m. p. 147°-8°). | Hematoxylin.—Sol. in alkalies intense purple-red.—Cf. Suborder II, A, 1, p. 207. Oxyhydroquinone, C, H, .(OH),(1, 2, 4).—V. s. aq., alc., or eth.; alm. i. CHCl, CS eh risye aye Ac. sol, exposed to air soon browns. —Aq. "sol. w. v. dil. FeCl, gives transient green which changes w. Na,CO,, first to dark blue and then to wine-red.—A conc. aq. sol. gives dark floc. ppt. w. FeCl. —M. p. of triacetate 96-5°. Protocotoin, C,,H,,O,.—Pr. fr. ale.—Gives blue-green color w. c. conc. HNQO,. *_Dibrom-deriv. fr. Br in CS, sol., scales, m. p. 170°. Resacetophenone, Me.CO.C,H;.(OH),.(1, 2, 4).—Cryst. d. s. aq. —Aq. sol. colored wine-red by FeCl,.M. p. of oxime, 198°-200° d. Dioxyphenanthrene, C,,H,.(OH),.—E. s. NaOH w. green color, quickly changing to red.—S. in conc. H,SO,+ trace of HNO, w. red color.—V. e. oxidized.—Diacetate, m. p. 159°. Benzoresorcin, Ph.CO.O,H;.(OH),.—Ndl. fr. h. aq.; d.s. c. aq.; e. s. ale. or eth.—Alc. sol. becomes brown-red w. FeCl. —M. p. of dibenzoate 141°. Benzopyrocatechin, Ph.CO.C,H,.(0H),.—V. d. s. c. aq.—Ale. sol. w. FeCl, gives rich green coloration, changing to red on addition of a drop of ammonium carbonate.—Re- duces Tollen’s reagent (cf. Test 101). Arbutin, C,;H,,0,, (?) (substance dried in vacuo at 100°).— (Statements concerning symbol and m. p. are conflicting; m. p. 165° and 170° are also recorded.)—Taste bitter.— Lustrous nd) e. s. h. aq. or alc.; i. eth.; more s. in dil. NaOH than in aq.—A 1% aq. sol. gives a transient VB-BV color w. FeCl,.—Boiled w. x’s of FeCl, sol. gives pungent odor of quinone !—(A glucoside hydrolyzed by dil. H,SO, to dextrose and hydroquinone.) Orcacetophenone, (Me)(OH),.C,H,.CO.Me.—Silky ndl. v. s. alc. or eth.; e. s. NaOH or NH,OH.—Aq. sol. black w. FeCl. Dioxyayiene Cad: .(Me,)(OH),(1, 3, 2,4).—Sbl. in ndl.; v. s. aq., alc., or eth.-—Gives intense violet color w. FeCl,. sects P s-Trimethylphendiol, Me,.C,H.(OH),.. — B. p. 275° c.— Sbl. in lft.—D. s. c. aq.; e. s. alc. or eth.—Aq. sol. gives transient green color and gray ppt. w. FeCl,—Reduces ammon. AgNO, sol. sah aged ome ete sy (Ce H,.0H),.C.Me,.—I. c. aq.; . h. aq.; e. s; alc. or eth. Dee Succinylosuccinate, C ,H,O,.Me,.—FeCl, gives red color w. ale. sol.—The free acid is unstable. 98 GENUS IV, DIV. A. (ORDER I, SUBORDER I.) rn Melting-point COR: 154 156 156 158 158 159 159 160 161 161 161 161 162-3 163 Boiling-point (Ce). PHENOLIC COMPOUNDS.—Colorless and Solid. Bicarvacrol, C,,H,,0,.—Silky ndl.; i. aq.; e. s. alc., eth., or bz. I, 2, 4-Trimethylphendiol(3, 5), Me,.C,H.(OH),. Anemonin, C,,H,O,—Vol. w. st.—Lustrous ndl. fr. alc., or plates fr. CHCI, -—D.s. h. aq. ore. ale.; 1. eth—-Ale "sol. reacts neutral. ap s. alkalies w. yellow-red to blood-red . color.—A few degrees above m. p. solidifies to yellow com- pound which decomposes at 290°.—Combines w. phenyl- hydrazine. p-Dioxydiphenylmethane, CH,.(C,H,OH),.—Sbl.—Not vol. w. st.—E. s. alc.; v. s. eth.; s. CHCl,; i. CS,; s. in NaOH and ppt’d by CO,.—Aq. sol. colored brown-yellow by FeCl,.—Aq. sol. of disodium salt is green.—Fusion w. KOH gives p-oxybenzoic ac. and phenol (Test 414). + Convolvulin, C,.H,,0,, (?).—Amorphous.—Alm. i. aq. or eth.; e.s. alc.—Mix a few mgr. w. adrop of c. conc. H,SO, After 5 min. a VR color appears, changing after 4 hr. to R.— Warm a little w. x’s of conc. H,SO,; disagreeable odor of rancid butter, changing to sharp odor if temp. is increased. —S. NaOH w. dec.—A glucoside fr. jalap root (Convol- vulus purga), aoa dextrose, etc., on hydrolysis by h. baryta water. Maltol, C,H,O.(OH),.—Sbl. in Ift.—D. s. bz. or ec. aq.; v. s. CHCl, or h. aq.; s. NaOH, but reppt’d by CO,.—Aq. sol. colored an intense violet by FeCl,—Reduces ammon., Ag sol. c., or Fehling’s sol. when hot. 2, 3- TiGeeie ont C, ,H,.(OH),.—Rhombic lft. fr. aq.— S. h. aq.; e. s. ale. or eth.—Gives intense dark-blue BAS. w. FeCl. } Zsculin, C,,H,,0,.—White lustrous odorless ndl, slightly bitter taste.—Loses cryst. aq. at 120°-130°.—S. in 600 pt. c., or 12-5 pt. h. aq.; d.s. c. alc. or eth.; e.s NaOH — The cold supersaturated aq. sol. gives blue-green color (BG) w. FeCl,.—V. dil. aq. sol., especially in presence of a trace of alkali, shows a magnificent light-blue (BT2) fluo- rescence! Shaken w. little HNO, gives yellow sol., which becomes deep blood-red upon addition of NH,OH!— Hydrolysis by h. dil. HCl gives dextrose and eesculetin — Gives the Molisch color reaction in Test II w. e-naphthol. — (In bark of the horse-chestnut ) 4; 4-Dioxytriphenylmethane, Ph.CH.(C,H,OH),.—Ndl. fr dil. alc.; 1. c., d. s. h. aq.; e s alc. or eth—Diacetate melts at 109°- 111°, o-Bicresol, (Me.C,H;.0H),.—D. s. h. aq.; e. s. ale. or eth— Diacetate m. p. 131°. Benzyhydroxylphenol, Ph.CHOH.C,H,.OH.—D. s.c aq.;e. 8, alc. or eth.; s. alkalies —Aq. sol. colored red by FeCl. d-Biphenol, (C,H, .OH),—B. p 342° Ndl, v. ds h. aq.; v. s. ale. or eth. —Aq. sol. gives ppt w. PbAc, —Diacetate melts at 94°. 3, 3’-Dioxybenzophenone, (C,H,OH),-CO.—E s. KOH but re- precipitated by CO,.—Fusion w. KOH gives phenol and oxybenzoic ac. B-Orcin, C,H,.(Me,)(OH),(1, 4, 3,5).—B. p. 277°-80° —Much less s. aq. than orcin —NH, H sol w. Ca(OCl), gives clear carmine-red color.—Boiled w. Mail NaOH and CHCl, gives deep-red sol. w. green fluorescence like orcin !—Tetra- brom-derivative, ppt’d by Br aq., cryst. fr. lgr. w. m. p. 101°.—Phthalic ‘anhyd. fusion Rives no color, 160-70d. 165-5 168 168 168-70 169 169 abt. 170 171 173-4 175 176 178 180 184 184-5 GENUS IV, DIV. A. 99 (ORDER I, SUBORDER I.) oe ae are hale ll Meet ae ae TS i ee ee Melting-point CC}; PHENOLIC COMPOUNDS.—Colorless and Solid. { Anthranol, C,H,:C,H(OH):C,H,.—Lustrous v. pale-yellow (about YT3) ndl—kE. s. h. bz. Does not dissolve fully in c. alkali, but becomes bright yellow and gives a yellow filtrate; reppt’d by CO,.—The alkaline sol. when boiled in presence of air absorbs O, giving much anthraquinone! —Dissolve a small quantity in cold fuming HNO,; dilute w. aq. and dissolve orange ppt. in alc. containing 1 drop NaOH sol.; an intense violet-red color is produced!— Ignition w. Zn dust gives anthracene (Test 912). Bithymol, C,,H,,0,+H,O.—I. aq.; e. s. alc., eth., or bz.; s. in alkalies w. orange color. Arbutin, cf. IV, A, m. p. 144°-6°. Trioxyacetophenone (Gallacetophenone), (HO),.C,H,.CO.Me.— Pearly lft., e. s. h. aq—S. m NaOH w. brownish color; in conc. H,SO, w. clear yellow color.—Picrate, yellow ndl., w. m. p. 133°.—Oxime, ndl. fr. toluene w. m. p. 162°-3°. a-Hydrojuglon, C,,H,.(OH),(1, 4,5) (fr. the walnut-tree, Ju- glans regia).—Cryst., s.in 200 pt. aq. at 25°; v. s. alc. or eth.; i. CHCl, or bz.; e. s. alkalies w. intense yellow color which changes in air to red.—Br or FeCl, gives juglon. + Hydroquinone, p-C,H,.(OH),.—Sbl. in Ift.—Taste slightly sweetish.—S. in 17 pts. aq. at 15°; e. s. ale. or eth.—The cold saturated aq. sol. gives a YO colored sol. w. FeCl, in Test 401.—Boiled w. excess FeCl, gives pungent odor of quinone.—Alkaline sol. browns in air.—Reduces AgNO, on warming, and Fehling’s sol. in the cold.—Identify by Test 411! I, 2, 4-Trimethylphendiol(3, 6), Me,.C,H.(OH),.—-D. s. c. aq.; e. s. h. aq., alc., eth., or bz. Diacetate, m. p. 112°. Phloridzin, C,,H,,0,,.—Taste bitter!—Silky ndl. wh. first melt at 108°-9°, losing 2H,O of cryst., and then solidifying at 130°. —S. in 1000 pt. c. aq.; e. s. h. aq. or alc.; alm. i. eth.; sol. in NaOH absorbs O, becoming red-brown.—Sol. dark violet w. FeCl,.—A glucoside readily hydrolyzed by boiling w. dil. H,SO, to phloretin and dextrose. Tetraoxytriphenylmethane, Ph.CH.[C,H,.(OH),],.—D. s. aq.; e. s. alc. or eth.—Kasily oxid. to resorcinbenzein. | 2-Acetylnaphthol(4), Me.CO.C,,H,.OH.—Ndl. e. s. alc_—FeCl, gives floc. ppt. w. aq. sol.—Ppt’d fr. sol. in alkali by CO,.— KMn0O, oxid to phthalic ac. (Test 318). 1, 4-Hydronaphthoquinone, C,H,.(OH),.—Long ndl. s. h. aq.; e. s. h. alc. or eth.; alm. i. CS,.—CrO, oxid. to a-naphtho- quinone.—Diacetate melts at 128°-30°. Phenyl p-Oxybenzoate, HO.C,H,.CO,Ph.—Saponification by Test V very easily gives p-oxybenzoic ac. and phenol (Test 414). 1, '7-Dioxynaphthalene, C,,H,.(OH),.—S. aq.; e. s. alc. or eth.— Aq. sol. gives deep-blue ppt. w. FeCl,;.—Alkaline sol. blackens in the air.—Diacetate melts at 108°. Benzoylsalicin (Populin), C,,H,.0,.—Cryst. w. 2H,O (lost at 100°).—Taste sweetish.—S. in abt. 2000 pt. c. aq.; s. cone. KOH.—Conc. H,SO, colors amethyst-red.—Saponified by h. Ba(OH), to salicin and benzoic ac. (Test 412). I, 3, 5-Trimethylphloroglucin, Me,.C,.(OH),.—S. alkali carbon- ates.—Br gives derivative w. m. p. 90°. Filixic Ac., C,,H,,0, (fr. Aspidium Filix mas.).—Mic. lft. fr. eth.—lI. aq.; alm. i. alc.; s. eth—Reduces ammon. AgNO. —Fusion w. KOH gives phloroglucin (cf. Test 415). 100 Melting-point (C.°). 185 185 186 186 190 190 190 194d. 198-200 200 200 200d. 200 or 210d. 200-5 201 202-3 200-9 (s. h.) GENUS IV, DIV. A. (ORDER I, SUBORDER I.) eR PHENOLIC COMPOUNDS.—Colorless and Solid. Dithymolethane, Me.CH.(C,,H,,OH),.—Dist. undecomposed.— Ndl. fr. bz., plates fr. ale—Oxid. by MnO, and dil. H,SO, gives thymoquinone (Suborder 2, m. p. 45-5°). } Coniferine, C,, H,.0,+2H,0.—I. c. aq.; v.s. h. aq. or dil. alka- lies—Warmed with conc. HCl turns cobalt-blue.-—Warmed w. conc. H,SO, gives violet sol. changing to violet-red.— Gives no ppt. w. PbAc,.—Gives no color w. FeCl. Iretol, C,H,.(MeO)(OH),(2, 1, 3,5).—Ndl. e. s. aq., alc., or eth. —Br aq. gives hexabromacetone.—HNO, oxid. to oxalic ac. (Test 317). Irigenin, C,,H,,0,.—Rhombohedra fr. dil. alc.; d.s. aq.; i. eth. or lgr.—Aq. sol. deep violet w. FeCl,. Phenolphthalol, (HO.C,H,),.CH.C,H,.CH,OH.—Pr. d. s. h. aq.; e. s. alc. or eth.; 1. bz. or CHCl,.—Becomes red w. conc. H,SO,.—Alkaline potassium ferricyanide oxid. to deep-red solution of phenolphthalein. 2, 7-Dioxynaphthalene, C,,H,(OH),.—Nadl., sbl. w. dec.—E. s. h. aq., alc., or eth.; alm. i. CS,.—Transient dark-red color w. Ca(OCl),.—Alkaline sol. darkened by air.—M. p. of diacetate 129°-30°. Hydroceerulignon, (MeO),.C,,.0,.(0H),.—Monoclinic pr. fr. ale.— V.d.s. aq. or eth.; s. h. ale. or bz.—Reduces c. ammon. Ag sol.—F eCl, on exposure to air causes separation of coeru- lignon. Methylene-di-@-Naphthol, CH,.(C,,H,OH),.—Mic. ndl., e. s. alc.; alm. i. CS,.—M. p. of diacetate 211° (i. alc.; e. s. bz.).— Picrate melts at 178°-9°. Diethyl-p-diphenol-methane, Et,.C.(C,H,.OH),.—Pr. fr. alc.; i. h. aq.; e. s. alc. or eth. Resorcinphthalein.— Yellowish crystals.—Cf. Suborder 2, } Picrotoxin, C,H;,0,, (from Menispermum Cocculus).— Cryst. s. 300-400 pt. c. aq.; e. s. alc. or h. aq.; e. s. in NaOH, the sol. soon becoming golden yellow.—The color of a sol. obtained by dissolving afew crystals in conc. H,SO, on eruci- ble cover is a strong orange-yellow (OY) !—Taste of aq. sol. (1:10,000) intensely bitter !—No pronounced color w. FeCl. —Gives ppt. w. Br aq.—Reduces AgNO, sol. when warmed. (Very poisonous.) Daphnin, C,,H,,0,.—(Loses 2H,O of cryst. at 100°.)—Colorless pr. w. bitter astringent taste !—D. s. c. aq.; e. s. h. aq. or h. alc.; i. eth.; s. NaOH or Na,CO, w. yellow color.—FeCl, colors the solution bluish.—HNO, gives red color in the cold, —Hydrolyzed by dil. acids to dextrose and daphnetin. (In bark of Daphne Mezereum.) Tannic Ac., C,,H, ,0,.—See ITI, A, 1, m. p. 210°. Taste astringent, Phenoglucin, C,H,O,+ 2H,O.—Taste very sweet.—Pr. fr. aq.— Gives pale-violet color w. FeCl,. ft Salicin, C,,H,,O,—Taste bitter—A glucoside.—Hydrolyzed by h. dil. H,SO, gives dextrose and saliretin; by emulsin gives dextrose and saligenin.—Cryst. s. 28 pt. aq. (15°); more s. in NaOH; i. eth.—Gives no color w. FeCl,.—The powder stirred into conc. H,SO, on crucible cover gives bright scarlet (OR) color! . Hydroquinonphthalin, C,.H,,0;—Oxid. agents give hydro- quinonphthalein. Phloroglucin.—See m. p. 217°-19°. GENUS IV, DIV. A. 101 (ORDER I, SUBORDER I.) Be |) Pome point PHENOLIC COMPOUNDS.—Colorless and Solid. 206 4-4’-p-(or a)-Dioxybenzophenone, CO.(C,H,OH)..—Dist. unde- composed.—Cryst. fr. h. aq., e. s. alc., eth., or alkalies — Ppt’d fr. Ba(OH), sol. by CO,.—No color w. FeCl, .—F usion w. KOH gives CO, and phenol. —Tetrabrom substitution product fr. alc. sol. of compound w. Ac sol. of Br in cold, m. p. 213°-14°. 206-8d. Anhydrobisdiketohydrindene, C, .H,,0;.—Sol. in alkalies intense red to violet; ppt’d by CO,.—Oxime d. at 210° without melting. 212 Phenolphthalidein, C,,H,,0,—S. alc. or eth.; s. alk. w. pale yellow and in conc. H,SO, w. intense violet ‘color. 212 Hydrophloron, C,H,.(Me,)(OH),(1, 4, 2, 5).—Sbl. in Ift., s. h. aq.; v. 8. alc, or eth.; d.s. CS, —Boiled w. FeCl, or dil. HNO, gives phloron. —Reduces Ag sol, 212-13 Acetonresorcin, Me.CO.(C,H,OH),+ H,O.—I. aq., CHCl, bz., or abs. eth.; s. NaOH.—Resorcin and acetone are among the products of decomposition by heat. 210-20 a-Tribenzoylmethane, (Ph.CO),.C:(HO)C.(Ph).—S. in CHCl, or aq.—Freshly prepared gives pale-yellow sol. in 1% Na,CO,, and a deep-red color w. FeCl,. After fusion or keeping goes over to neutral 8-modification, WwW. m. p. 225°-6°. 215-16 2, 6-Dioxynaphthalene, C,,H,.(OH),.—-Sbl. in pearly lft.—D. s. c. aq.; e. s. ale. or eth.—Aq. sol. gives yellowish-white color w. FeCl, .—M. p. of diacetate 175°. 215-20 I, 2, 4, 5-Letroxybenzene, C,H,.(OH),.—Silvery lft. fr. Ac.—E. s. aq., eth., or alc. —Quickly oxid. by FeCl, or by air in alka- line sol. to dioxy quinone. 217-19 (r. h.) { Phloroglucin, C,H,.(OH),.(1, 3,5).—Loses 2H,O cryst. on heating to 100°. “Spl. w. sl. decomposition. —Taste sweet- ish.—E. s. aq., alc., or eth.—A 1% aq. sol. in Test 401 w. FeCl, gives BV-V coloration, which fades rapidly.—Sol. in NaOH absorbs O, but less rapidly than pyrogallol.—A pine splinter first well soaked w. conc. HCl assumes a deep-red coloration (R-VR) when dipped in a dilute aqueous sol. of phloroglucin !—The aq. sol. gives a heavy ppt. of tribrom- phloroglucin, which when purified melts at 151°.—Identify by Test 415! 218c. G-Binaphthol, (HO.C, ,H,),.—Distillation gives 6-naphthol (Test 413).—Flat ndl. fr, alc.; i. aq.; s. alc.; e. s. eth. Gives greenish color w. FeCl, becoming bright red on heating.— Picrate, e. s. alc., has m. p. 174°. 218-19d. Fustin, C,.H,,0.3 (?). SrWhite lustrous ndl., e. s. h. aq. or ce. dil. NaOH; d. s. eth.—FeCl, gives green coloration changed to blue-violet and red by Na,CO, !—PbAc, gives yellow ppt.— (A glucoside; hydrolyzed by dil. H,SO, giving fisetin and a carbohydrate.) 220d. Methylenedipyrocatechin, CH,.[C,H,.(OH),],.—D. s. alc. or eth. 222 Di-p-Oxyhydrobenzoin, C,,H,,0,.—Cryst., e. s. h. aq. ; less s. alc. ; 1. eth.—(Forms a Na salt.) 223-4 Umbelliferon, C,H,O,.—I. c. aq.; s. ale. and h. aq.—S. w. in- tense blue fluorescence i in cone. H,SO,.—When warmed has odor like coumarin.—s. in cold KOH, but on heating the sol. to 60° gives umbelliferic ac. 224 4-Oxyxanthone, C,,;H,O,.—Sbl. easily—White ndl. fr. ale.— Acetyl derivative, mic. cryst. fr. dil. ale., m. p. 137°-8°. 223-6 (r. h.) 6-Tribenzoylmethane, (C,H,.CO),CH. Pall DOL Ce aC. CHOI, or bz.3 1, NaOH. 226-7 Hydroquinonephthalein, C,H, ,0;.(0H),.—Ndl. fr. eth—S. in alkalies w. deep-violet color. rere 102 GENUS IV, DIV. A. (ORDER I, SUBORDER I.) Melting point Boiling-point (Coy (C2): 222—40d. d. 230 231 235d. 257 Sl... 241d. 242 d. w. m. 245 248 abt. 250 250 d. w. m. 250 251d. 250-3 252d. 252-4 PHENOLIC COMPOUNDS.—Colorless and Solid. { Gallic Ac., (HO),.C,H,.CO,H(3, 4, 5, 1).—Cryst. w. 1H,O (lost at 120°) in silky ndl.; s. 130 pts. aq. at 12-5°.—Aq. sol. absorbs O from air and turns brown during titration; gives no ppt. w. sol. of gelatine (dif. fr. tannic ac.). Orcinphthalein, C,,H,,0;.(0H),.—Pr. i. aq.; e. s. ale. oreth. S. in alkalies w. intense dark-red color without fluorescence. 2-Oxyxanthone, C,,H,O,.—Lustrous yellowish ndl. fr. ale.— Acetyl derivative, ndl. fr. dil. ale., m. p. 161°. G-Quinovin, C,,H,.0,, (?).—(A glucoside of quinovic ace. and quinovase-ethylether found in Cuprea bark.)—Cryst. seales fr. dil. ale.; alm. i. aq. or abs. eth.; s. alkalies.—Sol. in conc. H,SO, is yellow, becoming cherry-red on exposure to air. Bihydroquinone, [C,H,.(OH).],.—Taste very sweet.—Lft. e. s. aq.; v.s. alc. or eth.—Aq. s. w. little FeCl, gives red color; x’s of reagent gives biquinone. Methylenedipyrogallol, CH,.[C,H,(OH),],.—Cryst. powd. 3, (3)-Oxyxanthone, C,,H,O,.—Colorless ndl., e. s. NaOH sol.— FeCl, added to ale. sol. gives brown color. Diresorcinphthalein, C,,.H,,0O,+34H,0.—Silvery lft. fr. aq.—S. in alkalies w. indigo-blue color. Tetraoxytetraphenyl-ethane, C,,H,,.(OH),.—Scales i. aq.; e. 8. alc. or eth. { Brazilin, C,,H,,0;—Cryst. in colorless ndl. w. 14H,O, soon assuming a broken orange-red color on exposure.—Taste at first faintly bitter, then very sweet /—Sol. in NaOH intense carmine-red (R); in cone. H,SO, YO.—f Boil gently in a test-tube resting on a perforated asbestos screen, as de- scribed in Test 311-2, for 15 min., 0-1 grm. brazilin, 0-15 erm.fused sodium acetate, and 2-0 cc. acetic anhydride. Cool. Add 10 cc. water to residue, and boil. Cool. Filter. Dissolve cryst. in 10 cc. boiling dil. ale. (1:1). Cool. Filter. Repeat eryst. and filtration twice more as above directed. Dry crystals at 100° and determine melting- point.— The product, tetraacetylbrazilin, melts at 149° (uncor). . 1, 5-Dioxynaphthalene, C,,H,.(OH),.—D. s. aq.; e. s. eth.—Re- duces Fehling’s or ammon. Ag sol.—CrO, oxid. to the quin- one.—Diacetyl compound has m. p. 159°-60°. Methylenediresorcin, CH,.[C,H;.(OH),.],.—The alkaline sol. ab- sorbs O from the air and reddens. Hesperidin, C,.H,,0,, (?).—Odorless, tasteless cryst. powder, s. 5000 pt. =. aq.; 1. eth.; d.s. ale.; s. NaOH but reppt’d by CO,.—The sol in NaOH on evaporating to dryness and treat- ing w. x’s H,SO, and warming gives red to violet color !— [A glucoside hydrolyzed by boiling w. dil. acids to glucose and hesperitin (latter melts at 224°-6°, and is s. in alkalies and cclored brown-red by FeCl,).] { Phenolphthalein, C,,H,,0,.— When amorphous e. s. eth.; when cryst. d. s. eth.; s. alc.; i. aq.—S. in NaOH or Na,CO, w. intense red color, approximately RV, but much purer than color of the standard. The color is discharged by large x’s of NaOH or by warming w. Zn dust. Tetraoxydinaphthylmethane, CH,.[C,,H;.(OH),],.—E. s. ale. or eth.—S. in conc. H,SO, w. yellow color, changing to deep red. Thymolphthalein, C,,.H,,O,.—_Ndl., e. s. ale.; s. eth.; alm. i. aq. NaOH gives intense blue sol. (purple by transmitted light), a a ae Melting-point Boiling-point CO.2): (C2). Se 253-5d. 253-6 a, 270d. 272 d. w. m. 275 280d. 300 310 GENUS IV, DIV. A. 103 (ORDER 1, SUBORDER I.) PHENOLIC COMPOUNDS.—Colorless and Solid. Phloretin, C,,H,,0,.—Lft. v.d.s. h. aq. or eth.; v.s.alce.—Sol. in alkalies absorbs O fr. air.—Boiled w. KOH gives phloretic ac. and phloroglucin.—Heated w. aniline at 170° gives scarlet sol.—Anilide, alm. i. aq. or eth., but s. in alc. w. deep-orange color. + Daphnetin, C,H,0,.(OH),.—Yellowish ndl. w. coumarin-like odor when warmed!—Sbl.—S8. h. aq.; v. d. s. eth.; s. Na,CO, w. orange color.—Aq. sol. gives green color w. FeCl;, becoming red w. Na,CO;.—Gives yellow ppt. w. PbAc,.—Diacetyl deriv., m. p. 129°-30°. | Zisculetin, C,H,O,.(OH),+H,0.—(After loss of cryst. aq. be- comes yellow.)—Lustrous ndl. v. d. s. c. aq.; s. h. aq.; alm. i. eth.; s. in NaOH w. yellow color.—FeCl, gives intense green color w. aq. sol. !—PbAc, gives yellow ppt. fr. sol.! r-(p)-Biphenol, [C,H,.OH],.—Sbl. in scales.—D. s. aq.; e. s. ale. or eth.—Aq. sol. gives no color w. FeCl, and very transient violet w. Ca(OCl),.—Sol. in H,SO, and trace of HNO, be- comes blue.—Ignition w. Zn dust gives biphenyl.—Diacetate, m. p. 159°-160°. Arabinose-resorcin, C,,H,,0,.—Amorph. powder, v. s. aq.; Vv. d. s. alc. or eth.—Aq. sol. blue-violet w. FeCl,; intense red- violet w. Fehling’s sol. p-Dioxystilbene, (HO.C,H,.CH:),.—E. s. eth.—Diacetate, d. s. h. ale.; m. p. 213°. a-Binaphthol, [C,,H,.OH],.—Sbl.—I. aq.; s. ale.; more s. eth._— Alec. sol. gives violet-red color w. FeCl, and ppt. of same color. Biresorcin, C,,H, 0,-+2H,0.—Cryst. s. h. aq.—FeCl, gives pale- blue color.—Heated at 100° for 10 min. w. 1 cc. H,SO,+1 ce. acetic anhyd. gives blue-violet sol.—M. p. of tetraacetate 158°. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER J] GENUS IV, PHENOLIC COMPOUNDS. DIVISION B,—LIQUID PHENOLIC COMPOUNDS. Boiling-point (Ce). 139-6 158 167-70 169 169-70c. 174-5 180-5 183 186-8 189-7c. 191 196 198e. 201 201-8 202-8 Specific Gravity. 0-987 (15°) 0-954 (15°) 0-994 (4°) 1-037 (9°) 0-941 (15°) 1-046°/, 1-009 (6°) 0-995 (14°) 0-998 (12°) 0-981 (0°) 1-050 (0°) PHENOLIC COMPOUNDS.—Colorless and Liquid. + Acetylacetone, Me.CO.CH,.CO.Me.—Odor like acetone and acetic acid.—S. in 8 pt. aq.—The color of aq. sol. (1:100) w. FeCl, (Test 401) is a very permanent OR-RO.—Dis- tinctly acid!—The aq. sol. gives heavy light-blue ppt. w. sol. of CuAc,.—Saponification by Test V gives acetone and acetic ac. (Tests 711 and 311). Hexanedione(2, 4), Me.CO.CH,.CO.Et.—Has acid properties.— Cu salt obtained by ppt’n of sol. in dil. ale. w. CuAc, sol., blue ndl. fr. alc., m. p. 197°-8°. . 3-Methylhexanedione(2, 4), Me.CO.CHMe.CO.Et.—Blue ppt. w. ammon. CuCl sol., m. p. 192° 3-Methylpentanedione(2, 4), Me.CO.CHMe.CO.Me. Methyl Acetoacetate, Me.CO.CH,.CO,Me.—E. s. aq!—Sol. dark cherry-red w. FeCl,!—Saponification by Test V-2 gives acetone and CH,OH. 2, 4-Heptanedione, Me.CO.CH,.CO.Pr.—Gives a Cu salt, m. p. 160°-1°. + Ethyl Acetoacetate, Me.CO.CH,.CO,Et.—An aq. sol. (1:100) gives a clear and very permanent RT1 color w. FeCl, (Test 401).—Saponification by Test V—2 gives acetone, C,H,OH and CO, (cf. Tests 711 and 814). + Phenol (cf. IV, A, m. p. 42-5°). Ethyl Methylacetoacetate, Me.CO.CHMe.CO,Et.—Sol. colored blue by FeCl,.—Saponification by Test V gives methyl ethyl ketone, C,H,OH and CQ,. Methyl Ethylacetoacetate, Me.CO.CHEt.CO,Me. — Violet-red color w. FeCl,.—Saponification by Test V gives methyl propyl ketone and CQ). o-Cresol (cf. Genus IV, A, m. p. 30°). Caffeol, HO.C,H,.CH,.0.Me.—Odor like coffee-—D. s. h. aq.; e s. alc. or eth.—Aq. sol. colored red by FeCl,.—Fusion w. KOH gives salicylic ac. (Test 319). Ethyl Ethylacetoacetate, Me.CO.CHEt.CO,Et.—Sol. colored blue by FeCl,—Saponification by Test V gives methyl propyl ketone, C,H,OH, and CO,. Ethyl Isopropylacetoacetate, Me.CO.CHPr.CO,Et.—Sol. colored pale red-violet by FeCl;.—Saponification by Test V gives methyl isobutyl ketone, C,H,OH, and CO,. + p-Cresol (cf. IV, A, m. p. 36°). + m-Cresol, Me.C,H,.OH.—Does not solidify at 0°.—The color w. a 1% aq. sol. and FeCl, (cf: Test 401) is BV-BVT1 (on mixing).—Odor like phenol.—Not sol. in 5 pt. conc. ammo- nia.—f{ Nitrate and purify the product, 2, 4, 6-trinitrocresol, by the procedure given in Test 414-2 for phenol. This tri- nitrocresol is a cryst. compound resembling picric acid in most of its properties, but melting at 106-5° (uncor.). 104 GENUS IV, DIV. B. 105 (ORDER I, SUBORDER I.) ES Boiling-point (CORSE 204-6 205 205-6 206 207c. 208:°5 211-5 213c. 214 217°5 221-2 224c. 225c. 227-5 231c. 231 231-5 236- 5-7 238-40d. 238—40 240—-41c. 242 243 Specific Gravity. 1-086 (15°) 0 5 9327°) 1-037 (0°) 0-9819/, 1-012°/, 1-025 (0°) 0-951 (17-5°) 1-111 (0°) 1-197 (0°) 1-015 (0°) 1-009 (0°) 0-986 (15°) 1-098 (15°) 1-098 (15°) 1-056 (15°) 1-144 (23°) 1-140 (23°) PHENOLIC COMPOUNDS.—Colorless and Liquid. Acetylmesityloxide, Me.CO.CH,.CO.C,H,.—S. in alkalies—Alc, sol. is colored intensely red by FeCl;.—Olive-green Cu salt, m. p. 123°. 1 Guiacol (cf. IV, A, m. p. 31°-2°). Veratrol, o-C,H,(OMe),.—Solid at +15°. Ethyl Allylacetoacetate, Me.CO.CHC,H,.CO,Et.—Sol. colored carmine-red by FeCl;.—Saponification by Test V gives allyl- acetone, C,H,OH, and COQO,. Phlorol, o-Et.C,H,.OH.—Not solid at —18°.—Violet color w. little FeCl;.—Fusion w. KOH gives salicylic ac. (Test 319). Ethyl Propylacetoacetate, Me.CO.CHPr.CO,Et.—Saponification by Test V gives methyl butyl ketone, C,H,OH, and CO,. 1, 3-Xylenol(1) (cf. IV, A, m. p. 26°). o-Isopropylphenol, Me,.CH.C,H,OH.—M. p. 15°.—Aq. sol. violet and then green w. FeCl. m-Ethylphenol, Et.C,H,OH.—M. p. abt. —4°.—Violet w. FeCl. Ethyl Isobutylacetoacetate, Me.CO.CH(C,H,).CO,Et.—Saponifi- cation by Test V gives isobutylacetone, C,H,OH, and €Q,. Homopyrocatechinmethylether, Kreosol, C;H;.(Me)(MeO)(OH)(1, 3, 4).—Mliscible w. alc. or eth.— Alc. sol. emerald-green w. FeCl;.—M. p. of picrate 96°. t+ Methyl Salicylate, o-HO.C,H,.CO,.Me.—Odor of oil of winter- green.—The color of the cold saturated aq. sol. w. FeCl, (Test 401) is RV, permanent for more than 15 minutes.— Saponification by Test V gives salicylic ac. and CH,OH (Tests 319 and 819). o-Propylphenol, HO.C,H,.Pr. Ethyl Isoamylacetoacetate, Me.CO.CH(C,H,,).CO,Et.—Saponi- fication by Test V—2 gives isoamylacetone, C,H ,OH, and CO). p-Propylphenol, HO.C,H,.Pr. Isocymophenol, C,H,.(Me)(Pr)(OH)(1, 3, 6).—Not solid at —25°. —S. aq.—Aq. sol. pale-violet w. FeCl,—Vapor induces coughing. + Ethyl Salicylate, o-HO.C,H,.CO,Et.—Odor of oil of wintergreen. —The color of the cold saturated aq. sol. w. FeCl, (Test 401) is RV (on mixing); VRT2-RVT1 after 15 minutes.—Saponi- fication by Test V—2 gives salicylic ac. and C,H,OH (Tests 319 and 814). { Carvacrol, Me.C,H;.(Pr)(OH)(1, 4,2).— Viscous oil which solidifies at —20°.—FeCl, gives a coloration, but only in very conc. alc. sol.; the color is then an impure green, which changes and fades rapidly.—M. p. of the phenylcarbamate 140°.—(Cf. Ber. 26, 2086.) Diethyl Acetylmalonate, C,H,0.CH.(CO,Et),.—Has a strong ae. reaction! Alc. sol. dark red w. FeCl,;—Phenylhydrazine derivative melts at 120°.—Saponification by Test V-2 gives acetone, acetic ac., and C,H,OH (Tests 711, 311). Propyl Salicylate, PrCO,.C,H,.OH.—Saponification by Test V—2 gives salicylic ac. and C,H,OH (Tests 319 and 820). Cerulignol, HO.C,H, ,.OMe.—Odor like creosote.—V. d.s. ¢. ad. : miscible w. alc. or eth.—Aq. sol. gives carmine ppt. w. FeCl . —aAle. sol. green w. FeCl, and blue w. Ba(QH)),. Methyl 4-Oxy-m-toluate, HO.C,H,(Me).CO,Me.—Oil of winter- green odor.—Saponification by Test V gives 4-oxy-m-toluic ac. and CH,OH (Test 819-1). Methyl 3-Oxy-p-toluate, HO.C,H,Me.CO,Me.—Saponification by Test V—2 gives 3-oxy-p-toluic ac. and CH,OH (Test 819-1). 106 GENUS IV, DIV. B. (ORDER I, SUBORDER I.) Boiling-point COE 243-4 247-5sl. d. 248 254 254-5 254-6 258-62 265-70d. 266-9 270 273 283-4 Specific Gravity. 1-063 (18-5°) 1-102 (23°) 1-097 (23°) 1-067 (15°) 1-088 (15°) 1-080 (16°) 1-122 (15°) 1-03615/,, PHENOLIC COMPOUNDS.—Colorless and Liquid. Methylresorcin Ether, m-HO.C,H,.OMe.—S. c. aq.; miscible w. alc. or eth.—Aq. sol. pale violet w. FeCl,. + Eugenol, C,H;.(CH,.CH: CH,)(OH),(1, 3, 4).—Odor of cloves. —V.d.s.aq.; e.s. alc., eth., or Ac.—Cold saturated ag. sol. gives a turbid YGT2 color in Test 401, w. FeCl,; the alc. sol. (1:50) gives a B color fading in 15 min. to GYT2. Ethyl 1-Methyl-2-oxybenzoate(3), Me.C,H,(OH).CO,Et.—Sapon equiv. 178.—The corresponding ac. gives violet color w. FeCl;.—Saponification by Test V—2 gives 1-methyl-2-oxy- benzoic ac. and C,H,OH (Test 814). Ethyl 3-Oxy-p-toluate, HO.C,H,(Me).CO,Et.—Saponification by Test V—2 gives 3-oxy-p-toluic ac. and C,H,OH (Test 814). Betelphenol, (CH,.CH: CH,).C,H,.(OH),(OMe)(1, 3, 4).—Ale. sol. iat blue-green w. alc. FeCl,. (In ethereal oil from Piper etle.) Diethyl Acetylsuccinate, C,,H,,0,.—Red-violet color w. FeCl,.— Saponification by Test V—2 gives acetic and succinic acids and C,H;OH (Tests 311, 320, and 814). Isoeugenol, (CH:CH.Me).C,H;.(OH).(1, 3, 4). — Solidifies in freezing mixture.—Alc. sol. green w. FeCl. { Ethyl Benzoylacetate, C,H,.CO.CH,.CO,Et.—S. without de- composition in c. dil. NaOH.—Ale. sol. gives red-violet color w. FeCl,.—Saponification by Test V—2 gives acetophenone, C,H,OH and CO, (Tests 712 and 814). Phenylacetylacetone, Ph.CH,.CO.CH,.CO.Me.—D. s. c. aq.; e. 8. dil. alkalies—AgC,,H,,O,, flocculent ppt. Isoamyl Salicylate, o-HO.C,H,.CO,C,H,,.—Saponification by Test V gives salicylic ac. and C;H,,OH (Test 319). Methyl Orcinyl Ether, MeO.C,H,.OH. — D. s. aq.; e. s. alc. or eth.—Browns on exposure to air. Ethyl Benzylacetoacetate, C,H,O0.CH(C,H,).CO,Et.—Saponifica- tion by Test V—2 gives Me.CO.(CH,),.Ph, C,H,OH, and CO,. NUMBERED SPECIFIC AND SEMI-SPECIFIC TESTS FOR PHENOLIC COMPOUNDS. [TESTS 401-500.] 401. Ferric-chloride Colorations. The test with ferric chloride, forming the first part of Generic Test IV, is designed rather to favor the development of a maximum color effect in the largest possible number of cases than to secure the most characteristic results for individual species. To obtain the ferric-chloride coloration attributed to any phenol in the description given in the tables, it is necessary to pay attention both to certain principles that will be now stated, and to the special supplementary directions concerning dilution, etc., that form part of many of the individual specific descriptions. The most desirable concentration for the phenol solution is one that will give a color of such quality and intensity that, when viewed horizontally in a six-inch test-tube, it will nearly match a spectrum color or ‘‘tint’’, rather than a “shade” or a “broken color” of the color standard. ‘This concentration varies greatly with the phenol, but in aqueous solu- tions is often met in a 1 per cent solution. Atcohol is usually a much less satisfactory solvent in these tests than water, but is sometimes to be preferred. The same phenol often gives different colorations in the two solvents. Hot solutions must never be used with either solvent. The colors from some phenols are permanent for hours; but more often are very transitory, the first coloration sometimes undergoing a complete change in hue, or entirely fading away within a few seconds or minutes. The coloration is occasionally accompanied by a precipitate. The appearance of a color is prevented by the presence of either free acid or alkali, or else its character is essentially modified (cf. pyrocatechin),. An excess of ferric chloride may destroy the coloring matter that is first formed, or obscure the proper coloration by blending it with yellow. The usual procedure in the specific test with ferric chloride is as follows: Place 5 cc. of the clear, cold solution of the phenol, which has the concentration speci- fied in the tables, in a six-inch test-tube. Add one or more drops of a ferric-chloride solu- tion (1 : 40) prepared by diluting one volume of the 10 per cent stock solution of the salt with three volumes of water. Use no more of the reagent than is required to produce a color suitable for comparison. Shake; and then, without delay, make a careful com- parison of the color produced with the color standard. Repeat the comparison after the - mixture has stood for five and for fifteen minutes. Comparisons should be made in clear diffused daylight, looking horizontally through the tube towards a white wall or card imme- diately behind it (cf. p. 232). 402. The Phthalein Fusion. Mix about 0.05 grm. of the phenol with an equal bulk of powdered phthalic anhydride in a dry test-tube. Moisten with one drop of concentrated sulphuric acid. Stand the tube in a small beaker containing an inch or two of sulphuric acid, oil, or molten paraffin, which has been heated up to a nearly constant temperature of 160°. Heat for three minutes. Cool. Add 2 cc. of cold water, and 1-2 cc. of sodium-hydroxide solution (1 : 10); i.e. 107 108 SPECIFIC TESTS FOR PHENOLIC COMPOUNDS. enough to give the solution quite a strong permanent alkaline reaction. Stir the fused mass at the bottom of the tube until most of it has dissolved. Dilute with an equal vol- ume of water and filter. Compare the color of the filtrate with the color standard (ef. p. 232), using such a dilution that the comparison can be conveniently made in a six-inch test-tube held before a white background. If the solution shows a fluorescence, examine its color with a black background. The colors observed in this test are frequently intense and characteristic. When the coloration given by a phenol has been compared with the color standard, it will usually be found mentioned among the tabulated properties and reactions of the species. 411. Hydroquinone. (Properties tabulated on p. 99.) 1. Dissolve 0.1 grm. of the substance in 3 cc. of warm water. Cool, and slowly add 2-3 cc. of a 10 per cent ferric-chloride solution. Shake. Filter off the precipitate of green-black glistening quinhydrone. Collect the filtrate in a small graduate and wash with cold water until the total filtrate measures 10 cc. Rinse the precipitate into a test-tube, using 6 cc. of water. Warm to just 40°, so as to partly dissolve the crystals. (Boiling would decom- pose the quinhydrone to quinone.) Cool to below 20°. Filter into a small graduate, and wash with cold water until the filtrate measures 10 cc. Dry the precipitate on a piece of porous tile supported over a drying-oven where the temperature will be 35° to 40° for twenty minutes, and determine its melting-point. Quinhydrone is obtained in this test in slender needles of a peculiar greenish-black color and beautiful metallic luster. Rapidly heated it begins to sublime at 145°-50°; gradually softens; and, finally, not far from 170° (uncor.) melts completely to a dark orange-red liquid. Even when cold it emits a faint pungent odor of quinone. 412. a-Naphthol. (Properties tabulated on p. 94.) 1. Dissolve 0.05 grm. of the naphthol in 10 ce. of a 1 per cent caustic-soda solution. Add five drops of chloroform, and boil 20 seconds. Compare the color immediately with the standard (cf. p. 232). a-Naphthol gives at first a clear blue (B). In 15 minutes the color changes to a bluish- green (GB-BG); in 4} hours to yellow-green (YG). 2. Dissolve 0.10 grm. of the substance, and 0.15 grm. of picric acid, in 10 cc. of boiling dilute alcohol (1:1). Allow to cool slowly. Filter off the orange (O) needles of picrate, which separate after short standing and shaking, and wash with 2 cc. of dilute alcohol (1:1). Dry in a warm place on a bit of porous tile. Determine the melting-point in a bath whose temperature is rising somewhat rapidly. The picrate, (C,,H,O.C,H,(NO,),0), melts at 188.5°-189.5° (uncor.). 413. @-Naphthol. (Properties tabulated on p. 96.) 1. Apply Test 412, 1.—The first coloration is blue (B); but unlike that from a-naphthol it fades rapidly, passing through GB and YT, of the color standard to colorlessness in 10 minutes. j 2. Dissolve 0.10 grm. of the substance, and 0.15 grm. of picric acid, in 6 ce. of boiling dilute alcohol (1:1). Then proceed as in Test 412, 2. The picrate, (C,,H,O.C,H,(NO,),0), crystallizes in long thin needles of an orange- yellow color (YO) which melt, when somewhat rapidly heated, at 155.5°-156.8° (uncor.). 414. Phenol. (Properties tabulated on p. 91.) 1. The ‘‘phthalein fusion” (Test 402) gives a bright violet-red (VR) solution after adding alkali due to formation of phenolphthalein. 2. Dissolve 0.05 grm. of the substance in 1 cc. of concentrated sulphuric acid. Pour with stirring into a mixture of 1 cc. of concentrated sulphuric acid and 1 ce. of concen-— trated nitric acid. Heat on a water-bath for 5 to 10 minutes. Pour slowly into 10 ce. SPECIFIC TESTS FOR PHENOLIC COMPOUNDS. 109 of cold water. Cool thoroughly. Filter. Wash the precipitate with a cold mixture of 2 cc. of water and 0.5 cc. concentrated hydrochloric acid. Recrystallize from a boiling mixture of 4 cc. of water and 1 cc. of concentrated hydrochloric acid. Cool well and filter. Wash as before with a cold mixture of 2 cc. of water and 0.5 ec. concentrated hydrochloric acid. Dry at 100°, and determine the melting-point. The product in this test is picric acid (trinitrophenol) melting at 122.5° (cor.). Picric acid crystallizes from the dilute hydrochloric acid in plates, that are at first nearly color- less, but which gradually become yellow on exposure to the air. It deflagrates when heated on platinum foil. A dilute aqueous solution of the compound stains the skin and dyes wool an intense yellow; and its taste is very bitter. The test is simple, and very satis- factory when the result is corroborated by other evidence; but it should be remembered that picric acid is also formed, though usually not with the same ease, by the nitration of some other compounds. Since picric acid can be dried at 100°, this test may be com- pleted more quickly than Test 3. It is, nevertheless, at least equally reliable. 3. Dissolve 0.05 grm. of the substance in 2 ce. of water, and add a saturated aqueous solution of bromine until the reagent is present in excess, the color of the liquid then re- maining permanently yellow. Filter off the bulky, curdy yellowish-white precipitate. Transfer to a small beaker. Cover the precipitate with water, and add acid sodium-sul- phite solution gradually until a strong odor of sulphur dioxide remains after stirring and warming to 40°. Filter. Wash well with cold water. Dissolve in 15 cc. of boiling 40 per cent alcohol. Filter off the precipitate which separates on cooling. Transfer to a piece of porous tile; allow to become thoroughly air dry, and determine the melting-point. The white, crystalline 2, 4, 6-tribromphenol obtained as the final product by this pro- cedure is very insoluble in cold water and melts at 92.5°-93.5° (uncor.). The precipitate with bromine water contains at first an excess of bromine, and consists of the compound C,H,Br,O, which loses one atom of bromine and is converted into the tribrom-derivative during the treatment with the sulphite solution. Salicylic acid also gives tribromphenol when treated with bromine water. The bromine-water test is most useful when phenol is present in small quantity in a dilute aqueous solution. 415. Phloroglucin. (Properties tabulated on p. 101.) Dissolve 0.1 grm in. 1 cc. of concentrated sulphuric acid by stirring. Pour the clear solution into a mixture of 1 cc. of concentrated sulphuric, and 1 cc. of concentrated nitric acids, cooling with cold water, and stirring until a precipitate appears. Allow to stand for five or six minutes; then pour into 10 cc. of cold water. Cool well and filter. Wash the precipitate with 2 cc. of water containing 0.5 cc. of concentrated hydrochloric acid. Recrystallize from a boiling mixture of 3 cc. of water and 1 cc. of concentrated hydrochloric acid. Cool and filter. Wash with 2 cc. of water containing 0.5 cc. of con- centrated hydrochloric acid. Dry at 100°-105°. The product, trinitrophloroglucin, crystallizes easily in pale-yellow needles melting at 165°-166° (uncor.). It stains the skin yellow, and deflagrates when heated on platinum foil like picric acid. 416. Pyrocatechin. (Properties tabulated on p. 94.) 1. Always apply the ferric-chloride color reaction as directed in the tables, adding 1 cc. of the ordinary laboratory sodium-carbonate solution in the latter part of the test. This test requires very little substance, and is one of the most satisfactory of its class. 2. Dissolve 0.05 grm. of the substance in 2.5 cc. of warm chloroform. Add 0.4 ce. of bromine. Evaporate to dryness on a water-bath. Dissolve the residue in 5 ce. of cold alcohol. Add 20 cc. of cold water. Shake, and then filter. Wash the precipitate with a little cold water. Redissolve in 5 ce. of alcohol, and reprecipitate with 20 cc. of cold water. Allow the precipitate to become air dry on a piece of porous tile, and determine its melting- point. 110 SPECIFIC TESTS FOR PHENOLIC COMPOUNDS. The product, tetrabrompyrocatechin, crystallizes in white needles. As obtained in this test, the crystals are often tinged with violet, and melt (not very sharply) at about 192°-3° (uncor.) after beginning to shrink and soften at 185°-187°, 417. Pyrogallol. (Properties tabulated on p. 96.) 1. To 2 ec. of water in a 6-inch test-tube add 1 drop of glycerine and 5 drops of a solution of 0.01 grm. of the substance in 1 cc. of water. Next add 2 cc. of concentrated sulphuric acid and boil for 20-25 seconds. Then, without delay, compare the color of the hot solution with the color standard (cf. p. 232). Use a white background behind the tube. The color given by pyrogallol in this test is a clear tint of violet-red (VRT 1-2). On continued boiling or standing, the color intensifies rapidly, but soon becomes impure and unsuited for purposes of comparison. 2. In a dry test-tube place 0.1 grm. of pyrogallol, 0.5 grm. of powdered anhydrous sodium acetate, and 1.0 cc. of acetic anhydride. Boil for one and one-half to two minutes, Add 10 cc. of water, and boil for fifteen or twenty seconds till the oily liquid solidifies, Cool. Filter, and wash with 10 cc. of cold water. Dry at 100°-105°. The product obtained in this test, pyrogallol triacetate, is in the form of white crys- tals which soften at about 155° and melt at 160.5°-161.5° (uncor.) when heated rather rapidly. Recrystallization from 4 cc. of strong alcohol raises the melting-point about 0.5? 418. Resorcin. (Properties tabulated on p. 95.) 1. One of the simplest, most delicate, and rapid of the tests for resorcin is the fluoresceis fusion, which is fully described under Test 318-1. If more convenient, substitute phthalir anhydride for the phthalic acid. Color reaction 114 with formic aldehyde furnishes another simple resorcin test. 2. Dissolve 0.1 grm. in 1 cc. concentrated sulphuric acid. Pour slowly with constant stirring into a cold mixture of 1 cc. concentrated nitric acid and 1 cc. concentrated sul- phuric acid. (It is well to place the mixed acids in a small round-bottomed dish resting on the top of a small beaker filled to the brim with very cold tap water.) Do not run in the resorcin solution fast enough to cause a permanent brown coloration in the acid. When all has been added, remove the dish from the cold water and allow to stand on the table for two or three minutes. Then pour the mixture of liquid and yellow crystals that have sepa- rated slowly into 10 cc. of cold water, keeping well cooled with running water. Filter. Wash with 5 cc. of cold water. Recrystallize from a boiling mixture of 10 cc. of cold water, 4 cc. strong alcohol, and 0.4 cc. concentrated hydrochloric acid. Cool well and shake. Filter. Wash with 5 cc. of cold water and dry at 100°. The product in this test, trinitroresorcin, consists of slightly yellowish crystals of melting-point 175° (uncor.). It stains the skin yellow like picric acid. The yield is good. 419. Thymol. (Properties tabulated on p. 92.) 1. The colors obtained in the phthalein fusion (Test 402), and described in the tables, are quite characteristic. This test should always be applied. 2. Dissolve 0.1 grm. of the powdered substance in 1 cc. of concentrated sulphuric acid. Add with stirring to a mixture of 1 cc. of concentrated nitric, and 1 cc. of concen- trated sulphuric acids contained in a very small dish. Allow to stand on the cover of a boil- ing water-bath for three or four minutes. Pour into 20 ce. of cold water. Cool well and shake vigorously. Filter. Wash the precipitate with 10 cc. of cold water. Crystallize from a boiling mixture of 10 cc. water, 4 cc. alcohol, and 0.4-0.6 cc. concentrated hydro- chloric acid. Filter. Wash with 5 ce. of cold water. Dry ona piece of porous tile in the air, or in a drying-oven below 50°. The product in this test is trinitrothymol, melting at 109°-110° (uncor.). The ecrys- tals, which are at first nearly colorless, like those of many other nitrophenols, turn lemon- yellow after a few hours’ exposure to the air. CHAPTER VI. GENUS Veo nies OF SUBORDER I, ORDER I. (Colorless Compounds of Carbon, Hydrogen, anid Gayyen.} The tables of this genus contain only the most important esters derived from the well- known volatile alcoholic compounds enumerated in the table on p. 116. Other esters are to be identified through their alcoholic and acidic saponification products by a method which will be given in connection with ‘‘ Procedure 2”’ of the generic test. Esters that are rapidly saponified by cold alkali, the ester-acids, ester-phenols, and the enolic esters, show a behavior with reagents which places them in Genus III or IV with the acids or phenols. Finally, a few esters like those of the aromatic diortho-substituted carbonic acids, which offer extraordinary resistance to the action of hot alkali, fall in later genera. GENERIC TEST V. APPLY PROCEDURE 1.—IF THE RESULT IS NEGATIVE, THE COMPOUND DOES NOT BELONG TO EITHER GENUS V OR VI. IF IT SHOWS THAT THE COMPOUND MAY BE AN ESTER OR ACID ANHYDRIDE, BUT FAILS TO POSITIVELY IDEN- TIFY IT WITH ANY SPECIES DESCRIBED IN GENUS V OR VI, PROCEDURE 2 SHOULD, IF POSSIBLE, THEN BE APPLIED._[PROCEDURE 2 MAY LEAD TO THE IDENTIFICATION OF ANY ESTER THAT SAPONIFIES TO AN ALCOHOL AND ACID DESCRIBED IN THESE TABLES, WHETHER THE ESTER IS ITSELF MEN- TIONED OR NOT, BUT IS LONGER THAN PROCEDURE 1.] PROCEDURE 1. Weigh out very carefully in a 3-inch lipped weighing tube about 0.1 grm. of the substance. Add 2 cc. of a nearly colorless and approximately normal solution of sodium or potassium hydroxide in pure strong alcohol from a thin-stemmed pipette. The pipette need not be accurately calibrated, but must be used with such precautions to ensure uniformity in delivery that the volume of liquid dis- charged by it in two successive experiments shall not differ by more than about 0.005 cc. Stopper the weighing tube tightly with a sound soft cork, which must be wired down with a thin copper wire in the manner shown in Figure 3. [The wire, after being first doubled, is twisted so as to form a small eye at A. It is then drawn tightly around the tube by twisting with pliers at B, and the free ends passed over the cork and through the eye. The ends are then seized with the pliers and drawn back with sufficient force to slightly imbed the wire at the edges of the cork. If the wire is now bent sharply back upon itself, as is shown at C, the stopper will be securely held during the subsequent heating.] Place 2 ec. of the same normal alkali that was added to the substance in a second tube stoppered like the first. , act 112 ESTERS Hang the two tubes from a glass rod by their wires, side by side, in a beaker of boiling water, and heat for thirty minutes. Or, better still, thrust the tubes through perforated cork stoppers, and heat half an hour at 100° in a bath of the kind described on p. 152 and shown in Figure 4. Then wash the contents of each tube into a separate small beaker, and titrate carefully with deconormal acid and phe- nolphthalein. From the results of the titrations calculate the ‘‘saponification equivalent” * of the compound by use of the following formula, in which the ge, By number of cubic centimeters of standard acid consumed in neutralizing the alkali used for the blank experiment is represented by a; and the quantity consumed by the alkali after being heated with the substance, by 6. Then— 1000 X grm. of ester taken Sap. Ed.= (py Xnormal strength of the standard acid If this equivalent is found to have a value greater than 500, pass on to Genus VII; for in this case the compound can not be a species described in either Genus V or VI. If, on the contrary, the equivalent has a value less than 500, a search must be made through the proper divisions of the tables of Genera V and VI for a species whose physical constants and saponification equivalent correspond to those found for the substance. If this search leads to the discovery of an apparently corre- sponding species, the identification may sometimes be satisfactorily completed by the application of special tests suggested in the text. In all other cases, provided the supply of substance remaining permits, it is best to saponify a larger quantity, * By “saponification equivalent ” is here meant the number expressing how many grams of a compound would be required to just neutralize 1000 cc. of normal sodium hydroxide solution in a saponification experiment. ESTERS 113 and isolate and identify its acid,* or alcohol, or both, by the methods given under Procedure 2. PROCEDURE 2. Saponify with aqueous alkali as directed below under A. Identify any neutral saponification products (alcohols, phenols, or ketones) as directed under B, below, and any acid saponification products according to C, p. 116. A (Saponification). Fit a 250-cc. round-bottomed flask with a clean, sound cork stopper perforated to receive the lower end of a return-flow condenser that has been mounted verti- cally on a heavy iron stand. Introduce about 2 grm. of the substance, accurately weighed, into the flask; and then, from a pipette, exactly 50 cc. of an aqueous normal solution of pure sodium hydroxide. Next drop in an ebullator-tube to prevent bumping (cf. p. 223) and boil briskly for about two hours, or even longer if the odor or appearance of the mixture gives indication that, while the substance has been attacked by the treatment, a portion of it remains unchanged. The flask should rest lightly on a square of iron gauze during the boiling, and the burner flame should be shielded from drafts of air; for any pause in the boiling that is more than momentary will cause the ebullator capillary to fill, after which such violent bumping may occur as to shatter the flask. The saponification completed, cool; add two drops of phenolphthalein solution, and titrate with normal sulphuric acid without removing from the flask. The saponification equivalent may now be calculated from the experimental data by substituting in the equation— 1000 no. grm. ester saponified eterno oc. alkali neutralized in saponifio. . — (III, A, 2), m.p. 57: 5°, 94.2 | 284 Ethyl Palmitate, C, H,,0,. — ¥e 62-6°¢ 27-8 176°d.(13mm.)| ‘‘ Bempoyiicere cere) CrHOn 28 270 Methyl Palmitate, C,,H,,0,.— (III, A,2), ‘* 62-6°c. 29 253° Triethyl pte I UTS C,,H,,O..— Cf. Genus III, A, 2, m. p. 29°. 29-30 | 366 | a. 360 Ethyl Brassidate, C,,H,,0,.— Ty ye 2) i, Dae ou 30 ‘« Tetrinate, C,H,,0,.— 139°; 32 Diethyl Benzalmalonate, C,,H,.0,.— ‘* 195°; also cine namic and malonic acids. O07 | 319 224d. Ethyl Stearate, C,,H,,0,.— a ‘f 69°53" c, 34 180 254 ‘* ~Mandelate, C,,H,.0,.— (IIL, A, 1)" ee 34 194 273 ‘* o-Hydrocoumarate, C,,H,,0;.—(III, A, 1), m. p. 82°-3°, 34 256 ‘* Benzilate, C,,H,,O,— (III, A, 2), a B. 150°. 34 140 197¢. ‘* Pyromucate, C,H,O,.— (III, A, 1), 132°—4°, 36 162 260c. Methyl Cinna-nate, C,,H,,0,.— (III, A,2), ‘‘ 133°; Test 313. 3g | 115 288d Dimethyl Sebacate, C,,H,.0,— (III, A, 1), ‘* 133°. 38 Methyl Stearate, C,,H;,0,— (III, A,2), ‘‘ 69-3° ce. 42 149 Diethyl Diphenate, C,.H,,0,.— a ae BOOP: 43-4 |} 210 295° Ethyl Veratrate, C,,H,,0,.— S ILS tea 44 196 292 ‘¢ Vanillate, C, ,H,.0,.— Ay oT See 44 111 Diethyl Terephthalate,C,,H,,0,— ‘‘ sbl. a. 300°; Test 318. 45-5 | 166 255° Methyl Anisate, C,H, ,0;.— fs m. p. 184-2°, 48 | 89 230 Dimethyl Tartrate, C,H,,0,— (III, A,1), ‘‘ 168°: Test 314, 51 204 290 Ethyl 6-Methylcoumarilate, C,,H,,0,.—(III, A, 2), m. p. 188°-9°. 52 166 Methyl Mandelate, C,H,,0,.— (III, A, 1), m. p. 118°. 52 119 Diethyl 4-Oxyisophthalate, C,,H,,0;.— (III, A, 2), m. p. 305° 54 59 163 -3c. } Dimethyl Oxalate, C,H.0,.— Belongs to Genus III, A, 1. 57 96 abt. 200 Diethyl Mesoxalate, C H.,0, — (TI, A, 1) moti 57 Ethyl Tikenzylatercaceges C,oH,.0;,—(III, A, 2), m. p. 89°. 56-8 325-8d. Tetraethyl Ethylenetetracarbonate C,,H,.0,.—Acid unstable. 59 228 Phenyl Methylethersalicylate, C,,H,,0,.—(III, A, 2), m. p. 98-5°, 59 196 283 Methyl Veratrate, C, ,H,,0,.— be Mi 9 bo 59-5 295-297d. | Ethyl meaner ee C,;H,,0;.— Benzoic, acetic, and acetone, 118 GENUS V, DIV, A. 119 (ORDER I, SUBORDER I.) Melt- oe Benen: Boiling-point | ESTERS.—Solid Esters whose Neutral Saponification Products Fao) Stade CORSE are Soluble in Cold Water and Readily Volatile with Steam. Generic Position and Properties of the Acidic Saponification Products, 61-5 | 127 |207 (16-5 mm.)} Dimethyl Hemipinate, C,.H,,0,.—(III, ie 2),m. p. 161°. 62-5 | 182 285-7 Methyl Vanillate, C,H, ,0,.— ae cUies 68 131 324 Diisobutyl Tartrate, CHton — (III, A,1), *‘ 168°; Test 314. 64-5 | 97 pee Teontitiniates C,H ,,0,.— (III, A, 2), m. p. a. 300°; Test 68-9 | 198 314c, Phenyl Benzoate, C,,H, ,0,.— (III, ae 2),m. p. 121°; Test 312. 70 159 Diphenyl Phthalate, C,,H,,0,.— ** 184°; Test 318-1, 72 166 282 Ethyl m-Oxybenzoate, C,H,,0,.— ‘S ez00. 72-5 | 224 Phenyl Cinnamate, C,,H,.O,.— a Semlboo Lestalos 73 480 Ethyl Melissate, C,.H,,0,.— ie sees OC)? 73 85 Hexaethyl Mellitate, C,,H.,0,..—(III, A, 1), ‘‘ 286°(clos’d tube) 74-5 | 242 Methyl Benzilate, C,,H,,0;— (III, A,1), ‘‘ 150°. 75 182 Ethyl 2, 5-Dioxybenzoate, C,H,,0,.— (III, A, 2), m. p. 199°. 73-8 | 290 Phenyl p-Phenoxybenzoate, C,,H,,0;,.—(III, A, 2),‘‘ 159-5° 76 305d. Ses ena s-Ethanetetracarbonate, C,,H,.O,.—(III, A, 1), m. p- 77 186 290 Methyl! $-Naphthoate, C,.,H,,0,. als ae 2), m. p. 184°. 77-5 | 246 Ethyl Piperate, C,,H,,0,.— he SPAM ip 78 301-2 Diphenyl Carbonate, C,,H,,0;. 79 78 285 Trimethyl Citrate, C,H,,O,.—(III, A, 1), m. p. 153°; Test 314. 79-5 Ethyl Benzosalicylate, C,,H,,0,. 85 89 282 Dimethyl Racemate, C,H,,0,.—(III, A, 1), m. p. 205°; Test 314. 85 178 Methyl m-Coumarate, C,,H,,0,.—(III, A,2), ‘* 191°. 96 95 Dimethyl 4-Oxyisophthalate, C,,H,,0;.—(III, A, 2), m. p. 305°. 102 72 192 (th. i.) ‘* Fumarate,C,H,0,— - 3 sbl. 200°. 102 105 ‘¢ 4-Oxyphthalate, C,,H,,0;,— (III, A, 1), m. p. 181°. 109 | 2909 Phenyl Phenylethersalicylate, C,,H,,O;— (III, A, 2), ‘‘ 113°. 109 | 258 { Peucedanin, C,,H,,O,.0CH,.—Tasteless, odorless, ndl. from Peucedanum officinale. ayy aq.; e.s. h. ale. or ‘eth —tT Mix a warm saturated alc. sol. w. an equal vol. conc. HCl and boil half a minute. Cool. Wash the white cryst. ppt. w.c. alc. Recryst. fr. h. ale. The product of these operations, oreoselon, melts at 173° (uncor.). iit 198 270-80d. Methyl! a-Anthracenecarbonate, C,,H,,0,.— (III, A, 2), m. p. 206°. ise, 135 330 Diphenyl Succinate, C,,H,,0,— (Ill, A, 1), m. p. 185°; Test 320. 130d. | 121 a Oxalate, C,,H,,0,.— sf poe o> > Testral 131 152 Methyl p-Oxybenzoate, C,H;0,.—(III, A, 2), m. p. 210°, 138 | 65-5 Tetramethyl s-Ethanetetracarbonate, C,,H,,0,.—(III, A, 1), m. p. 169°. 140 97 Dimethyl Terephthalate, C,,H,,0,.—(III, A, 2), sbl. a. 300°; Test 318-3. 158d. | 183 Diethyl Mucate, C,,H,.0,.— aS me pesto 146 | 164 abt. 330° ‘¢ a-Truxillate, C,,H,,0,.— = ee 4a 187 71 Hexamethyl Mellitate, C,,H,,0,..— (III, A,1), ‘‘ 286° (closed tube). 192d. | 238 Methyl Gallate+ 3H,0,C,H,,0,— (III, oe 2), ‘* 222°-40°. 260-70 Ethyl pereityicaroonet C,,H,,03.— of 95°--7°. es a COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER TJ] GENUS V, ESTERS. DIVISION B,—LIQUID ESTERS WHOSE NEUTRAL SAPONIFICATION PRODUCTS, ETHYL, PROPYL, ISOPROPYL, ALLYL, AMYL AND ISOAMYL, BUTYL AND ISOBUTYL, HEXYL, HEPTYL, OCTYL AND BENZYL ALCOHOLS, ACETONE, AND PHENOL, ARE READILY VOLATILE WITH STEAM. Boiling- point Cape 32-3 54-4 57°5 68-71 77 79-9 80-3 81 82-5 90-3 90 - 6c. 92-3 98-3 98-5 98 - 5c. 101 102 102-3 103-5 106-9 109 - 2c. 110-1 Sapon. Equiv. ! ESTERS.—Liquid Esters whose Neutral Saponification Products are Readily Volatile with Steam. Generic Position and Properties of the Acidic Saponification Products. + Methyl Formate, C,H,O,.—G. 0-998°/,.—Acid (III, B, 1), b. p. 100-8°; Test 315. (Belongs with Acids, Gen. III, B, 1.) Ethyl Formate, C,H,0,.—G. 0-938°/,.—Acid (III, B, 1), b. p. 100-8°; Test 315. t Methyl Acetate, C,H,O,.—G. 0-958°/,.— Acid (III, B, 1), b. p. 118°; Test oll; Isopropyl Formate, C,H,O,.—G. 0-883(0).—Acid (III, B, 1), b. p. 100-8°; Test 315. Ethyl Acetate, C,H,0,.—G. 0-924°/,—-Acid (III, B, 1), b. p. 118°; Test 311. Methyl Propionate, C,H,0,.—G. 0-937°/,.—Acid (III, B, 1), b. p. 140-79; Test 311. Methyl Acrylate, C,H,0,.—G. 0-973(0).—Acid (III, B, 1), b. p. 140°. Propyl Formate, C,H,O,.—G. 0-918°/,. Acid (III, B, 1), b. p. 100-8°; Test 315. Allyl Formate, C,H,O,.—G. 0-932(17-5).—Acid (III, B, 1), b. p. 100-8°; Test 315. Isopropyl Acetate, C,H,,0,.—G. 0-917(0).—Acid (III, B, 1), b. p. 118°; Test 311. Dimethyl Carbonate, C,H,0,.—G. 1-065(17).—Acid carbonic. Methyl Isobutyrate, C,H,,0,.—G. 0-912°/,—-Acid (III, B, 1), b. p. 155°; Test 311. Ethyl Propionate, C;H,,0,.—G. 0-912(0).—Acid (III, B, 1), b. p. 140-7°; Test 311. Isobutyl Formate, C;H,,0,.—G. 0-905°/,.—Acid (III, B, 1), b. p. 100-8? Test 315. Ethyl Acrylate, C,H,0,.—G. 0-939(0).—Acid (III, B, 1), b. p. 140°. Methyl Trimethylacetate, C,H,,O,.—Acid (III, A, 1), m. p. 35-5°, Propyl Acetate, C,H, ,0,.—G. 0-909°/,.—Acid (III, B, 1), b. p. 118°; Test $11. Methyl Butyrate, C;H,,0,.—G. 0-919°/,—Acid (III, B, 1), b. p. 162-5°; Test 311. Allyl Acetate, C;H,O,.—G. 0-938(0).—Acid (III, B, 1), b. p. 118°; Test 311. Butyl Formate, C,H,,0,.—G. 0-911(0).—Acid (III, B, 1), b. p. 100-8°; Test 315. Methyl Ethyl Carbonate, C,H,O,.—G. 1-002(27).—Acid carbonic. } Ethyl Isobutyrate, C,H,,0,.—G. 0-890°/,.— Acid (III, B, 1), b. p. 155°; aest 311. 120 GENUS V, DIV. B. 121 (ORDER I, SUBORDER I.) Boiling- point O),* be 116-3 116-7 115-20 118-5 (th. i.) 119 119-9 120-7 123-3 124-5 125 126 127-3 127c. 128-5 130-4 131 (th. i.) 133-5 134 (th. i.) 134-3 134-7 136 139 141-5 142 142-3 143 144-5 148 148 149-6 150 (th. i.) 150 151 151-2 (th. i.) 152 153 (th. 1.) 153-6 154-5 155 (th. i.) Sapon. Equiv. ESTERS.—Liquid Esters whose Neutral Saponification Products are Readily Volatile with Steam. Generic Position and Properties of the Acidic Saponification Products. | Isobutyl Acetate, C,H,,0,.—G. 0-892°/,.—Acid (III, B, 1), b. p. 118°; Test 311. Methyl Isovalerianate, C,H,,0,.—G. 0-901°/,.—Acid (II, B, 1), b. p. 176°. Ethyl Methacrylate, C,H,,0,.—Acid (III, B, 1), b. p. 162°. Cae cece C,H,,0,.—G. 0-875(0).—Acid (III, A, 1), m. p. Ethyl Propiolate, C,H,O,.—Acid (III, B, 1), b. p. 144°. ‘* Butyrate, C,H,,0,.—G. 0-900°/,— Acid (III, B, 1), b. p. 162-5°; Test 311. Methyl a-Crotonate, C;H,O,.—G. 0-981(4).—Acid (ITI, A, 1), m. p. 72°. } Isoamyl Formate, C,H,,0,.—G. 0-894°/,.—Acid (III, B, 1), b. p. 100-8°; Test 315. Propargyl Acetate, C,H,O,.—G. 1-005?°/,—-Acid (III, B, 1), b. p. 118°; Test 311. Butyl Acetate, C,H,,0,.—G. 0-902(0).—Acid (III, B, 1), b. p. 118°; Test 311. Diethyl Carbonate, C,H, ,0,.—G. 0-9767°/,—Acid carbonic. Methyl Valerianate, C,H,,0,.—G. 0-910(0).—Acid (III, B, 1), b. p. 186°. Methyl Methoxyacetate, C,H,O,.—G. 1-089(0).—Acid (III, B, 1), b. p. 203°. Ethyl Isoacetoacetate, C,H, 0;—CO, and acetone; Test 711. any! Formate, C,H,,0,.—G. 0-902(0).—Acid (IIJ, B, 1), b p. 100-8°; Test 315. Ethyl Methoxyacetate, C,H, 0,.—G. 1-074(0).—Acid (III, B, 1), b. p. 203°. Allyl Isobutyrate, C,H,,0,.—Acid (III, B, 1), b. p. 155°; Test 311. ziby Methylethylacetate, C,H,,0,.—G. 0-870??/,,.,—Acid (III, B, 1), Pp brie t Ethyl Isovalerianate, C;H,,0,.—G. 0-885°/,— Acid (III, B, 1), b. p. 176°. Methyl Pyruvate, C,H,O,.—G. 1-154(0).—Acid CIII, B, 1), b. p. 165°. Ethyl Isocrotonate, C,H, ,0,.—G. 0-927(19).—Acid (IIT, B, 1), b. p. 169°. {+ Isoamyl Acetate, C,H,,0,.—G. 0-884(0).—Acid (III, B, 1), b. p. 118°; Test 311. Ethyl Angelate, C;H,,0,.—G. 0-935(0).—Acid (III, A, 2), m. p. 45°. Allyl Butyrate, C;H,,0,.—Acid (III, B, 1), b. p. 162-5°; Test 311. Ethyl a-Crotonate, C,H, ,0,.—G. 0-9217°/,— Acid (III, A, 1), m. p. 72°. ‘¢ Allylacetate, C,H,,0,— Acid (III, B, 2), b. p. 188°. ‘¢ Valerianatc, C;H,,0,.—G. 0-894(0).—Acid (III, B, 1), b. p. 186°. Amy] Acetate, C;H,,0,.—G. 0-896(0) .—Acid (III, B, 1), b. p. 118°; Test 311. Methyl Ethoxyaceiate, C,H, ,0,.—G. 1-015(0).—Acid (III, B, 1), b. p. 206°. ‘¢ Caproate, C;H,,0,.—G. 0-904(0).—Acid (III, B, 2), b. p. 205-7°. Ethy] Oxyisobutyrate, C,H,,0;.—Acid (III, A, 1), m. p. 79°. aM Lakin beste C,H,,0,—G. 0-898(18).—Acid (III, B, 1), b. p. OY fara? Ethyl Diethylacetate, C,H, ,0,.—G. 0-883(0).—Acid (III, B, 1), b. p. 190°. Methyl Glycollate, C;H,0;..—G. 1- 187(0).—Acid (III, A, 1), m p. 78° Ethyl Ethoxyacetate, C,H,,0;.—G. 1-000(0).—Acid (III, B, 1), b. p. 206°. ‘¢ Methylpropylacetate, C,H,,0,.—G. 0-882(0).—Acid (III, B, 1), b. p. eke Hexyl Formate, C,H,,0,—G. 0-898(0).—Acid (II, B, 1), b. p. 100-8°: est 315. Allyl Isovalerianate, C,H. ,0,.—Acid (III, B, 1), b. p. 176°. Ethyl a-Ethoxypropionate, C,H,,0;.—G. 0-950(0).—Acid (IIT, B, 1), b. p. 195°-8°. 122 GENUS V, DIV. B. (ORDER I, SUBORDER I.) Boiling- | Sapon. ESTERS.—Liquid Esters whose Neutral Saponification Products Poe), Equiv. are Readily Volatile with Steam. Generic Position and Properties of the Acidic Saponification Products, 156c- 128 | Ethyl Tiglate, C;H,,0,.—G. 0-926(21).—Acid (III, A, 1), m. p. 64-5°. 156-9 144 | Isobutyl Butyrate, C,H,,0,.—G. 0-888°/,.—Acid (III, B, 1), b. p. 162-5°; Test 311. 158-9 Ethyl Orthocarbonate, C,H,,0,.—G. 0-925. 160c. 104 ‘¢ Glycollate, C,H,O;.—G. 1-108(0).—Acid (III, A, 1), m. p. 78° 160-2 144 | Isoamyl Propionate, C,H,,0,.—G. 0-888°/,— Acid (III, B, 1), b. p. 140-79; Test 311. 161 130 | Ethyl Isobutylacetate, C,H, ,0,.—G. 0-887(0).—Acid (III, B, 2), b. p. 207-7°. 159-62 128 ‘* Tetramethylenecarbonate, C,H,,0,.—Acid (III, B, 2), b. p. 195°. 165 146 | Methyl Oxydiethylacetate, C,;H,,0;—G. 0-990(16-5).—Acid (III, A, 1), las jena ie 165 142 | Ethyl a-Ethylcrotonate, C,H,,0,.—G. 0-920(13).—Acid (III, A, 2), m. p. 41-5°. 165 144 | Butyl Butyrate, C,H,,0,—G. 0-888(0).—Acid (III, B, 1), b. p. 162-5°; Test 311. 165 132 | Ethyl a-Oxybutyrate, C,H,,0,.—G. 1-004(0).—Acid (III, A, 1), m. p. 43°. 166-6 144 ‘« Caproate, C,H, .0,.—G. 0-889(0).—Acid (III, B, 2), b. p 205-7°. 168 - 2c. Dipropyl Carbonate, C,H,,0;.—G. 0-949(17) —Acid, carbonic. 168 - 5c. 160 | Ethyl a-Ethoxybutyrate, C,H,,0,.—G. 0-903(0). 168-8 158 | Isoamyl Isobutyrate, C,H,,0,.—G. 0-876°/,— Acid (III, B, 1), b. p. 155°; Test 311. 169-2 144 | n-Hexyl Acetate C,H, ,0,.—G. 0-890(0).—Acid (III, B, 1), b. p. 118°; Test SLL: 170: 5c. 118 | Propyl Glycollate, C;H,,0;.—G. 1-064(0).—Acid (III, A, 1), m. p. 78°. 173 144 | Methyl Oenanthylate, C,H,,0,.—G. 0-887(0) —Acid (III, B, 2), b. p. 223°. 173-7c. 132 sy Ethyl Oxalate, C,H,0,.—G. 1-156(0).—Acid (III, A, 1), m. p. 99°; Test 317. 175 160 | Ethyl Oxydiethylacetate, C,H,,0,.—G. 0-961(18-7).— Acid (III, B, 2), Draped 175 146 | Ethyl a-Oxyisovalerianate, C;H,,0,.—Acid (III, A, 1), m. p. 83°-6°. 176-7 144 | Heptyl Formate, C,H,,0,—G. 0-894(0).—Acid (III, B, 1), b. p. 100-8°; Test 315. es 158 | Ethyl Isoamylacetate, C,H,,O,.—Acid (III, B, 2), ». p. 209°. 177-5 156 | Isobutyl Angelate, C,H,,0O,.—Acid (III, A, 2), m. p. 45°. 178 80 Dimethyl Dimethylmalonate, C,H,,0,—G. 1-071(15).—Acid (III, A, 2), m, pa lB2>: 178 160 | Ethyl Acetoxyl-a-propionate, C,H,,0,.—G. 1-046(17).—Acid (III, A, 1), mM. p.106_. 178 - 4c. 130 | Ethyl $-Methoxyisocrotonate, C,;H,,0;,.—G. 1-039(15).—Acid (III, A, 2), m. p. 128-5°. 178-6 158 | + Isoamyl Butyrate, C,H,,0,.—G. 0-882°/,.—Acid (III, B, 1), b. p. 162-5°: Test 311. 179 73 | Methyl Isosuccinate, C,H,,0,—G. 1-107(15).—Acid (III, A, 1), m. p. 135° 181-5e. 66 ‘¢ Malonate, C;,H,0O,.—G. 1-160(15).—Acid (III, A, 1), m. p. 182°. 183 172 | Ethyl Dipropylacetate, C,,H,.0,.—Acid (III, B, 2), b. p. 219-5°. 184 ‘¢ Dimethylacetoacetate, C,H,,0;.—G. 0-991(16).—CO, and isopropyl acetone. : 186-1ce. 73 | + Diethyl Oxalate, C,H,,0,.—G. 1-082(18-2).—For reactions of ester cf. page 74. (Belongs in Genus III, B.) 190 Diisobutyl Carbonate, C,H, .0,.—G. 0-919(15).—Acid, carbonic. 190 146 | Ethyl a-Oxyvalerianate, C,H,,0,.— Acid (III, A, 1), m. p. 31°. GENUS JV, DIV. B. 123 (ORDER I, SUBORDER I.) POMDE: Sapon. ESTERS.—Liquid Esters whose Neutral Saponification Products tC). Equiv. are Readily Volatile with Steam. Generic Position and Properties of the Ac; ic Saponification Products. 190 158 eee Acetate, C,H, ,0,.—G. 0-874(16).—Acid (III, B, 1), b. p. 118°; Test 193 158 | Methyl Caprylate, C,H,,0,.—G. 0-894(0).—Acid (III, B, 2), b. p. 237-5°. 194 172 | f{ Isoamy]l Isovalerianate, C,,H.0,.—G. 0-87(0).—Acid (III, B, 1), b. p.176°. 195 168 | Ethyl Diallylacetate, C,,H,,0,.—Acid (III, B, 2), b. p. 227° ¢. 195-2 (th.i.)} 73 pacety! Succinate, C,H,,0,.—G. 1-126(15).—Acid (III, A, 1), m. p. 185°; est 320, 195-5 140 | Ethyl Sorbate, C,H,,0,.—Acid (III, A, 2), m. p. 134-5°. 196 (sl. d.)} 63 | Dimethyl Acetylenedicarbonate, C,H,O,.—Acid (III, A, 1), m. p. 178°-9°. 196 136 | Phenyl Acetate, C,H.O,.—G. 1-093°/,— Acid (III, B, 1), b. p. 118°; Test 311. 196 Ethyl Ethyleneacetoacetate, C,H,,0;.—G. 1-048(15).—CO, and acetopro- pyl alc. 196-5 94 | Diethyl Dimethylmalonate, C,H,,0,.—G. 1-002(15).— Acid (III, A, 1), m, p.-192-. 198 87 | Diethyl Isosuccinate, C,H,,0,.—G. 1-021(15).—Acid (III, A, 1), m. p. 135°. 198c. 80 | + ‘‘ Malonate, C,H,,0,.—G. 1-077(0).—Acid (III, A, 1), m. p. 132°. 198 158 | Octyl Formate, C,H, ,0,.—G. 0-893.—Acid (III, B, 1), b. p. 100-8°; Test 315. 199¢c. 136 | + Methyl Benzoate, C,H,O,.—G. 1-103(0).—Acid (III, A, 2), m. p. 121°; Test 312. 199 Ethyl a-Propionylpropionate, C,H,,0;—G. 0-995(0).—CO, and diethyl ketone. 200-5 (th. i.) Ethyl Methylethylacetoacetate, C,H,,0,—G. 0-947”/,;.;—CO, and sec, butyl acetone. 203-7 172 | n-Amyl Valerianate, C,,H,,.0,.—G. 0-881(0).—Acid (II, B, 1), b. p. 186°. 200-5 Diethylacetylacetone, Me.CO.C.Et,.CO.Me.—Acid (III, B, 1), b. p. 118° and diethylacetone. 204-5 170 | Isoamyl Tiglate, C,,H,,O,—Acid (III, A, 2), m. p. 64-5°. 205c. 144 | Ethyl Levulinate, C;H,,0,—G. 1-033(0).—Acid (III, B, 1), b. p. 239°. 205 (th. i.) | 72 | Dimethyl Maleate, C,H,O,—G. 1-153(14).—Acid (III, A, 1), m. p. 130°. 205-1 172 | Hexyl Butyrate, C,,H,,0,—G. 0-883(0).—Acid (III, Brel) bape lozane: Test 311. 206c. 79 | Dimethyl Mesaconate, C;H,,0,.—G. 1-136(4).—Acid (III, A, 1),m. p. 202°. 206 150 | Benzyl Acetate, C,H,,0,.—G. 1-057(16-5).—Acid (III, B, 1), b. p. 118°; Test 311. 207 94 | Diethyl Ethylmalonate, C,H,,C,.—G. 1-008"*/;;—Acid (III, A. 1), m. p. Le 5, 207°5 101 | Diethyl Methylethylmalonate, C,,H,,0,.—G. 0-994(15).—Acid (III, A, 1), evn Neyga eae 207°5 172 | Ethyl Caprylate, C,,H,,0..—G. 0-887(0).—Acid (III, B, 2), b. p. 237-5°. 207 -7c. Dibutyl Carbonate, C,H,,0,.—G. 0-941(0) .—Acid, carbonic. 208-2c. | 80 | Methyl Ethyl Succinate, C.,H,,0,—G. 1-093(0).—Acid (III, A, 1), m. p. 185°; Test 320. 208 Ethyl a-Butyrylpropionate, C,H, ,0;.—G. 0-988(0). 210 172 ‘¢” Mesitonate, C,H,,0,.—Acid (III, A, 1), m. p. 74°. 210 172 | n-Octyl Acetate, C,,H,.0,—G. 0-885(0).—Acid (III, B, 1), Datevins: Test 311. 210-5 79 | Dimethyl Citraconate, C;H,,0,—G. 1- 121(15).—Acid (III, A, 1), m. p. 80°. 211c 150 | Phenyl Propionate, C,H,,0,,—G. 1 -054(15).—Acid (III, B, 1), b. p. 140-7°; Test 311. 210-2-5 Methyl Itaconate, C,H, ,0,.—G. 1-140(14.7) .—Acid (III, B, 1), b. p. 161°. 212c. 150 | } Ethyl Benzoate, C,H, ,0,,—Acid (1H, Ap2), mp. 121°> Test 3iZ. cae es ted eli et se ENT SEE 124 Boiling- point (CEA 213-5 (th. i.) 213 213-4 213*5c. 214 214 (th. i.) 214 (th. i.) 216 216-5ce. 215-20 217-5 218 218-5c. 220 221 221 221 (th. i.) 221 221-5 220-3 222- 5c. 223 223°5 222-5 223-6 225 (th. i.) 225 225-6d. 226-5 226-8 225-30d. 227-5 (th. i.) 227-5 227 - 8c. Sapon. Equiv. 172 93 101 82 150 168 85 87 186 86 150 101 176 108 164 101 108 100 108 186 88 101 86 108 100 164 148 186 93 GENUS’ V,, DIV. B. (ORDER I, SUBORDER I.) ESTERS.—Liquid Esters whose Neutral Saponification Products are Readily Volatile with Steam. Generic Position and Properties of the Acidic Saponification Products, Methyl Pelargonate, C, .H.,,0,.—G. 0-892(0).—Acid (III, B, 2), b. p. 253°-4°, Diethyl Ethylenemalonate, C,H,,0,.—G. 1-065(15).—Acid (III, A, 1),m. p, 140°. Diethyl Isopropylmalonate, C,,H,,0,—G 0-997?°/,,.—Acid (III, A, 1), m. p. Bis Dipropyl Oxalate, C,H,,0,—G. 1-038(0).—Acid (III, A. 1), m. p. 99°; Test 317. Ethyl Methylpropylacetoacetate, C,,H,,0;.—G. 0-959(15).—CO, and methyl propyl acetone. p-Cresyl Acetate, C,H,,O,.—G. 1-066°/,.—Acid (III, B, 1), b. p. 118°; Test SB Ethyl Pyrotritarate (Uvate), C,H,,0,— Acid (III, A, 2), m. p. 135°. Diallyl Oxalate, C,H,,0,—G. 1-055(15-5).—Acid (III, A, 1), m. p. 99°; Test 317. + Diethyl Succinate, C,H,,0,—G. 1-072(0).—Acid (III, A, 1), m. p. 185°; Test 320. Isoamyl Isobutylacetate, C,,H,.0,.—Acid (III, B, 2), b. p. 207-7° ¢. Ethyl Isobutylacetoacetate, C, ,H,,03.—G. 0:951(17-5).—Cf. Genus IV, B. ‘¢ Diethylacetoacetate, C,,H,,0;.—G. 0-974(20).—CO, and diethyl ace- tone. Diethyl Fumarate, C,H,,0,.—G. 1-063(10).—Acid (III, A, 2), sbl. 200°. Methyl Phenylacetate, C,H,,O,.—G. 1-044(16).—Acid (III, A, 2), m. p. 76-5. Diethyl Propylmalonate, C,,H,,0,—G. 0-993(15).—Acid (III, A, 1), m. p. 96°. Methyl a-Phenylpropionate, C,,H,,0,.—Acid (III, B, 2), b. p. 264°. Diethyl Methylisopropylmalonate, C,,H,,0,.—G. 0-990(15).—Acid (III, A, 1), m, p. 124°. Ethyl o-Toluate, C,, Diethyl(mal.)s-D paninyiedecumaee C,)H, ,0,. 1); m. p. 129°. Diethyl Methylpropylmalonate, C,,H.0,.—Acid (III, A, 1), m. p. 106°. es Allylmalonate, C,)H,,0,—G. 1-014(15).—Acid (III, A, 1), m. p. 103°. Diethyl Diethylmalonate, C,,H.»0,—G. 0-992(15).—Acid (IIT, A, 1), m. p. iW H,,0,.—Acid (III, A, 2), m. p. 102°. —G. 1-022(0).—Acid (III, A, Methyl Caprate, C,,H,.0,.—Acid (III, A, 2), m. p. 31-3°. Diethyl Tartronate, C,H,,0,.—Acid (III, A, 1), m. p. 185°-7°, a} Etnylsuccinate, C,,H,,0,.—G. 1-030(21).—Acid (ITT, A, tye. 98°. Diethyl Maleate, C,H,,0,.—G. 1-074(15).—Acid (III, A, 1), m. p. 130°. as Isobutylmalonate, C,,H,,0,—G. 0-983(17).—Acid (III, A, 1), m. M10 ce2 Dane Fumarate, C,,H,,0,.—Acid (III, A, 2), sbl. 200°. Ethyl Tranetheleneaceroater C,H,,0;.—G. 1-070(15).—M. p. +9°— Acid CLAS 2yemrpoia. Ethyl m-Toluate, C,,)H,,0,.—Acid (III, A, 2}, m. p. 110-5°. ‘¢ @G-Dioxybutyrate, C,H,,0,.—Acid (ITI, A, 1), m. p. 74°-5°. ‘¢ Pelargonate, C,,H,.0,.—G. 0-866(17-5). Acid (III, B, 1), b. p. 253°, ‘¢ Tsoamylacetoacetate.—Cf. Genus IV, A. Diethyl Itaconate, C,H,,0,.—G. 1-050(15).—Acid (III, A, 1), m. p. 161°. GENUS V, DIV. B. : 125 (ORDER I, SUBORDER I.) a ——- Boiling- | Sapon. ESTERS.—Liquid Esters whose Neutral Saponification Products fost Equiv. are Readily Volatile witn Steam. Generic Position and Properties of the Acidic Saponification Products, 228 178 | Methyl Ethylphenylacetate, C,,H,,0,.—Acid (III, A, 2), m. p. 42°. 228 164 | Ethyl p-Toluate, C,,H,,0,.—Acid (III, A, 2), m. p. 176°-7°. 228 166 |! Methyl Methylethersalicylate, C,H,,O;.—Acid (III, A, 2), m. p. 98-5°. 228 - 3c. 94 | Dipropyl Malonate, C,H,,0,—G. 1-027(0).—Acid (III, A, 1), m. p. 132°. 228 -7c. Diisoamyl Carbonate, C,,H,.0;.—G. 0-912(15).—Acid, carbonic. 229 (th.i.) | 93 | Diethyl Mesaconate, C,H,,0,—G. 1-060(4). Acid (III, A, 1), m. p. 202°. 229 101 arcu) Oxalate, C, H1,0,-—G. 1-002(14).—Acid (ITI, A, 1), m. p. 99%; est 317. 229c. 164 | Ethyl Phenylacetate, C,,H,,0,.—G. 1-086(16).—Acid (III, A, 2), m. p. 76-5°. 229- 5c. 150 SrOPy apts C, >H120,—G. 1-032(16).—Acid (III, A, 2), m. p. 121°; est - 230 162 | Allyl Benzoate, C,,H,,O,.—Acid (III, A, 2), m. p. 121°; Test 312. 230 178 | Ethyl a-Phenylpropionate, C,,H,,0,— Acid (III, B, 2), b. p. 264°. 231 93 | Diethyl Citraconate, C,H,,0,.—G. 1-047(15).—Acid (III, A, 1), m. p. 80°. 231 188 | Ethyl a-Oxycaprylate, C,,H,.0,.—Acid (III, A, 2), m. p. 69-5°. 230-5 101 | Diethyl iS eteong ek ear C,)H,,0,.—G. 1-0138(0).—Acid (III, A, 2),m: p. 195°. 232 190 | Methyl a-Methylhydrocinnamate, C,,H,,0,.—Acid (III, A, 2), m. p. 37°. 233-5 (th.i.)| 108 | Diethyl Butylmalonate, C,,H,.0,—G. 0-988(15).—Acid (III, A, 1), m. p.76°, 235 180 | Ethyl Methylethersalicylate, C,,H,,0,.—Acid (III, A, 2), m. p. 98-5°. 235-6 ‘« Dipropylacetoacetate, C,,H,.0,—G. 0-959°/,—CO, and dipropyl- acetone. 237 res a pete Besoate: C,,H,,0,.—G. 1-002(15).—Acid (III, A, 2), m. p. 121°; est. olZ. 237c. 94 | Diethyl Glutarate, C,H,,0,—G. 1-025(21).—Acid (III, A, 1), m. p. 97-5°. 236-8 93 if Glutaconate, C,H,,0,.—Acid (III, A, 1), m. p. 132°. 237-8 178 | Ethyl m-Tolylacetate, C,,H,,0,—\G. 1-018(17-5).—Acid (III, A,2),m. p.61°. 236-40 108 | Diethyl Isopropylsuccinate, C,,H.0,—Acid (II, A, 1), m. p. 117°. 238-5 176 | Methyl Hydrocinnamate, C,,H,,0,.—G. 1-047(0).—Acid (III, A, 2), m. p. 48-7°. 240 178 | Ethyl p-Tolylacetate, C,,H,,0,.—Acid (III, A, 2), m. p. 91°. 240 168 ‘* Cuminate, C,,H,,0,.—Acid (III, A, 2), m. p. 116-5°. 40 sl. d. Diethyl Diglycollate, C.H,,0;,—Acid (III, A, 1), m. p. 148°. 240 120 $a Diallylmalonate, C,;H0,.—G. 0-996'*/,;.— Acid (III, A, 1), m. p. 133°. 239-41 Ethyl Dialiylacetoacetate, C,,H,,0,.—G. 0-948?°/,,.;.—CO, and diallyl ace- tone. 241 178 | Ethyl 1 3-Dimethylbenzoate, C,,H,,0,.—Acid (III, A, 2), m. p. 166°. 241 115 | Diethyl Isoamylmalonate, C,,H,,0,.—Acid (III, A, 1), m. p. 93°. 243 -4c. 101 | Dibutyl Oxalate, C,,H,,0,.—G. 1-010(0) .—Acid (III, A, 1), m. p. 99°; Test 317 244 200 | Ethyl Caprate, C,,H,,0,.—G. 0-862.—Acid (IH, A, 2), m. p. 31-3°. 245 180 | Methyl Ethylethersalicylate, C,)H,,0;.—Acid (III, A, 2), m. p. 19-4°. 245 101 | Diethyl Adipate, C,,H,,0,.—Acid (III, A, 2), m. p. 153° ¢. 247-1c. 101 | Diisopropyl Succinate, C,H,,0,.—G. 1-019(0).—Acid (III, A, 1), m. p. 185°; Test 320. 247-3c. 178 | Butyl Benzoate, C,,H,,0,.—G. 1-000(20).—Acid (III, A, 2), m. p. 121°; Test 312. — 247-9e. 178 | Ethyl Hydrocinnamate, C,,H,,0,.—G. 1-034(0).—Acid (ITT. A, 2), m. p 48-7°. 126 Boiling- point (C.°). 248 249-5 250 -8c. 249-52 251 250-3 251-5c. 255 256-7 259 261 263 263 265 265c. 265-7 269 269 - 5c. 270 270-5 271 272 275 275 276d. 278 -3d. 280 282 282-6 284 (th. i.) 285 285-5 t——~ — . Sapon. Equiv. 210 99 161 107 194 108 85 178 212 192 194 115 120 115 226 228 180 208 72 176 206 ey, 86 224 82 103 oF 115 175 Pet 128 GEN US. Vo tDhV a (ORDER I, SUBORDER I.) ESTERS.—Liquid Esters whose Neutral Saponification Products are Readily Volatile with Steam. Generic Position and Properties of the Acidic Saponification Products. Methyl Undecylenate, C,,H,.0,.—Acid (III, A, 2), m. p. 24-5°. Diallyl Succinate, C,,H,,0,— Acid (III, A, 1), m. p. 185°; Test 320. Dipropyl Succinate, C,,H,,0,.—G. 1-016(4).—Acid (III, A, 1), m. p. 185°; Test 320. Diethyl Pentamethylenedicarbonate, C,,H,,0,—Acid (III, A, 2), m. p. 159°-60°. Ethyl Ethylethersalicylate, C,,H,,0O;—G. 1-101.—Acid (III, A, 2), m. p. 19-4°, Ethyl Diisobutylacetoacetate, C,,H,,0;,—G. 0-947(10).—CO, and diisobuty] acetone. Dibutyl Malonate, C,,H,.0,.—G. 1-005(0).—Acid (IIT, A, 1), m. p. 132°. Diethyl i-Malate, C,H,,0;—G. 1-1247'/,—Acid (III, A, 1), m. p. 133°; Test 314. Ethyl Benzoylformate, C,,H,,O,.—G. 1-121(17-5).—Acid (III, A, 1), m. p. 65°-6°. Ethyl Undecylenate, C,,H,,0,.—G. 0-883(15).—Acid (III, A, 2), m. p. 24-5°. Isoamyl Benzoate, C,,H,,0,.—G. 1-004(0).—Acid (III, A, 2), m. p. 121°; Test 312. Ethyl m-Ethoxybenzoate, C,,H,,0,.—G. 1-088(0).—Acid (III, A, 2), m. p. Vic. Diisoamyl Oxalate, C,,H,.0,—G. 0-968(11).—Acid (III, A, 1), m. p. 99°; Test 317. Dimethyl Camphorate, C,,H.0,—G. 1-075?°/,— Acid (III, A, 2), m. p. L802 7 Diisobutyl Succinate, C,.H,.0,.—G. 0-974(15),—Acid (III, A, 1), m. p. 185°; Test 320. Isoamyl Orthoformate, C,,H,,0,—G. 0-864(23).—Acid (III, B, 1), b. p. 100-8°; Test 315. Ethyl Laurate, C,,H,,0,.—G. 0-867(19).—Acid (III, A, 2), m. p. 43-6°. ‘* Anisate, C,)H,,0,.—Acid (III, A, 2), m. p. 184-2°. Isoamyl Salicylate, C,,H,,0;—Cf. Genus IV, B; Test 319. Trimethyl Aconitate, C,H,,O,.—Acid (III, A, 1), m. p. 191°. } Ethyl Cinnamate, C,,H,,0..—G. 1-066(0).—Acid (III, A, 2), m. p. 133°; Test 313. n-Hexyl Benzoate, C,,H,,0,.—G. 0-999(17).—Acid (IIT, A, 2), m. p. 121°; Test 312. Diisopropyl Tartrate, C,)H,,O,.—G. 1-13(20).—Acid (III, A, 1), m. p. 168°; Test 314. Triethyl Aconitate, C,,H,,0,.—G. 1-074(14).—Acid (III, A, 1), m. p. 191°. Ethyl Camphocarbonate, C,,H..0;.—G. 1-0567°/,— Acid (III, A, 2), m. p. 128°, Triethyl Ethenyltricarbonate, C,,H,,O,.—G. 1-095*°/,—Acid (III, A, 1), mapas ec Diethyl{ + ]Tartrate, C,H,,0,.—G, 1-206(20).—Acid (III, A, 1), m. p. 168°; Test 314. Dimethyl Phthalate, C,,H,,.0,.—Acid (III, A, 2), m. p. 184°; Test 318-1. Diethyl Suberate, C,,H,,0,.—G. 0-985(15).—Acid (III, A, 2), m. p. 140°. ‘¢ Carbopyrotritarate, C,,H, ,0,.—Acid (III, A, 2), m. p. 230°-1°. ‘« Isophthalate, C,,H,,0O,.—Acid (III, A, 2), m. p. a. 300°; Test 318-2. Diethyl Camphorate, C,,H,,0,.—G. 1-029(16).—Acid (III, A, 2), m. p. 180° c. Boiling- poin (G.7). 290 291-2 294 295c. 295 298-5 295-305 305 307-8 308 308-9 309c. 308-5-11 310 (th. i.) 314 323-4c. a. 360 Sapon Equiv. 122 92 111 256 258 86-7 234 129 212 200 200 284 166 226 212 228 GENUS V, DIY. B. 127 (ORDER I, SUBORDER I.) ESTERS.—Liquid Esters whose Neutral Saponification Products are Readily Volatile with Steam. Generic Position and Properties of the Acidic Saponification Products Methyl £-Benzoylpropionate, C,,H,,0;.—Acid (III, A, 2), m. p. 116°. Diethyl Azelate, C,,H,,0,.—G. 0-991°/,.—-Acid (III, A, 2), m. p. 106°. Triethyl Citrate, C,,H..O0,—G. 1-137?°/,—Acid (III, A, 1), m. p. 153°; Test 314 { Diethyl Phthalate, C,,.H,,0,—G. 1-118?°/,.—Acid (III, A, 2), m. p. 184°; Test 318-1. Ethyl Myristate, C,,H,.0,.—Acid (III, A, 2), m. p. 53-8°. Diisoamyl Succinate, C,,H,,0,—G. 0-961(13).—Acid (III, A, 1), m. p. 185°; Test 320. Triethyl Tricarballylate, C,,.H,.O,.—Acid (III, A, 1), m. p. 166°. Octyl Benzoate, C,,H..0,.—Acid (III, A, 2), m. p. 151°; Test 312. + Diethyl Sebacate, C,,H,,0,.—G. 0-965(16).—Acid (II, A, 2), m. p. 133°. Methyl o-Phenylbenzoate, C,,H,,0,.—Acid (III, A, 2), m. p. 110°-1°. Ethyl @-Naphthoate, C,,H,,O,.—Acid (III, A, 2), 1. p. 184° ¢. ‘< —a-Naphthoate, C,,H,,0,.—Acid (III, A, 2), m. p. 160°. ‘< Diheptylacetate, C,.H,,0,.—Acid (III, A, 2), m. p. 26°-79- eee tpea cus acetate, C,H,,0,.—G. 1-195°7,.—Acid (IIT, A, 1), m. p. Etbvl o-Phenylbenzoate, C,,H,,O,.—Acid (III, A, 2), m. p. 110°-1°. Benzyl Benzoate, C,,H,,0,.—G. 1-114(18-5°).—Acid (III, A, 2), m. p. 121°; Test 312. Methyl Phenylethersalicylate, C,,H,,0,.—Acid (III, A, 2), m. p. 117° CHAPTER VIIL GENUS VI. ACID ANHYDRIDES AND LACTONES OF SUBORDER I, ORDER I. (Colorless Compounds of Carbon, Hydrogen, and Oxygen.) To this genus belong all species of the suborder, which, while not attacked rapidly enough by cold alkali to give Tests III or IV, yield a saponification equiva- lent of less than 500 in Test V, and form the sodium salt of an acid as their sole organic saponification product. No independent Generic Test VI exists, the claim of any species to membership in the genus being settled by the outcome of the exam- ination of the reaction products obtained in Test V (p. 111). The number of important species described under Genus VI is smaller than for any other genus in Order 1. It has already been mentioned elsewhere that many of the simpler and more important anhydrides, like acetic, benzoic, and succinic, and phthalid, are sufficiently reactive towards either cold decinormal or normal alkali to be entitled to positions with the acids or phenols. The number of species which might otherwise have established a valid claim for admission to the genus has been still further diminished by the difficulties that lay in the way of procuring pure preparations of representative types for direct examination, and the utter impossibility of drawing safe conclusions, a priori, as to the behavior of many of them towards alkali from the vague or conflicting statements that may be gleaned from a study of their literature. These unavoidable omissions, which can only be remedied by later investigations, consist almost exclusively of rare and unim- portant compounds. The fact that Genus VI is a skeleton genus to a greater extent than most others, has, therefore, little practical significance, except to the investigator in a few special fields. 128 COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I]. GENUS VI, ACID ANHYDRIDES AND LACTONES DIVISION A,—SOLID ACID ANHYDRIDES AND LACTONES WIIICH DO NOT NEUTRALIZE COLD SODIUM HYDROXIDE SOLUTIONS READILY ENOUGH TO GIVE TESTS III OR IV, 2. Melting-point fU je | 25 63-4 64 67 71-7 73 86-7 102-5 103-5 128 128-30 134 160-61 169-70 218c. Rea antenna a ACID ANHYDRIDES AND LACTONES.—Colorless and Solid. Melilotic Anhyd., 0-0.(.C,H,.C,H,.CO.).—B. p. 272°.—Odor like vanilla grass or Tonka bean !—S. c. aq.; d. s. h. aq.; e. s. CHCl,.—Boiled w. alkali gives melilotic ac., m. p. 82°-3°.—Br, substitutes in CS, sol. giving compound w. m. p. 106° (pr. fr. CHCl,). 3-Methoethylol(3’)-heptanon(6)-olid(1, 3’),C,,H,,0;—B. p. 330°.— (An _ oxid. product of pinene, etc.).—Cryst. v. e. fr. h. aq.; s. aq.; v. s. CHCl,; much less s. eth.—Sodium hydroxide and Br added to aq. sol. give CBr,—Neut. equiv. 184. Palmitic Anhyd., (C,,H;,0),.0. + Coumarin, o-O(.C,H,.C,H,.CO.).— Fragrant odor like vanilla grass or Tonka bean !—B. p. 290°-0-5°.—Alm. i. c. aq.; s. h. aq.; e. s. ale. or eth.—Does not give Test III or IV.—Test V gives coumaric ac. !—The solution in alkali has a peculiar greenish-yellow color !—Adds Br, in CS, sol. (Cryst. fr. alc., m. p. 105°.) Stearic Anhyd., (C,,H,,0),.0. + Phthalid. o-O(.CH,.C,H,.CO.).—B. p. 290° (th. i.).—Ndl. fr. h. aq.; v. d.s. ¢. aq.; e. s. alc.—Alkaline KMnO, gives phthalic acid (Test 318-1) easily.— Test V gives o-Oxymethylbenzoic ac. (III, A, 2), m. p. 120°._{Finely powdered dissolves after shaking 1-2 min. in Test I1V-2, and so properly belongs in Genus IV.]! Glycolid, C,H,O,.—_Lft. fr. alc., d. s. c. ale. or eth.; v. s, acetone.—Protracted boiling w. aq. gives glycollic ac. Meconine, C,,H,,0,. (from mother-liquors of opium alkaloids).—Sbl. in lus- trous ndl.—(Cf. Genus III, A, 2.) Benzoylperoxide, (PhCO),.0,.—Rhomb. cryst., e. s. eth. or bz.—Explodes on heating !—Boiled w. KOH sol. gives benzoic ac. (Test 312) and oxygen. Lactid, C,H,O,.—Cryst. fr. h. alc., alm. i. c. aq.— Boiled w. aq. gives lactic ac.— (Cf. Genus III, A, 2.) Glycollic Anhyd.—Powd. i. aq.—(Cf. Genus ITI, A, 2.) Benzoin.—Slightly attacked in Test V.—(Cf. Ketones, VII, A.) Saccharin, C,H,,0,.—Pr. of bitter taste. 100 pt. aq. at 15° dissolve 13 pt.—Opt. act.[+]; salts however [—].—Ether extracts fr. strongly alk. sol. in Na,CO,.— Aq. sol. boiled w. CaCO, gives soluble uncryst. Ca saccharate.—Gives Test 801! Santonin, C,,H, .0,.—Cryst., s. in 5000 pt. c., or 250 pt. h. aq.; s. ¢. alc.; d.s.c.eth.; e. s. CHCl,.—Opt. act.—Cryst. rapidly turn yellow in air!—Does not redden litmus.—Alcoholic KOH colors red !—Warming w. alkali gives santonic ac. + Cantharidin, C,,H,,0,.—Well-formed cryst., alm. i. c. or h. aq.; v. d. s. ale. or eth.—Alc. sol. placed on skin quickly produces painless blisters !—2 pt. heated at 100° for 15 min. w. 3 pt. phenylhydrazine hydrochloride, 4-5 pt. NaAc, and 30 pt. aq. gives a hydrazonehydrate cryst. fr. ale. w. m. p. 194° c. —y Test V gives sodium cantharidate. The cantharidin may be recovered unchanged by boiling the cantharidate sol. for a few minutes after acidifi- cation w. dil. H,SO,; the cantharidic ac. in the heating loses water and gives i. cantharidin, which precipitates out. 129 130 GENUS VI, DIV. A. (ORDER I, SUBORDER I.) ae et ACID ANHYDRIDES AND LACTONES.—Colorless and Solid. 220 Polyglycolid, (C,H,O,)2—White powder, v. d. s. h. aq.—Reacts neutral, but by persistent boiling w. aq. or KOH gives glycollic ac.—Prepare aniline derivative, Bl., 30, 102. 220-1 Camphoric Anhyd.—B. p. 91°.—(Cf. Genus III, A, 2.) 223-4 Umbelliferone, C,H,O,—(Cf. Genus IV, A).—Odor when warm, fragrant, like coumarin. 334-5 Biphthalyl, C,,H,O,.—Sbl. in ndl.; i. aq.; alm. i. ale. or eth., s. h. glacial acetic ac. or conc. H,SO,.—The sol. in conc. H,SO, shows blue fluorescence, but becomes transiently emerald-green if a trace of nitric acid is added.—Warmed w. KOH sol. gives diphthalylaldehydic ac. COLORLESS COMPOUNDS CONTAINING ©, H, AND O [SUBORDER I OF ORDER 1.) GENUS VI, ACID ANHYDRIDES AND LACTONES. DIVISION B,—LIQUID ACID ANHYDRIDES AND LACTONES WHICH DO NOT NEUTRALIZE COLD DECINORMAL SODIUM HYDROX- IDE READILY ENOUGH TO TITRATE LIKE SPECIES OF GENUS III. Oe aaa ACID ANHYDRIDES AND LACTONES.—Colorless and Liquid. 167 sl.d. | a-Levulinic Anhyd., C,H,O,.—M. p. 18°-18-5°.—E. volatile in air—S. in 21 pt. aq. at 15°, but ppt. by K,CO,.—‘‘5 hours’ boiling w. aq. gives levulinic ac.” 204 $-Methyl-;-butyrolactone, O(.CH,.CHMe.CH,CO.).—G. 1-077°/,—S. in 14-2 pt. aq.—BaA, ndl.; v. s. aq.—Pure ac. unknown. 206c. 7-Butyrolactone, O(.(CH,);.CO.).—G. 1-129'*/,—Misc. w. aq.; separated fr. conc. sol. by K,CO,.—Volat. w. st.—Reduces ammon. AgNO,.—‘‘ Boiled 5 min. w. N/,, NaOH is only 4 converted into salt of acid.’””—Oxid. by CrO, to succinic ac. (Test 320). 206 a-Methyl-;-valerolactone, O(.CHMe.(CH,);.CO.).—S. 20-25 pt. aq.; sat. sol. becomes turbid on warming, but clears at 80°.—Acid v. unstable. 207c. y-Isocaprolactone, O(.CMe,.C,H,.CO.).—M. p. 7°-8°.—G. 1-015'*%?/,—S,. in 2 pt. c. aq.; sat. sol. becomes turbid on warming, but clears at 80°.—K,CO, separates lactone fr. conc. aq. sol.—Free ac. cryst. but unstable, especially on warming.—Ag salt ppt. cryst. in flat ndl. fr. h. aq. 206-9 Coumalin, O(.(CH),.CO.).—G. 1-2001%°/,—Agreeable coumarine-like odor !— M. p. +5°.—Misce. w. aq. but separated fr. sol. by K,CO;.—Aq. sol. neutral, even after warming.—Neutralizes N/,, NaOH very slowly, giving yellow sol.—Neutralized and then boiled w. x’s alkali gives crotonic aldehyde (odor). 207-S8c. t 7-Valerolactone, O(.(CH,),.CO.).—G. 1-057'8/,—Sapon. Eq. 100.—Misc. w. aq.—Ppt’d from the conc. neutral aq. sol. by K,CO,.—Half converted into salt of acid after 7 min. boiling w. equivalent quantity N/,,, NaOH; pro- tracted boiling w. aq. gives only 6-6% acid.—Ac. very unstable. Its Ag salt (AgC,;H,O,), large triclin. ndl. fr. h. aq. 208-9 $-Levulinic Anhyd., C,H,O,.—G. 1-108(0°).—V. s. aq.—Hydrolyzed v. slowly and incompletely by h. aq.—Dec. by c. Ba(OH), sol. to levulinie ac. in 12 hours. 215 Valerianic Anhyd., (C,H,O),.0.—G. 0-9297*7/,—‘‘Slowly hydrolyzed by boil- ing aq.’’—Vapor produces coughing. When fresh has apple-like odor— Sapon. equiv. 93.—Cf. Genus ITI, B, 2. 215 a-Ethyl-r-butyrolactone, O(.CH,.CH,.CHEt.CO.).—G. 1-035(16°).—S. in 10-11 pt. c. dl i a ‘ ~ f ir Weer Bi gg COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER J]. GENUS VII, KETONES. Boiling-point CORE 56- 5c. 80-6 87-5-8 95 98-102 102c. 102 -7c. 106 (th. 1.) 114 114-5 116 118c. 122 122-4 123-7 126 127 128 128-30 129-5-30c. 130c. 132 DIVISION B,—LIQUID KETONES. Specific . Gravity. 0-819°/, 0-805(19-8) 0-973(22) 0-822°/, 0-812(15) 0-834°/, 0-800(16) 0-830°/, 0 ef 80217 /, OFS18'**/, 0-861(15) 0-818(17-5) 0-8067°/, 0-810(21) 0-830(0) 0-920(21-7) 0-834?"/,7.5 0-85829/, 0-9427-5/, 0-825(21) KETONES.—Colorless and Liquid. t Acetone, Me.CO.Me.—Misc. w. aq., alc., or eth.—Odor alco- holic-ethereal.—Identify by Test 711! { Methyl Ethyl Ketone, Me.CO.Et.—Odor like acetone.—Oxid, by Test 702 gives acetic ac. only! . } Diacetyl, Me.CO.CO.Me.—Yellow liquid w. peculiar sweetish- pungent odor. (Belongs to Div. B of Suborder IT.) Methyl Isopropyl Ketone, Me.CO.Pr.—Oxid. by Test 702 gives Ac and COQ,. 2-Methylbutenon(1, 3), Me.CO.CMe:CH,. t Methyl Propyl Ketone, Me.CO.Pr.—Test 702 gives acetic and propionic acids. t Diethyl Ketone, Et.CO.Et.—CrO, oxid. to acetic and propionic acids (cf. Test 702).—Gives NaHSO, comp. w. difficulty. + Pinacoline, Me.CO.C.Me,.—Alm. i. ag.—Peppermint-like odor. —No NaHSO, comp.—Test 702 oxid. to trimethylacetic ac. —Treated w. Cl cold gives C,H,,Cl,0, m. p. 51°; b. p. 178°.— Becomes opaque and yellow in 10 sec., cold, in Test VII-2. Acetyltrimethylene, Me.CO.C,;H,;. — Polymerized by mineral acids.—_KMn0O, gives trimethylenecarbonic ac. Ethyl Isopropyl Ketone, Et.CO.Pr. . Methyl Isobutyl Ketone, Me.CO. Bu.—Strong camphor-like odor. —Test 702 oxid. to isobutyric, isovalerianic, and acetic acids (disagreeable odor).—Gives a NaHSO, comp. Methylethylacetone, Me.CO.CH(Me)Et.—Peppermint-like odor. —Test 702 gives acetic ac. (Test 311). Ethylideneacetone, Me.CH: CH.CO.Me.—S. aq. Ethyl Propyl Ketone, Et.CO.Pr.—Test 702 oxid. to Ac, pro- pionic and butyric acids. Diiosopropyl Ketone, (Me,.CH),.CO.—No comp. w. NaHSO;.— CrO, gives acetic and isobutyric acids (Test 702). 2, 2-Dimethylpentanone(3), Et.CO.C.Me,.— Camphor odor. — Test 702 gives Ac and trimethylacetic ac. Methyl Butyl Ketone, Me.CO. Bu. Acetylcarbinolethylether, Me.CO.CH,.OEt.—Misc. w. aq.—Rc- duces Tollen’s AgNO, reagent —In HCl sol. gives acetore and ethyl alc. w. Na amalgam. Allylacetone, Me.CO.(CH,),.CH:CH,.— Unpleasant odor.—Test 702 oxid. to acetic and oxalic ac. (Tests 311 and 317). + Mesityl Oxide, Me,.C: CH.CO.Me.—Peppermint odor.—I. aq. ; v. s. ale.—Boiled w. v. dil. H.SO, yields acetone (Test 711). —Gives no NaHSO, comp.—Shaken w. phenylhydrazine re- acts w. evolution of heat (product oily). Solution opaque and yellow in 5 sec. in cold, in Test VIJ-2. Cyclopentanone, C,H,CO.—Peppermint odor —Dil. HNO, gives glutaric and succinic ac.—Semicarbazon, m. p. 200°-5° d. 3, 3-Dimethylpentanone(2), Me.CO.C(Me,)Et.—Test 702 oxid. to dimethylethylacetic ac. 141 142 GENUS VII, DIV. B. (ORDER I, SUBORDER I.) Boiling-point (CS): 135 136 135-40 137 -5-9 141-3 144c. 144 147d. 149-50 151 151-2 155 155-6 155 163-5-4-5 169 170 170-1 172-5 173-4 173-4 174-5 176-7 179-81c. 180 181-2 190 192-3 194 (th. i.) 196-8 202 (th. i.) oe) Kay (=: i io) ry Specific Gravity. -907(15) -815!7/, -815(20) -817(22) -91429/, -818 (17-2) -914(0) -829(21) -837(0) -831(0) .900(15) -94770/, -931(25) -909(20) -850(0) -817(19) -819?°/, -860(20) -000(15) -969(0) -827(16) -833(20) -82520/, -947(19) -97020-8/, -032(15) KETONES.—Colorless and Liquid. Methyl Tetramethylene Ketone, Me.CO.C,H,.— Peppermint odor. —Gives a NaHSO, comp. Ethyl Isobutyl Ketone, Et.CO. Buu—Test 702 oxid. to acetic and isovalerianic ac. 2, 3-Dimethylpentanone(4), Me.CO.CHMe.CHMe.. 3-Ethylpentanone(4), Me.CO.CHEt,.—Gives a bisulphite comp. 1-Methylcyclopentanone(3), Me.C,H;,.CO.—Opt. active [+]. Methyl Isoamyl Ketone, Me.CO.C,H,,.—Test 702 oxid. to acetic, isovalerianic and isocaproic ac. Dipropyl Ketone, Pr.CO.Pr.—I. aq.—Test 702 oxid. to pro- pionic and butyric acids.—Gives no NaHSO, comp. Acetylcarbinol (Acetol), Me.CO.CH,OH.—Misc. w aq., alc., or eth.—‘‘Faint, sickly odor’ !—Reduces Fehling’s sol. cold.—Combines w. 2 mols. phenylhydrazine at 100° forming methylglyoxalosazone, m. p. 145°.—Phenyl- hydrazone oily.—‘‘Soon acquires acid reaction.” Posi- tion in tables in -doubt. 2-Hexinone(5), Me.CO.CH,.C : C.Me. 3, 3-Dimethylhexanone(4), Et.CO.C.(Me.,) Et. Methyl Amyl Ketone, Me.CO.C,H,,.—Oxid. by Test 702 to acetic and valerianic acids.—Gives a NaHSO, comp. Propyl Isobutyl Ketone, Pr.CO. Bu.—Gives no NaHSO, comp. Propionylcyclobutane, Et.CO.C,H, Gives a NaHSO,; comp. Cyclohexanone, (CH,),:CO.—Odor like acetone.—EH. s. aq.— Dil. HNO, oxid. to adipic ac.—Gives comp. w. NaHSQO,. Diacetone Alc., Me.CO.CH,.CMe,.OH.—Misc. w. aq. or ale.— Sol. in conc. H,SO, gives mesityl oxide. [+ ]-1-Methylcyclohexanone(3), Me.C,H,0. Ethyl Amyl Ketone, Et.CO.C,H,,.—-Gives no comp. w. NaHSO,. 2-Methylheptanone(6), Me.CO.(CH,),.CHMe,. Methyl Hexyl Ketone, Me.CO.C,H,,.—Oxid. by HNO, gives cenanthic and acetic acids.—Gives comp. w. NaHSO,. Dipropylacetone, Pr..CH.CO.Me. 2-Methylheptene(2)-one(6), C;H,,-CO.—KMnO, oxid. to ace- tone and levulinic ac.—Gives purple-red color to pine splinter moistened w. HCL. as.-Diallylacetone, (C,H,),.CH.CO.Me. Hydracetylacetone, Me.CH(OH).CH,.CO.Me.—S. aq., alc., eth., or CHCl,.—Gives phenylhydrazone, m. p. 85°-7°. Suberone, C,H,,:CO.—Peppermint odor.—Adds Br easily. Methylbutyroue, C,H,,0.—Conc. HNO, oxid. to cenanthie ac. 2, 6-Dimethylheptanone(4), (Me,.CH.CH,),.CO.—NaHSO, gives no comp. Ethyl Hexyl Ketone, Et.CO.C,H,,.—Solid at —8°. }+[+]}Fenchone, C,,H,,O (from oil of fennel.)\—Odor pleas- ant and camphorous!—M. p. +5°-6°.—Heated w. P.O, gives m-isocymene.—S. without decomposition in cone. H,SO,.—Gives an oxime, m. p. 164°-5° (x. h.). t Acetonylacetone, Me.CO.(CH,),.CO.Me.—K. s. aq., alc., or eth.—Gives pyrrol test (Test 703) w. splinter.—Combines w. x’s phenylhydrazine on warming to osazone, cryst. fr dil. alc., m. p. 120°. ; 4-Methyloctonone(2), C,,H,,0. + Acetophenone, Me.CO.Ph.—Alm. i. aq.—M. p. 20.5°.—Gives Test VII-2 readily in the cold.—Identify by Test 712! GENUS VII, DIV. B. 143 (ORDER I, SUBORDER I.) eee ences erences eee ri icc Boiling-point (C,?). 200-5 203 204-5 200-10 © 206c. 206-7 206-8 207 208-9d 211 210-15 215 217 218 220-2 221-2 221-2 222 224 223-6 224-5 224-5 O- Specific Gravity. 939(12) -913(20) -841(17) -913(0) 8242057, -900(20) -896(20) -016(0) -825(20) -948?9/, -010(3) -009(0) -932(20) -928(19) 1-013 -829(17-5) -998(17-5) -996(19) -989(20) KETONES.—Colorless and Liquid. Camphorphoron, Me,C:C,;H,O.Me.— Odor spicy. — Tribrom- comp., m. p. 52°. { Thujone (Tanacetone), C,,H,,O (fr. tansy-oil, Tanacetum vulgare).—Odor somewhat like tansy.—Opt. active [+]. —(NaHSO, comp. i. eth., forms very slowly.)—Dist. fr. P.O, gives cymene —Boiling w. FeCl, gives carvacrol.— a-oxime, m. p. 54-5°——5 cc. Br+5 grms. thujone and 30 ce. Igr. (cold) gives tribrom-deriv., d.s. alc., m. p. 121°-2°. Ditetramethylene Ketone, (C,H,)..CO.— Peppermint odor. — NaHSO, comp. e. s.—Combines w. phenylhydrazine. Isopropyl Hexyl Ketone, Me,.CH.CO.C,H,;.—Gives no NaHSO, comp. a-Menthone, C,,H,,0.—Faint peppermint odor. Does not give Test 702.—Opt. active [+].—P,O, gives a terpene, b. p. 170°-3° and a diterpene b. p. 320°-5°, Propyl Hexyl Ketone, Pr.CO.C,H,,—M. p. —9°.—Gives no NaHSO, comp. [+]}Menthone, C,,H,,0.—Similar to [—}menthone. — Oxime syrupy. +{—]}Menthone, C,,H,,O.— Odor peppermint-like.— D. s. aq.; misc. alc. or eth.—Oxime by Test VII-1, m. p. 118°-19°. Acetylpropyl Alc., Me.CO.(CH,),.CH,OH.—Slow dist. gives unstable anhydride, b. p. 72°-5°.—Misc. aq.; e. s. alc. or eth.—NaHSO, comp. e. s. aq. or alc.—May be oxid. by CrO, mixture to levulinic ac. Methyl Octyl Ketone, Me.CO.C,H,,—M. p. +3-5°.—Odor orange-like.—Gives a NaHSO, comp. Eucarvol, C,,H,,0.—Boiled w. conc. sol. of KOH in CH,OH gives unstable blue color. Methyl Benzyl Ketone, Ph.CH,.CO.Me.—Cf. Div. A, m. p. 27°. Isopropyl Phenyl Ketone, Pr.CO.Ph.—Phenylhydrazone, m. p. 71°.—Oxime, m. p. 58°. Propiophenone, Ph.CO.Et.—M. p. +21°.—Gives no NaHSO, comp.—Oxime melts at 52°-53°. - Propyl Phenyl Ketone, Pr.CO.Ph—No NaHSO, comp.— Test 702 gives benzoic and propionic acids (Tests 312 ane Ll je { Pulegone, C,,H,,0.—Odor of pennyroyal (Mentha pule- gium).—Gives a NaHSO, comp. (forms very slowly); i, ale. or eth.—Opt. active [—].—Adds Br,.—Oxime, m,.p. 157° silky ndiv dsssaic.! Dihydrocarvone, C,,H,,0O.—Opt. active [+ or —].—Gives NaHSO, comp. slowly.—Adds Br,.—Oxime, m. p. 87°-9°. p-Methyl Tolyl Ketone, Me.CO.C,H,.Me.—Oxid. by KMnO, gives terephthalic ac.—Dibrom-derivative, m. p. 100°. Methyl Nonyl Ketone, Me.CO.C,H,,.—Chief constituent of oil of rue (Ruta graveolens). Freezes at +6°; m. p.+15°.—Test 702 gives acetic and pelargonic acids. Ethyl Benzyl Ketone, Et.CO.C,H,.—Gives no NaHSO, comp.— Test 702 gives benzoic and propionic acids (Tests 312 and oll). t 2-Methyl-1, 4-Xylyl Ketone, Me.CO.C,H;.Me,.—(Sol. in Test VII-2, becomes opaque and yellow after heating 1 min.)— No NaHSO, comp.—HE. s. alc. or eth.—Oxime, m. p. 58°. m-Methyl Tolyl Ketone, Me.C,H,.CO.Me.—Gives isophthalic *° _ on oxid. by alkaline KMnQ,. a ~ 144 Boiling-point Specific (O22); Gravity. 225-6 0-993(17-5) 226¢ 0-826(20) 226 230-2 232-3 235 0-989(0) 235-6 0-989?3/,, 235-6 237-8 237 - 5-8-5 237-9 237-40 238-9c. 238-9 239-40 240 -5-1 241-5-2-5 244-5 245 -5-6- 5c. 246-7 (th. i.) 1-019(0) 246-5 249 251 251-2 253-5 254c 0-975(15) 255-8 256-60 259 (th. i.) 0-978(15) 259 0-957(19) 259 1-052(15) 259 GENUS VII, DIV. B. (ORDER I, SUBORDER I.) KETONES.—Colorless and Liquid. Isobutyl Phenyl Ketone, Bu.CO.Ph.—Test 702 gives benzoic and isobutyric acids —Gives no NaHSO, comp.—Oxime, m. p. 74°, { Caprone, (C,H,,),.CO.—M. p. 14-6°.—Gives no NaHSO, comp. —Sol becomes opaque and the undissolved drop deep yel- low in Test VII-2 (This is the highest symmet. fatty ketone in its series known to give Test VII-2.) Diisoamyl Ketone, (C,H,,),..CO.—Yellow oil. Diethylacetophenone, Ph.CO.CHEt,. p-Tolylacetone, Me.C,H,.CH,.CO.Me.—Gives no NaHSO, comp. —Oxime, m. p. 90°-1°. Acetylmesitylene, Me.CO.C,H,.Me,. Benzylacetone, Ph.CH,.CH,.CO.Me.—Test 702 oxid. to benzoic and acetic acids.—Gives NaHSO, comp., rather d. s. aq. Isopropyl Tolyl Ketone, C,H,.CO.C,;H,,—Oxime, m. p. 92°. Ethyl p-Xylyl Ketone, Et.CO.C,H;.Me,. Butyl Phenyl Ketone, Bu.CO.Ph. Ethyl p-Tolyl Ketone, Et.CO.C,H,.Me.—Nitration w. fuming HNO, gives comp. having m. p. 50°-1°.—Oxime, m. p. 86-7°. Allylacetophenone, Ph.CO.CH,.C,H,.—Adds Br, easily. a-Methylbenzylacetone, Me.CO.CH(Me)(C,H,). Ethyl m-Xylyl Ketone, Et.CO.C,H;.Me,.—Phenylhydrazone, m. p 126°.—Oxime, m. p. 72°. 2-Isopropyl-1, 4-Xylyl Ketone, C,H,.CO.C,H,.Me,.—Odor like mushrooms.—Oxime, m. p. 76°. 3 Benzoyltrimethylene, Ph.CO.C,H;.—Br acts only at high temp. —Oxime, lft. fr. lgr., m. p. 90°-2°. Isoamyl Phenyl Ketone, C,H,,.CO.Ph. 4-Isopropyl 1, 3-Xylyl Ketone, C,H;.CO.C,H;.Me,.—Oxime, m. p. oT {-Methylhydrindone, C, ,H, ,0.—Peppermint odor.—KMnO,oxid. to phthalic ac.—Sol. in cone. H,SO, fluoresces blue-violet. Methyl o-Xylyl Ketone, Me.CO.C,H;.Me,.—E. s. alc. or eth.— KMn0O, oxid. to p-xylic ac.—Oxime, m. p. 85°. Methyl Pseudocumyl Ketone, Me.CO.C,H,.Me,.—M. p. 10°.— E. s. ale. and eth. 2-Propyl 1, 4-Xylyl Ketone, Pr.CO.C,H;.Me,.—Aromatic oil.— Oxime, m. p. 47°. 4-Propyl 1,3-Xylyl Ketone, Pr.CO.C,H,;.Me,.—E. s. alc. or eth.—Odor turpentine-like. Xylitone, C,,H,,O0.—Geranium odor.—I. aq.—Easily oxid.— KMn0O, gives CO,, acetic, and a-dimethylsuccinic acids.— Resinified by cone. acids. Methyl a-Duryl Ketone, Me.CO.C,H.Me,.—E. s. alc. or eth. p-Acetylcumene, C;H,.C,H,.CO.Me.—Nitrates to comp. having m. p. 49°.—Oxime, m. p. 70°-1°. 4-Isopropyl 1,2-Xylyl Ketone, Pr.CO.C,H;.Me,. — Turpentine odor.—Oxime, m. p. 68° Methyl o-Cymyl Ketone, Me.CO.C,,H,;.—Aromatie oil. p-Acetylpropylbenzene, Me.CO.C,H,.Pr.—Oxid. by alkaline KMn0O, gives terephthalic and benzoic acids. (Tests 318-3 and 312.) 2-Isopropyl 1, 4-Isocymyl Ketone, Pr.CO.C, ,H,,.—Oxime is oily. Benzoylcyclobutane, C,H,.CO.Ph.—Oxime, d. s. lgr., m. p. 92°. Methyl set Ketone, Me.CO.C,H.Me,.—Phenylhydrazone, Mepis. Boiling-point (Gra ye 260-5c. 266-9 270-7 270-72 295-6 300-4 305-7 308-10 a. 300 312-14 314-16 315-16 322 (th. i.) 325-30 Specific Gravity. 0-944(19) 1-134(0) 0-826(17) 1-108(0) 1-076(0) 1-062(0) 1-088(17-5) GENUS VII, DIV. B. 145 (ORDER I, SUBORDER I.) KETONES.—Colorless and Liquid. Cumylacetone, Pr.C,H,.CH,.CH,.CO.Me.—Oxime, m. p. 56°. Ethyl o-Cymyl Ketone, Et.CO.C, ,H,;. Phenyl Hexyl Ketone, Ph.CO.C,H.,,. oxime, m. p. 55°. 2-Isobutyl 1, 4-Isocymyl Ketone, Bu.CO.C, ,H,,.—Oxime is oily. a-Methyl Naphthyl Ketone, Me.CO.C,,H;.—V. s. alc. or eth_— Oxime, m. 145° _—Picrate, iv ale- sol), m.p. 116° -—Br substitutes readily. Diheptylacetone, Me.CO.CH.(C,H, ;)..—Gives a NaHSO, comp. a-Propanoylnaphthene, Et.CO.C,,H;,—V. s. alc. or eth— Oxime, m. p. 57°-8° —Picrate, yellow ndl., m. p. 77°-8°. a-Isopropyl Naphthyl Ketone, Pr.CO.C,,H;. Ossi i palaos, —Picrate, m. p. 66-7°. p-Ethylbenzophenone, Ph.CO.C,H,.Et.—Gives isomeric oximes. iteopropyl SEDO Ketone, Pr.CO.C,,H;.—V. s. alc.—Oxime, maple 2. m-Phenyl Tolyl Ketone, Ph.CO.C,H,.Me.—V. s. alc. or eth.— Oxime, m. p. 100°-1°. o-Pheny] Tolyl Ketone, Ph.CO.C,H,.Me.—Gives isomeric oximes. a-Phenyl-m-Xylyl Ketone, Ph.CO.C,H,.Me,—Gives isomeric oximes. Dioctylacetone, Me.CO.CH.(C,H,,).. —Aromatic oil. —Lft. m. p. 17°.—Gives an NUMBERED SPECIFIC AND SEMI-SPECIFIC TESTS FOR THE KETONES. [TESTS 701-800.] 7o1. Colorations with Sodium Nitroprusside. Shake five drops of the ketone with 2 cc. of cold water. If the substance does not dissolve completely, filter through a wet filter. Add to the clear solution two drops of a 1% aqueous solution of sodium nitroprusside, and then two drops of sodium-hydroxide solution (1:10). Without any unnecessary delay, carefully note the color, and then quickly divide the solution into two equal portions, a and b, in small glass “ weighing-tubes.”’ To portion 6 add three drops of glacial acetic acid, and immediately note the color. Allow both solutions to stand for twenty minutes, and again carefully compare the color of each with the color standard. Many of the aldehydes as well as ketones of Order I give colorations in this test; but its most important practical application is its use as a convenient specific reaction for acetone and acetophenone. It distinguishes these ketones readily from all related ketone species with which either is likely to be confused. In the case of acetone, portion a at first is orange (O), but changes to a clear yellow (Y-YT1) within twenty minutes. Portion 6 after the acidification with acetic acid is a red (R-RT1) when viewed against .a white background, with a very slight tendency to purple, that is most noticeable when the solution is viewed by a strong transmitted light. This hue will be found unchanged at the end of twenty minutes, though its intensity will have fallen about one tint, i.e. to (RTI-RT2). The persistency of this hue in acetic-acid solution is the most characteristic part of the test when used to distinguish acetone from its homologues. in the case of acetophenone, the color of portion a is at first red with a very slight tendency to violet-red, just as in part b of the acetone test after acidification. This changes to yellow before the end of twenty minutes. Portion b upon acidification with acetic acid changes at once to a strong blue (B-VB), whose hue is not materially changed at the end of twenty minutes, although it will have faded nearly one tint to about (BTI-VBT1). The most characteristic part of the acetophenone test is the strong blue coloration of portion b. Homologues of acetophenone, CH,.CO.R, like methyltolyl- and methylxylyl ketone, do indeed give pale violet or bluish colorations, but they are much fainter than T3 of the color standard. Fatty-aromatic ketones, like ethyl-phenyl ketone, which contain no methyl radical in combination with —CO.R, appear not to give any blue coloration at all. [Sodium-nitroprusside solution does not keep well, and should not be more than a few days old when used.] 146 SEMI-SPECIFIC TESTS FOR THE KETONES. 147 702. Oxidations with Chromic Acid. The aliphatic ketones and alcohols may all be easily oxidized by chromic acid to mixtures of fatty acids. These mixtures may then often be resolved into their constituents, and the latter identified by forming their silver salts. The method is not especially difficult if the acids are not too near one another in the homologous series. The oxidation of an unsymmetrical ketone or secondary aleohol may occur in two ways; i.e. the splitting of the molecule may take place on either side of the carbonyl or hydroxyl group, as illustrated in the following reactions for the oxidation of ethyl-propyl ketone: CH,.CH,.CO.CH,.CH,.CH, +30 =2CH,.CH,.CO,H, or CH,.CH,.CO.CH,.CH,.CH, +30 =CH,.CO,H +CH,.(CH,),.CO,H. Frequently, however, the tendency for one of the reactions to take place is so much greater than for the other, that only one acid will actually be formed in quantity large enough for isolation. The chromic acid mixture for these oxidations is prepared by dissolving 10 grms. (2 molecules) of crystallized commercial chromic anhydride in a mixture of 60 cc. of water and 8 cc. (3 molecules) of concentrated sulphuric acid. Calculate how much of the mix- ture will be needed for any oxidation, by assuming that each cubic centimeter contains 0.05 grm. of “available oxygen,” and that the reaction will take place according to the theoretical equation without secondary oxidations—which is not strictly true, since some ot the substance will always remain unattacked. Perform the oxidation in a round-bot- tomed flask having a capacity of at least five times the volume of the solution. The flask should be fitted with a return-flow condenser. It is best to use as much as one or two grams of substance for each experiment. Support the flask on a piece of wire gauze, and boil briskly until the reduction of the chromic acid is complete. This will not require more than an hour if the substance is at all soluble in the mixture. Bumping may be prevented by dropping an ebullator tube (cf. p. 223) into the flask before bringing to a boil. The oxidation being ended, connect the flask with an inclined condenser; add a fresh ebullator tube, and distil rapidly until only a few cubic centimeters of liquid remain in the flask. Add 25 cc. more water, and distil again. . If only volatile fatty acids are to be sought, place the combined distillates in a flask. heat nearly to boiling, without attempting to remove any oily or solid matter that may be held in suspension; add an excess of moist silver oxide; and shake persistently to hasten the neutralization of the organic acids. Then dilute with hot water,—from 100 to 1000 cc., according to the solubility of the silver salts that it is expected will be formed,— bring to a boil, and filter hot. Repeat the extraction of the residue on the filter with a second but smaller quantity of boiling water. Filter. Unite this filtrate with the first, and separate the mixed silver salts by fractional crystallization. Since the solubility of the salts diminishes as their molecular weight increases, those of higher molecular weight will separate first, when a saturated solution is cooled or evaporated.* The determination of silver in the salts is made by drying to constant weight at 100° in a porcelain crucible, igniting to destroy organic matter, and then weighing the residue of * In the case of the mixture of silver caproate and acetate, that is formed when 1 grm. of secondary octyl alcohol or methylhexyl ketone is oxidized, a single recrystallization from boiling water of the salt that separates from the original hot saturated solution on cooling, gives a silver caproate that contains the theoretical percentage of silver. The purification of the more soluble silver acetate in the mother liquors requires two or three additional crystalliza- tions, in which the first crystals that separate are each time rejected. The separation of two salts whose acids lie nearer to each other in the homologous series is more difficult. 148 SPECIFIC AND SEMI-SPECIFIC TESTS FOR THE KETONES. metallic silver. The following table gives the percentage of silver, and the approximate solubility of a few of the silver salts of the more important of the fatty volatile acids: Per Cent, Ag. 100 Parts of Water Dissolve Silver Acetate, Ag COH.Oj 0 64.67 at 20°1.04 pts. | at 80°2.52 pts. ‘< ~ Propionate, Ag Oe), cae 59.67 ‘Sa 84.68 ve 2.08 %2 ‘* Butyrate, FW ACA URS). 55.38 EO; 46 cre se bla ‘« Isobutyrate, RE a Bae ae he fou, #40) 0675-5 1500 tas ‘* Valerianate, Agr UC H.O;ees 51.67 eo S0! te ‘70° 0. 64ae ‘¢ ~~ Methy] ethylacetate, pe ame Mock Ay Ls Liss ** 80° 2 eens ‘* ~ Tsovalerianate, le gS ae S s 0:25 ts (tO. 3Gee5 ‘* Caproate, Apc. Ose 48.43 pee si toy ee ‘t. 05345 5 703. Pyrrol-red Reaction for 7-Diketones. Plaee one drop of the ketone if a liquid, or about 0.01 grm. if a solid, in a small test- tube, add 1 cc. of glacial acetic acid, three drops of concentrated ammonia, and a freshly cut splinter of soft pine wood, and boil gently for half a minute. Remove the splinter from the tube and moisten it at once with a drop of concentrated hydrochloric acid. If no pro- nounced color is produced in this way, return the splinter to the test-tube, add five drops of concentrated hydrochloric acid, and boil again for about one minute. y-Diketones of Genus VII, as well as certain species like diethyl diacetylsuccinate in other genera whose symbols contain the group —CO.CH,.CH,.CO— undergo condensation with ammonia in this test to pyrrol derivatives, which, in the presence of the mineral acid, produce an intense red stain upon the wood. With the simple y-diketones like acetonyl- acetone the stain appears instantly and with the greatest brilliancy when the wood is moistened with hydrochloric acid in the first part of the test. The subsequent boiling with hydrochloric acid is, however, necessary to develop the color in the case of bodies like diethyl diacetylsuccinate. 711. Acetone. (Properties tabulated on p. 141.) 1. Apply the color reactions with sodium nitroprusside described in Test 701, bear- ing in mind that since nearly all soluble ketones and aldehydes give colorations of some kind when thus treated, the result will be significant only when the colors obtained corre- spond closely to the specified hues of the color standard. This procedure is to be especially recommended for the preliminary examination of aqueous solutions and distillates supposed to contain at least several per cent of acetone. In examining such a solution, simply substitute 2 cc. of it for the same volume of the solu- tion of definite concentration prescribed in the general directions. Very dilute solutions should first be somewhat concentrated by a rectification with the assistance of a small distilling-tower. If a solution contains only 1% of acetone, the color of “portion a” will at first be yellow-orange (YO), instead of orange; while “portion b,” with acetic acid, will give a very pale tint of red, R%'S, instead of R-RT1, which, after standing for twenty minutes, will fade to a tone of the same hue, but so pale as to be barely distinguish- able. 2. Place in a dry six-inch test-tube two drops of the ketone and 0.4 cc. of cold water. Add 0.4 cc. of benzaldehyde, 2.0 cc. of strong alcohol, and 0.5 cc. of a ten per cent aqueous sodium-hydroxide solution. Mix by shaking. Boil very gently over a small flame for one minute, counting the time from the moment when the mixture first actually boils. Tf no precipitate appears, cool and shake vigorously. Filter off the crystals,* and wash ~ ¥ If the precipitate, instead of consisting of crystals, is an oil or pasty mass, the procedure given requires no modification. Such products usually become crystalline, either during the washing with alcohol, or upon the cooling of the solution prepared from the washed oil. SPECIFIC TESTS FOR THE KETONES. 149 with 2 ce. of cold strong alcohol. Recrystallize from 2 cc. of boiling alcohol. Cool, and, if necessary, shake persistently until crystals appear. Filter. Wash with 1 ce. of cold alcohol. Press on filter-paper or porous tile. Then transfer to a watch-glass and dry half an hour or longer at 100°. In taking the melting-point raise the temperature at the rate of about one degree in twenty seconds. The product formed in this test is dibenzylideneacetone (C,H;.CH:CH),.CO. It crystallizes in pale yellow lustrous plates which melt at 111.0°-112° (uncor.). Observations on the application of Procedure 2 to aqueous solutions of acetone.—lIf a solution contains less than 75% of acetone, take 1 cc. instead of two drops as above directed, and add no water. The quantities of the other reagents and the method of procedure may be allowed to remain unchanged. The test has been used for solutions containing as little as 2% of acetone. But with solutions between 5% and 2%, cooling and shaking after heating frequently gives only an emulsion. The addition of 1 cc. of strong cold alcohol and shaking will, in such cases, produce a crystalline precipitate, which can then be treated in the usual manner. If the quantity of crystals obtained from an acetone solution after the first filtration is small, wash with 1 cc. of alcohol (instead of 2.0 cc.), and recrystallize from 1 cc. of boil- ing alcohol (instead of 2 cc.). If no crystals then appear on cooling and shaking, add cold water (0.5 cc.-1.0 cc. is usually enough) until the solution becomes turbid. Shaking will then produce crystals. Wash these with 0.5 cc. of cold alcohol (instead of 1 cc.). Crystals thus obtained from dilute alcohol will be found to melt at 0.5°-1.5° lower than those from strongalcohol. It is, on the whole, advisable to concentrate very dilute acetone solutions by distillation rather than to test them by this method at very low concentrations. For the detection of traces of acetone by this method, see Vorlander, Hobohm B. 29, 1840. 712. Acetophenone. (Properties tabulated on p. 136.) 1. Apply color reaction 701 with sodium nitroprusside. This is a very satisfactory and simple preliminary test. A single drop of the ketone will be enough for the prepara- tion of the saturated aqueous solution required. If a negative result is not obtained in the experiment, proceed to part (2) of the test, which follows. 2. Place two drops of the ketone and four of phenylhydrazine in a dry test-tube. Heat until the mixture begins to boil. Cool. Add ten drops of glacial acetic acid, then 10 ce. of water, and shake. Collect on a filter and wash thoroughly with water. Dissolve in 12 ce. of boiling 50 per cent alcohol. Allow to cool. Filter off the abundant precipitate of thin flat ervstals, and wash with 2 cc. of cold 50 per cent alcohol. Remove the mother- liquor by pressing on a porous tile, and recrystallize from 12 cc. of boiling 50 per cent alcohol. Allow to cool slowly. Filter. Wash with 3 cc. of 50 per cent alcohol. Remove the mother-liquor on a porous tile, and then dry ten to fifteen minutes at 50°-60° in the dark. Determine the melting-point at once. Acetophenonephenylhydrazone is a rather unstable body, and is liable to undergo slight decomposition in drying. According to Reisenegger and Just, the pure compound melts at 105°. As obtained in this test it is perhaps not perfectly pure, as it shows signs of softening at 100°, and is completely melted at 103°. 713. Benzoin. (Properties tabulated on p. 139.) Place in a dry test-tube 0.05 grm. of the compound and 0.4 ce. of acetyl chloride. Add one drop of concentrated hydrochloric acid. Allow to stand two or three minutes, until the vigorous action that will occur ceases. Then heat very gently over a small flame until everything is dissolved, removing the tube from time to time to prevent overheating. Cool with running water for 5-10 seconds. Add 2.5 cc. of strong alcohol, and then 5 cc. 150 SPECIFIC TESTS FOR THE KETONES. of cold water. Cool well, and shake until the precipitate has separated sufficiently to leave the mother-liquor nearly clear. Filter. Wash with 2 cc. of cold dilute alcohol (1:2). Heat te boiling with 9 cc. of dilute alcohol (1 : 2). Boil briskly for 10-15 seconds, and filter hot from any undissolved residue. Cool and shake as before. Filter. Wash with 2 cc. of cold dilute alcohol (1 : 2). Remove mother-liquor by pressing on a piece of porous tile. Dry in the air on a fresh piece of porous tile for 20-30 minutes. The product in this test is acetylbenzoin, crystallizing in small white needles and melting at 79.5-80.5 (uncor.). 714. Benzophenone. (Properties tabulated on p. 137.) Convert 0.05 grm. into benzophenoneoxime, following the regular procedure of Generic Test VII-1, except that the period of heating should be extended to ten minutes. After the precipitation of the oxime with acid, collect in the point of a small filter, and wash thoroughly with 10-15 ec. of cold water applied in small successive portions. Dry for half an hour at 100° on a piece of porous tile, and determine the melting-point. Benzophenoneoxime is obtained in this test as a flocculent white precipitate soluble in acids or caustic alkalies, and melting at 141°-142° (uncor.). 715. Camphor. (Properties tabulated on p. 139.) Convert into camphor oxime by the method of Generic Test VII-1, using twice the specified quantities of substance, hydroxylamine-hydrochloride solution, and caustic-soda solution, and boiling for one hour instead of for five minutes. In all other details follow the general directions literally. After the precipitation of the oxime following the neutralization with acid, collect on a very small filter, and wash with at least 10 cc. of cold water applied in small portions, the filter being allowed to drain after each addition. Transfer the washed precipitate from the point of the filter to a piece of porous tile. Dry at about 50°, and determine the melting-point. Camphor oxime as obtained by the foregoing method is a white, indistinctly crystal- line powder melting at 118°-119° (uncor.). CHAPTER X. GENUSSY Lipa LGOn@is OF SUBORDER I, ORDER I. (Colorless Compounds of Carbon, Hydrogen, and Oxygen.) Genus VIII embraces all species of the suborder that contain the hydroxyl radical and have not been described in the foregoing genera. The few ketones that do not react readily with hydroxylamine or phenylhydrazine, but meet the requirements of Test VIII for alcohols, also receive mention in this section of the tables. GENERIC TEST VIII. IF THE COMPOUND UNDER EXAMINATION IS SOLUBLE IN LESS THAN FIFTY PARTS OF COLD WATER, SEE PROCEDURE 1 BELOW, THE APPLICATION OF PRO- CEDURES 2 AND 38 BEING UNNECESSARY. IF IT DOES NOT DISSOLVE IN FIFTY PARTS OF COLD WATER AND IS A LIQUID AT THE TEMPERATURE OF 75°, APPLY PROCEDURE 2 ONLY. IF IT IS NOT SOLUBLE IN FIFTY PARTS OF COLD WATER AND IS SOLID AT OR BELOW ‘75°, SEE PROCEDURE 38. PROCEDURE 1. (The Test by Solubility.) If the solubility of the compound in cold water is not already known, deter- mine it approximately by the method given on p. 38. Any compound, either solid or liquid, that has failed to give the earlier generic tests, and which is completely dissolved by fifty parts of water at 20°, can not be a hydrocarbon, and should be looked for among the species of Genus VIII. PROCEDURE 2. (The Test with Sodium.) If the compound is not soluble in fifty parts of cold water and is a liquid at temperatures below 75°, place about five drops in a narrow glass “ weighing-tube ”’ (internal diameter 5-6 mm., length 75 mm.) that has been carefully dried out just before use. Support the tube in a vertical position by thrusting it through a perforated cork held in a clamp. Place a piece of clean sodium, from which the crust has been removed, in a small porcelain dish containing a clear dry hydrocarbon oil. Grasping the sodium under the oil with crucible tongs or forceps, cut out a bright bit of the metal, about half as large as a grain of wheat (.01—.02 grm.), by the aid of a penknife. Seize the fragment with the forceps. Touch it quickly to a piece of dry filter-paper to remove most of the adhering oil; and then, without delay, drop it into the liquid in the weighing-tube. Allow to stand at the tempera- ture of the laboratory for two minutes, and observe any disengagement of gas, or change in appearance of the metal. 151 152 ALCOHOLS. At the end of this time, if the sodium has not disappeared, lower the clamp holding the tube so as to immerse the end of the latter in clear paraffin oil, the sulphuric acid mixture described on page 218, or any other anhydrous non-volatile liquid, previously heated to 75°, and contained in a beaker supported on a lamp- stand.* Continue the heating with the bath at 75° for about five minutes, carefully watching for the disengagement of gas, and for the disappearance of the sodium, or the formation of any incrustation or coloration on its surface. [The test at 75° will be omitted in the case of compounds that boil below this temperature.] If a brisk effervescence, which continues well sustained until the sodium is either dissolved or the contents of the tube are changed to a thick paste, takes place in either part of this test, the compound is an alcohol. If the evolution of gas is rather slow, but is nevertheless well sustained after the first minute—espe- cially if the bubbles approach the size of a small pin-head, or if the sodium shows signs of being more than superficially attacked—the compound is very likely to be found described with the alcohols. If there is no effervescence, and the sodium remains unattacked during both parts of the test, the compound is not an alcohol. The same conclusion is usually to be drawn whenever there is a very scanty gas evolution which diminishes percep- tibly after a minute or two—especially if the bubbles (which may be quite numerous) are nearly all microscopic in size. [For remarks on the interpretation of doubtful cases, read the ‘‘ observations” on this test on page 154.] PROCEDURE 3. (The Test by Acetylation.) As the test by acetylation is rather long, and is often not indispensable, it is well to precede its application by an examination of the descriptions of species having the proper melting-point both in Genus IX, Div. A, and in Genus VIII, Div. A, Sec. 3. If this does not lead to an identification, the employment of the acetylation test which follows will sometimes become desirable. Weigh out accurately in a dry, thick-walled, six- inch test-tube, standing upright in the metal support usually furnished with analytical balances for such uses, 0.1000 to 0.1100 grm. of the unknown com- pound. A soft, sound, tight-fitting cork stopper = Peer Ss e— y-—) w * Vig. 4 represents a convenient form of bath for general use in heating small tubes to definite temperatures in Tests V—1, VII-1, and some of the numbered specific tests, as well as in the present procedure. The beaker has a height of 10 cm. and a diameter of 7.5 cm. The cover is best made from brass, or may be constructed from tinned iron or wood. Its three perforations are fitted with cork stoppers to bear the tubes and a thermometer. The diameters of the two larger perforations should be 23 to 25 mm. The cover, be- sides supporting the tubes, protects their upper portions from the radiated heat of the bath—which in some tests is a considerable advantage—and excludes dust when the bath Fig. 4. is laid aside between experiments. ALCOHOLS. 153 should be provided for the tube, and weighed with it. The substance having been weighed, drop in upon it—best from a safety pipette especially reserved for the purpose (cf. page 236)—0.40 cc. of good acetic anhydride, taking care not to allow the anhydride to wet the upper part of the tube, and ascertain the exact weight of the anhydride by weighing again. Next remove the cork, which must be inserted during the weighings, and hold the lower part of it, which will come within the test-tube, in clean hard paraffin that has been melted and heated to above 100° in a small porcelain evaporating-dish. The immersion in the hot paraffin should be continued for about half a minute, or long enough to bring about the expulsion of all the small air-bubbles that are seen to detach themselves from the cork as the hot paraffin penetrates and fills the minute cavities in its surface. By a quick movement shake off most of the excess of paraffin, and then quickly insert the cork in the test-tube; press it firmly into place; and hold it until the wax hardens. Next thrust the tube through a circular hole cut by a brass cork-borer in a square piece of asbestos-board, and place the latter like a cover on a small beaker, so that the lower end of the test-tube shall be 1 cm. below the surface of the hot liquid bath within. The beaker is filled to within 2 cc. of its lip with paraffin- or cottonseed-oil, glycerine, concentrated sulphuric acid, melted paraffin, or some other stable liquid of high boiling-point, which has previously been brought to a nearly constant tem- perature of between 95° and 105° by heating with a very small flame. Or, if such an apparatus is at hand, heat the tube in the covered bath shown in Fig. 4 on page 152. Continue the heating at this temperature for fifteen minutes. Then remove the tube from the bath; cool; unstopper; and add 10 cc. of normal aqueous sodium- hydroxide solution from an accurately calibrated 10-cc. pipette. Reinsert the stopper firmly, and shake well, cooling with running water from time to time tf the mixture tends to become warm. Again remove the stopper and wash it with distilled water, collecting the washings in a 75-cc. beaker. If the undissolved reaction product is solid or pasty, it may enclose unneutralized acetic anhydride. Hence the lumps must now be well crushed and churned up, while still in contact with an excess of alkali, by means of a glass rod with a flattened end. Then, rinse the mixture into the beaker containing the washings from the stopper, and titrate the free alkali with decinormal hydrochloric or sulphuric acid, using phenolphthalein as the indicator. Finally, calculate from the data obtained how many milligrams of the acetic anhydride heated with the substance have combined with it to form a neutral acetate. If the loss of anhydride due to this cause (“acetylation”) exceeds 6 mgrms. when 0.1000 to 0.1100 grm. of substance was weighed out for the experiment, the compound is probably an alcohol, and should be sought in Genus VIII. If the loss of anhydride is less than 6 mgrm., it is probably not an alcohol, but may be a species described in Genus IX. The calculation of the weight in milligrams of the anhydride con- sumed in acetylation will be facilitated by substituting the proper quantities in the following formula: Wt. in milligrams of anhydride consumed =a—[51.6(d-e)]. In this formula: a=merm. pure anhydride* weighed out (i.e. apparent wt. X percentage purity). * A 100-cc. bottle of an anhydride whose percentage purity has been determined by careful titration should be specially reserved for these tests. The reagent will always contain traces 154 ALCOHOLS. b=the exact normility of the approximately decinormal acid. Gem Bet a aay - normal alkali. d=cce. of above acid equivalent to 10 cc. of above alkali.* reek Ona le “required to neutralize alkali remaining uncombined (from 10 ce. por- tion) after shaking with products of acetylation experiment. Observations on Generic Test VIII. “ The Test by Solubility (1)”’ requires no special comment. In “ The Test with Sodium (2)” the correct interpretation of the phenomena requires good judgment and some experience on the part of the observer. Very few commercial specimens of compounds of Genus IX are so free from traces of moisture as to give off no gas at all. The ability to make the right decision is most quickly gained by examining the behavior of a few representative compounds. Heat is employed in the second part of the test, partly to increase the number of species to which it is applicable, and partly to make the result more decisive when the alcohol is one that is attacked slowly in the cold. The temperature of 75° is one at which it is not known that any species of Genus LX is decomposed by sodium. At a much higher temperature, however, sodium attacks some of the hydrocarbons (e.g. melted anthracene) with considerable violence. Whenever the sodium test proves inconclusive, it may be supplemented by Procedure 3. ! “The Test by Acetylation (3),” although requiring careful manipulation, will give no trouble if directions are closely followed. But if the cork stopper is not protected by paraffin, or if the test-tube is heated on a rapidly boiling water-bath so that the paraffin softens, or if a rubber stopper is used, the results will be worthless. The average accidental loss of acetic anhydride in a properly conducted experiment is a little less than 1 mgrm. Heating with the anhydride at 100° for fifteen minutes as recommended in the regular procedure is insufficient to com- pletely acetylate many of the solid alcohols; but it appears that most monatomic alcohols whose acetates are insoluble in cold water will be found to combine with very nearly the theoretical quantity of anhydride if the heating is prolonged to thirty minutes. Procedure 3 is not yates to soluble polyatomic alcohols of Div. A Sec. 1, because they usually give soluble acetates which are rapidly saponified upon shaking with cold normal alkali. No more acetic anhydride is found to dis- appear in an acetylation experiment with ethylene glycol or erythrite, for instance than in a blank test. of acetic acid, but it will be allowable, for the present purpose to base the calculation of the per- centage purity on the assumption that all alkali consumed in the titration is neutralized by anhydride only. On account of its peculiar action on phenolphthalein, in titrating acetic anhydride, always dissolve it first in an excess of alkali, and then add the indicator and titrate back with acid. * d= 10 - Calculations will be simplified by recording the numerical value of d on the label of the alkali bottle. COLORLESS COMPOUNDS CONTAINING OC, H, AND O [SUBORDER I OF ORDER Th GENUS VIII, ALCOHOLS. DIVISION A, SECTION 1,—SOLID ALCOHOLS SOLUBLE IN LESS THAN 50 PARTS OF COLD WATER. [Containing all soluble solid species of the suborder not described in the preceding genera.] os ia SOLID ALCOHOLS.—Colorless and soluble in less than 50 parts of cold water. 35-8 7 Pinacone, Me,.C(OH).C(OH).Me,.—B. p. 172°-3°.—Clear cryst. w. faint pecu- liar odor.—S. c. aq.; e. s. h. aq. or c. ale.—Boiled w. dil. H,SO, gives a very strong peppermint-like odor of pinacoline !—The hot aq. sol. on cooling de- posits a hydrate, m. p. 56°. 46-7 m-Tolylene Alc., C,H,.(CH,.OH),.—V. s. aq.; s. eth.—Oxidation gives iso- phthalic ac. (Tests 905 and 318-2). 49-5 (a)-Dimethylpinacone, Et.C(OH)(Me).C(OH)(Me).Et.—Fairly s. aq.; e. s. alc. or eth. 51-5 Diisopropyl Glycol, Pr.CH(OH).CH(OH)Pr.—B. p. 222°-3°.—E. s. alc., or eth.— Combines w. CaCl,. 52-3 tert.-Butylcarbinol, Me,.C.CH,.OH.—B. p. 112°-3°!—Odor camphorous.— ‘‘Somewhat”’ s. aq.—Test 702 gives trimethylacetic ac——Very volatile. 52-3 Methylphenylethylene Glycol, Me.CH(OH).CH(OH).Ph.—E. s. aq., alc., or eth.— Tends to separate oily fr. solutions. 56 Pinacone Hydrate, C,H,,0,.6H,O.—4-sided tbl—Sbl. at ord. temperature.— Loses aq. over H,50O,, or on dist., giving pinacone.—H. s. h. aq. 64 Phthalic Alc., o-C,H,.(CH,.0H),.—Tbl. fr. eth.—V. s. aq., alc., or eth.—Conc. H,SO, resinifies—Test 905 gives phthalic ac. 67-8 Styrolene Alc., Ph.CH(OH).CH,.OH.—B. p. 273° (th. i.).—V..s. aq., alc., or eth. —Oxid. by Test 702 to benzoic ac. (Test 312) —65% H,SO, gives hydro- carbon, C,,H,.. 87 Isomannide, C,H, ,0,.—B. p. 274° d.—Hygroscopic cryst., v. s. aq.; 8. alc.; 1. eth.—Warmed w. 2 pt. PCl, gives chloride, m. p. 49°. 102 {[—]Arabite, C,H,.(OH),.—Warty masses, v. s. aq. or h. 90% alc.—Does not reduce Fehling’s sol.—Aq. sol. + borax weakly opt. act. [—]. 112-13 p-Tolylene Alc., C,H,.(CH,.OH),.—Ndl., v. s. aq., alc., or eth.—Oxid. by Test 702 gives terephthalic ac. (Test 318-3). 121 Rhamnite, Me.(CH.OH),.CH,.OH.—Triclinic pr. fr. ale.—Opt. active.—V. s. aq. or alc.; alm. 2. eth. 126 } Erythrite, C,H,.(OH),.—B. p. 330°.—Clear cryst.—Taste sweet.—V. s. aq.; d.s. ale.; i. eth.—Does not reduce Fehling’s sol —The aq. sol. dissolves CaO in the cold. The sol. coagulates on boiling —Schotten-Baumann reaction gives tetrabenzoate, mic. cryst. fr. Ac, m. p. 186-5°-7°. 150 Pinolhydrate, C,,His0,.—B. p. 270°-1°.—S. in 30 pt. aq. at 15°; e.s. alc. or eth.! Br, dropped into cooled 5% CHCl, sol. gives cryst. dibromide, d. s. CHCl, m. p. 131°-2°.—Warmed w. dil. H,SO, gives oily pinol, b. p. 183°-4°. 163-4 [—]Mannite, C,H,.(OH),.—Nadl., v. s. aq.; d.s. absolute alc.—Aq. so]. + borax is strongly [—]. 166 +[+]Mannite, C,H,.(OH),.—Taste sweet.—NdL., s. in 6-4 pt. aq. at 18°; v. d. s. abs. alc.; i. eth.—Aq. sol. + borax is strongly [+]; alone is opt. i.—Pre- vents ppt. of Fe,O, fr. FeCl, by NaOH.—Oxid. by HNO, (cf. Test 205) gives no mucic ac. (dif. fr. dulcite).—Sbl. slowly when kept for some time at tem- perature somewhat above m. p.—1.8 pt. mannite dissolved in 3.6 pt. conc’ HCland shaken with 3.2 pt. benzaldehyde gives cryst. ppt. of mannitetri- benzacetol, m. p. 207°; v. d.s.aq.; s. eth.! 155 156 Melting-point (O28): 168 173 184-5 188c, 188-5 203c. 225c. 234 or 225 (?) 253 GENUS VIII, DIV. A, SECT, 1. (ORDER I, SUBORDER I.) SOLID ALCOHOLS.—Colorless and soluble in less than 50 parts of cold water. i.-Mannite, C,H ,.(O0H),.—Plates v. s. h. aq.; v. d.s. abs. ale.—Aq. sol. + borax is optically 1. Rhamnohexite, Me.(CH.OH) ,.CH,.OH.—Pr., e. s. aq.; s. h. ale.—Opt. act. [+], I, 3,5-Cyclohexantriol (Phloroglucite), C,H,.(OH),.—Cryst. fr. aq. Faint but pure sweet taste. (Cryst. w. aq. which is easily expelled at 100°.)—E. s. aq. or alc.; 1. eth. [+ or —]Perseite, C;H,,O;,—Ndl., s. 18 pt. aq. at 18°; d.s. c. ale.—Aq. sol. opt. i—Does not reduce Fehling’s solution. Dulcite C,H,.(OH),.—Nearly tasteless.—Cryst. s. in about 25 pt. c. aq.; e.s. h. aq.; alm. i. alc. or eth.—Oxid. by HNO, (cf. Test 205) yields some mucic ac. !—Opt. i. even after addition of borax to sol.—Reactions similar to those of mannite. rac.-Perseite, C,H,.(OH),;.—Cf. [+ or —] compound, m. p. 188° ¢. Inosite, C,H,.(OH),.—Taste sweet.—Efflorescent cryst. w. 2H,O fr. cold aq.; cryst. fr.aq. above 50° anhydrous.—4. in 5-7 pt. aq. at 24°; i. abs, alc. or eth. —Opt.i— ‘Abit of inosite evaporated to dryness w. a little dil. HNO, on a crucible cover gives a reddish-colored mass when treated w. a little ammonia and CaCl, and again evaporated.” [+] Quercite, C,H,.(OH),.—Cryst. s. in 8-10 pt. c. aq.; d.s. ale.; i. eth. Boiled w. dil. H,SO, and MnO, gives pungent quinone odor.—Oxid. by HNO, gives oxalic ac., but no mucic ac. (ef. Test 205). Pentaerythrite, C.(CH,.OH),.—Tetragonal cryst. s. 18 pt. aq. at 15°.—Opt. i— Oxid. by dil. HNO, to glycollic and oxalic acids. SMLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER J]. GENUS VII, ALCOHOLS. DIVISION A, SECTION 2,—SOLID ALCOHOLS NOT SOLUBLE IN 00 PARTS OF COLD WATER. seb ae vont Bena point SOLID ALCOHOLS.—Not soluble in 50 parts of cold water. 24 143-5(15 mm.)| Dodecyl Alc., C,,H,,-OH.—Silvery Ift. fr. dil. alc. 27-8 s-Tetramethylpinacone, Et,.C(OH).C(OH).Et,.— Alm. i. aq.; v. s. alc. or eth. 33 254 } Cinnamyl Alc., Ph.CH:CH.CH,.OH. — Aromatic hyacinth- like odor —D. s. aq.; v. s. alec or eth. Dropping Br in cold CHCl, solution gives bromide, m. p. 74°; 1. aq.; e. Ss. alc. or eth. 34 223 (th. i.) GN el none Me.C,H,.CH,.OH.—S. 100 pt.c. aq.; e.s. alc. or eth. 35 218 Terpineol, C,,H,;,0H.—Cf. Div. B, 2, b. p. 218°.—Lilac odor! 38 167(15 mm.) | Tetradecyl Alc., C,,H...OH. 41-2 Dihexylcarbinol, (C,H,,),.CH.OH.—V. s. CHCl, or bz. 42 210 +[—]-Menthol, C,,H,,.OH.— Cryst. w. strong peppermint odor!—D. s. aq.; e. s. ale, eth., or conc. HCl.—May be identified by conversion into its benzoate of m. p. 54-5°. (Cf. Beckmann, A, 262, 31.) 42 dist. Phenylbenzylcarbinol, Ph.CH,.CH(OH).Ph.—Boiling w. 20% H,SO, gives stilbene. 45 258-8 Anisic Alc., p-MeO.C,H,.CH,.OH.—Conc. H,SO, gives a reddish resin.—Oxid. by dil. HNO, gives anisic ac. 50 344 + Cetyl Alc., C,,H,,0.—Cryst. in small lft. fr ale-—(When fused gives off H easily in Test VITI-2.) 51 Piperonyl Alc., CH,O,.C,H,.CH,.OH.—Dec. on dist. w. forma- tion of piperonal (heliotrope odor) !—Long cryst. not vol. w. st.—D. s. c. aq.; v. 8. alc. or eth. 52-3 p-Phenyltolylcarbinol, Me.C,H,.CH(OH).Ph.—Silky ndl. 52-3 tert.- Butylcarbinol.—Cf. Sec. A. (‘‘Somewhat s. aq.’’) 54-4-5 220d. a-Oxyhydrindene, C,H,.OH.—Naphthalene-like odor. 59 210-5(15 mm.) | Octadecyl Alc., C,,H;,,.0H.—Silvery lft. fr. alc. 59 217 sha ieerk ri) Me.C,H,.CH,.OH.—D. s. c. aq.; e. s. ale. or eth. 60 303c. a-Naphthylmethyl Alc., C,,H,.CH,OH.—Ndl., somewhat s. . aq.; ¥. 8: ale or. eth, 67 -5-8 297-8 Benzhydrol, Ph,.CH.OH.—Silky ndl., s. in 2000 pt. c. aq.; v. s. alc. or eth.—Kasily oxid. in Test 702, giving ben- zophenone (Test 714). 68-9 Carnaubyl Alc., C,,H,.OH.—CrO, gives carnaubic ac.—Fr. dil. alc. cryst. w 73-3% aq. 69 Ditolylcarbinol, (C;H,),.CH.OH.—I. aq.; v.s. alc. 75 220(15 mm.) | Cetene Glycol, C,,H;..(0H),.—I aq.—Cryst fr h. alc 75-6 Dilauryl Alc., (C,,H,,),.CH.OH.—Tbl. fr. eth. 79 | Ceryl Alc., C,,;H,;.0H.—S. alc—Heated w. soda-lime gives cerotic ac. 157 158 GENUS VIII, DIV. A, SECT. 2. (ORDER I, SUBORDER 1.) Melting-point B oiling-point (C.°). (Coy; SOLID ALCOHOLS.—Not soluble in 50 parts of cold water. 80-0-5 @-Naphthylmethyl Alc., C,,H,.CH,.OH.—Lft. e. vol. w. st.— V. iG. ¢24030e. Seale or-eth: 82 Cerosine, C,,H,,O.—Lft. i. c. ale.; d.s.h. eth.; alm. i. c. eth. 84-5 Dipalmitylcarbinol, (C,,H;,),.CH.OH.—Silky cryst. fr. alc. 85 Myricyi Alc., C;,H,,.0H (fr. carnauba wax).—Small ndl- fr. eth.—W. soda-lime at 200° gives melissic ac. 90 Methyl-p-tolylpinacone, C,,H,,.(OH),.—Sbl.—Hexagonal tbl. fr. alc.; 1, aq.,.v. 8. ale. or eth, 101-4 Coccerylic Alc., C;,H,.0,.—Cryst. powder fr. ale.—Oxid. by CrO, in Ac sol, gives pentadecylic ac.—(Fr. cochineal.) Isohydrobenzoin, C,,H,,.(OH),.—Cryst. fr. aq.; efflorescent.— S. in 526 pt. aq. at 15°, or 820 pt. at 100°; e. s. ale. or eth.—Oxid. by Test 702 gives benzoic ac.—Diacetate (fr. acetyl chloride), lft. fr. h. ale.; m. p. 117°-18°. Acetophenonepinacone, (Ph.C(OH).Me)..—Ndl., i. aq.; e. s. alc. or eth.—In tube at 280° gives acetophenone and methylphenylcarbinol—Acetic anhyd. gives a _hydro- carbon, C,,H,,. Quebrachol, C,,H,,.0H. — Lft. fr. ale——Cryst. also w. x H,O (easily lost).—I. c. aq: or alkalies; v. s. eth., bz., or ace- tone.—A sol. in CHCl, shaken w. equal vol. of H,SO, (sp. gr. 1-76) becomes purple-red after 5 minutes. Phytosterine, C,,H,,.0H. — (In peas, beans, etc.) — From CHCl, or eth. in ndl.; cryst. fr. dil. ale. w. 1H,0.—S. in 6-65 pt. eth. at 20°.—Color reactions w. H,SO, same as for cholesterine. (Cf. m. p. 148-5°.)—Acetate, lft. fr. alc., m, psi120°. Retenefluorene Alc., C,,H,,,OH.—Silky ndl., fr. ale.— Alm. i. aq.; e. s. ale.—Oxid. gives retene ketone.—Acetate, m. p. 70°-1. Paracholesterine, C,,M,,00H.—(In Aethalium septicum.)— Cryst. w. aq. fr. dil. alc.; silky ndl. fr. eth. or CHCl,; i. aq. —Gives same color reactions as cholesterine w. H,SO, in CHCl, sol. Isocholesterine, C,,H,,.0H.—(In suint.)—Gelatinous flocks fr. alc., d.s.c. alc.; e. s. h. ale. or eth.—Does not give the cholesterine reaction w. H,SO, and CHCl, but gives a brown color.—When evaporated w. a few drops of conc. HNO, leaves yellow spot which becomes yellow-red w. ammonia. Hydrobenzoin, Ph.CH(OH).CH(OH)Ph.—B. p. a. 300°.—Ad- amantine lft. fr. dil. alc.; s. in 400 pt. c., or 80 pt. h. aq.; e. s. h. ale-—Oxid. by CrO; gives benzaldehyde.—E. acted upon by PCI, in cold.—Heated w. acetyi chloride or anhydride gives diacetate, pr. fr. eth., d. s. c. ale., m. p. 134°. Cholestol, C,,H,,0. — Ndl.— Dist.— With CHCl, or acetic anhyd. and H,SO, gives the same colors as cholesterine. Cupreol, C,,H,,.0H.—(In cinchona barks.)—Cryst. w. aq. which is lost in desiccator.—I. aq.; e. s. eth.—CHCl, sol. shaken w. H.SO, (sp. gr. 1-76) gives blood-red color.— Opt. active [-— ]. { Cholesterine, C,,H,,.OH.[-+H,0, lost over H,SO,].—Dist. in vacuo above 360° —S. in 5 pt. h. ale.; ¢.s. eth. or CS,.— Dissolve a few cgrms. in 2 cc. chloroform and shake w. 2 cc. H,SO, (sp. gr. 1-76). The CHCl, becomes blood-red, cherry- red, and finally a beautiful purple color w. strong green fluo- rescence in the acid layer. The CHCl, poured into a dish soon changes through blue and green to a dirty yellow!—This color reaction is also given by several other alcohols stand- ing near cholesterine in this section.—Identify by Test 821 ! 119-5 120 125 132-3 133-4 134-4-5 137-8 138 139 140 148-5c. A RR I GENUS Vill, DIV Ay SHOT. 2, 159 (ORDER I, SUBORDER I.) eas te SY ees uaa SOLID ALCOHOLS.—Not soluble in 50 parts of cold water. 149-50 Paraphytosterine, C,,H,)..OH.—D. s. c. alc.; e. s. eth. or CHCl. 150 Diphenyltolylcarbinol, Me.C,H,.C(OH).Ph,.— Hexagonal tbl. fr. Igr.—E. s. alc. or eth.; less s. lgr.—Dist. undec. 153 Fluorene Alc., C,;H,.OH.—S. alc., eth., orbz.—W. conc. H,SO, turns blue !—Oxid. by Test 702 gives diphenylene ketone. 154 Ergosterine, C,,Hj..0H.+H,O (from Ergot).—B. p. 185° (20 mm.).—Pearly lft. fr. ale.—S. in 500 pt. c. or 32 pt. h. 94% alc.; s. h. eth. or c. CHCl,.—Sol. in conc. H,SO, is orange- red, becoming red and then violet on addition of aq. The orange sol. when shaken w. CHCl, does not color the latter. (Dif. fr. cholesterine.) 162 { Triphenylcarbinol, Ph,.c.OH.—B. p. a. 360° undec.— HE. s. alc., eth., or bz.—Stable. 164-5 Phenyltolylpinacone, C,,.H,,.(O0H),.—E. s. bz.; d.s. ale.; s. eth. —H. oxid. by CrO, giving phenyltolyl ketone.—Decomposed by heating with acids. 166-7 Chrysofluorene Alc., C,,H,,.CH.OH.—E. s. alc. or eth.—S. conc, H,SO, w. red-violet color.—Alc. sol. on addition of conc. H,SO, becomes blue. 168d. Benzopinacone, Ph,.C(OH).C(OH)Ph,.—S. in 39 pt. h. ale-—In melting splits into benzophenone (Test 714) and diphenyl- carbinol. 170 Hydranisoin, C,,H,,0,.(0H),.—V. d. s. c. aq., c. ale., or eth.; e.s. h. ale.—Oxid. by CrO, mixture to anisic ald. and anisic ac. uy ge Illicyl Alc., C,.H,,OH. (fr. bird lime).—B. p. a. 350°.—I. aq.; d.s.c. alc. or eth.—M. p. acetate 204°-6°. 182d. Anthrapinacone, C,,H,,.(OH),.—Nadl. fr. bz. 183 Homocholesterine, C,,H,.0. (fr. Dalmatian insect powder).— V. s. eth. or CHCl,; d.s. ale-—Gives the cholesterine color reactions. 192 sl. d. Camphene Glycol, C,,H,,.(OH),.—Sbl. above 100°.—D. s. h. aq.; V..S; ac, or eth,; d.s. ler: 203-4 + [+ ]}Borneol ( Borneo Camphor), C,,H,;.0H.—B. p. 211°-12°.— Sbl. in lft.—Odor scarcely distinguishable fr. that of com- mon camphor !—E. s. lgr.; v. d. s. aq.; e. s. ale. or eth.— Does not give an oxime. (Dif. fr. ordinary camphor.) 208-8 [—]}Borneol, C,,H,;,,0H.—Closely resembles the [+] comp.— (Occurs in several natural oils.) 210-5 i-Borneol, C,,H,;.0H.—Closely resembles the [+] comp. 216 Isoborneol, C, ,H,;,0H.—Closely resembles the [+ ] comp.—Opt. active [+ ]. 258c. Betulin, C,H,O, (fr. birch bark).—Ndl. fr. ale.—Sbl. w. dec. —S. in 148 pt. cold, or 23 pt. h. alc.; s. h.eth.; d.s.c. eth.— Heated w. acetic anhyd. gives diacetate, pr. s. eth., m. p. 217°.—Emits odor like morocco leather when strongly heated. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER 1 OF ORDER I]. GENUS VIII, ALCOHOLS. DIVISION B, SECTION 1,—LIQUID ALCOHOLS (AND SOLUBLE ETHERS) WITH SPECIFIC GRAVITY LESS THAN 0-90 AT 20°/4?°. Boiling-point (C32). —24 +10-8 14 35 35 35-5 38-9 39 45-5 46 50 51-2 54 56-7 61-2 62-3 62-3 63-6 66 66 69c. Specific Gravity. 0-725(0) 0-897(0) 0-71915/, 0-859(0) 0 . 16350 7h os 0-747(0) 0+ 87215/, 0-77(11) 0-831(0) 0-745(0) 0-834(0) 0-83(12) 0-769(20) 0-755(0) 0-79815/, . 0-725(21) ALCOHOLS.—Colorless and liquid, with Specific Gravity less than 0-90 at 20°/4°. Methyl Eth., Me,.0.—Is absorbed in large quantity by c. cone. H,SO,; the sol. on dil. w. aq. evolves the gaseous ether un- changed. Methyl Ethyl Eth., Me.0.Et.—Odor ethereal. Ethylene Oxide, C,H,O.—Misc. w. aq.—Aq. sol. reduces Tollen’s reagent.—f Gives ppt. of MgO after long standing w. cone. MgCl, sol—W. HCl gives chlorhydrine.—W. aq. and Na amalgam gives C,H,;.OH. { Ethyl Eth., Et,.0.—Mobile liq. of ethereal odor; s.in 12 pt. aq. at 17-5°. Propylene Oxide, Me.(CH.CH,).0.—S. in 3 vol. aq.; misc. w. alc. or eth.—Heated w. aq. gives propylene glycol_—Heated w. conc. MgCl, sol. ppts. MgO.—Reduced by aq. and Na amalgam to isopropyl! alc. Vinyl Ethyl Eth., C,H,0.Et.—Gives Test 901.—Distil w. dil. H,SO,. The distillate gives reactions for acetaldehyde and ethyl ale. (Cf. Tests 111 and 814.) Methyl Propyl Eth., Me.O.Pr. Vinyl Eth., (CH,:CH),.0.—Gives Test 901.—Probably gives some acetaldehyde when dist. w. dil. H,SO,. 1 Methylal, CH,.(OMe),.—Described in Genus I. Methyl Allyl Eth., Me.0O.C,H,.—Gives Test 901.—B. p. dibro- mide, 185°. 1, 3-Propylene Oxide, (CH,.CH,.CH,).0.—B. p. a. 320°.—Misc. w. aq.—Boiled w. conc. aq. KOH gives polymeric oxides. Isobutylene Oxide, Me,.(C.CH,).0.—Combines w. aq. w. evol. of heat, giving isobutylene glycol. Ethyl Isopropyl Eth., Et.0.C,H,—Dec. by 1% H,SO, at 150° into its constituent alcohols. s-Dimethylethylene Oxide, (Me.CH.CHMe):0O.—Unites quickly w. h. aq. to form corresponding glycol. Methyl Propargyl Eth., Me.0.C,H..—Gives lemon-yellow gelati- nous ppt. w. ammon. AgNO,! Ethyl Isopropenyl Eth., Et.0.CMe:CH,.—Dec. by 1% H,SO, quickly and completely in the cold into acetone and ethyl ale. (Cf. Test 711-1.) Allylene Oxide, Me.(C:CH).O.—S. aq. but separated fr. sol. by K,CO,.—Very stable. Ethyl Propyl Eth., Et.0.Pr. Ethyl Allyl Eth., Et.0.C,H,.—Gives Test 901.—Dec. by heating w. 2% H,SO, to ethyl and allyl alcohols (cf. Tests 814 and 811). t+ Methyl Alc., Me.OH.— Misc. w. aq.— Odor alcoholic. — Identify by Test 819! Isopropyl Eth., (C,H,),0. 160 Boiling-point (C.°). 78 78°4 80 81-2 82-8c. 82-9c. 83-4 90-7 (th. 1.) 94-3 96- 6c. 97-Ac. 99-8 101-8 104-5-6 106-5 112-5 114 115-16 116-5 117 117c. 117-6 118-5 Specific Gravity. 0-875(0) 0.794157... 0-833?9/, 0-880(0) 0-789?°/, 0-78076/, 0-891(0) 0-744(21) 0-805(18) 0-871(0) 0-804?°/, 0-827(0) 0-814(15) 0-874(0) 0-817(0) 0-833(0) 0-840?, 0-8342°/, 0-832(0) 0-873(0) 0-8107°/, 0-839(0) 0-824(0) GENUS VIII, DIV. B, SECT. 1. a 161 (ORDER I, SUBORDER I.) ALCOHOLS.—Colorless and liquid, with Specific Gravity less than 0-90 at 20°/4°. I,4-Oxypentane, Me.(CH.(CH,),):0.—S. in 10 pt. c. aq.; more s. c. than h.; v. s. alc. or eth_—Not attacked by aq. at 200°.—When heated w. a 60% HBr sol. gives C,H, ,Br3. t+ Ethyl Alc., Et.OH.—Odor alcoholic.—Misc. w. aq.—Identify by Test 814! Ethyl Propargyl Eth., Et.0.C,H,—Penetrating odor.—D. s. aq.; misc. alec.—Unsat.—Gives yellow ppt. w. ammon. CuCl.—Heated w. 1% H,SO, gives propargyl and ethyl alcohols. Pentamethylene Oxide, (CH,),.0.—Less s. in h. than c. aq.; misc. alc. or eth.—Does not unite w. aq. at 200°. {Isopropyl Alc., Me.CH(OH).Me.—Misc. w. aq.—Test 819-1 gives amber ring.—Test 801 applied in the cold to a 1% aq. sol. gives an immediate ppt. of 1odoform.—lIdentify by Test 818! | Trimethylcarbinol, Me,.c.OH.— M. p. 25°.—V. s. aq.— Deliq. — Odor mild alcoholic.— The color produced in Test 819 resembles that given by methyl alc.!—Does not give iodoform in Test 801. Glycol Dimethyl Eth., C,H,.(OMe),.—HI gas gives glycol and methyl iodide. t Propyl Eth., Pr,O.—Gives Test 907. Allyl Eth., (C,;H,;),.0.—Gives Test 901. } Allyl Alc., CH,:CH.CH,OH.—Odor very penetrating and mustard-like !—Misc. aq.—Gives Test 901.—Test 819-1 gives a brown ring.—Identify by Test 811! { Propyl Alc., Pr.OH.—Odor mild alcoholic.—Misc. aq.—— Test 819-1 gives amber-colored ring.—Identify by Test 820! t sec.-Butyl Alc., Me.CH(OH).CH,.Me.—Odor mild alcoholic. —E. s. aq.—1% aq. sol. gives some iodoform in the cold after a few seconds by Test 801.—Test 819-1 gives a pale lemon-yellow ring below a pale rose-red ring. {+ Dimethylethylcarbinol, Me,.C(OH).Et.—Odor mild alcoholic. —Not v. s. aq.—Color given in Test 819-1 is similar to that from methyl alc.—Does not give iodoform in Test 801. 1,5-Oxyhexane, Me.(CH.(CH,),):0.—Odor ethereal_—Rather d. s. aq.—Does not unite w. aq. at 230°.—Combines w. HCl to form its chlorhydrine. ft Isobutyl Alc., Me,.CH.CH,.OH.—Odor alcoholic.—sS. in 10-5 pt. aq.—Test 819-1 gives amber-colored ring.—Identify by Test 817! Methylisopropylcarbinol, Me,.CH.CH.(OH)Me.—Oxid. by Test 702 w. cold, very dil. CrO, gives acetone, methylisopropyl ketone, and acetic acid. Vinylethylcarbinol, CH,:CH.CH(OH).Et. — Unsat. 901.) Methylallylcarbinol, CH,:CH.CH,.CH(OH).Me.—S. in 8 pt. aq. —Oxid. by KMnO, gives 7-pentenylglycerine. Diethylcarbinol, Et,.CH.OH. Crotyl Alc., Me.CH:CH.CH,.OH.—See Test 901. { Butyl Alc., C,H,.OH.—Odor alcoholic.—S. in 12 pt. aq.— Identify by Test 813! Dimethylisopropylcarbinol, odor. Methylpropylcarbinol, Me.CH(OH).Pr.—S. in 6 vol. aq.—lIs said to give iodoform in Test 801. (Cf. Test Me,.(C;H,)C.0H. — Camphorous 162 Boiling-point (CoN 119-5 120-1 123¢. 123 123-5 128 128-7 130 130 130-1 131 134 135c. 136 137 137-8 (th. i.) 138-9 140 140: 3c. 140-2 147 147-8 148-50 150 15lc. 154 (th. i.) 154 Specific Gravity. 0-844(0) 0-835(0) 0-824(20) 0-863(0) 0-838(0) 0-833°/, 0-8102°/, 0-827(0) 0-868(18) 0-834(0) 0-833(0) 0+828(0) 0-34218/,, 0-829?/, 0-82329/, 0-840(20) 0-838(0) 0-819(17-5) 0-876(0) 0-830(15) 0-820(20) GENUS VIII, DIV. B, SECT. 1. (ORDER I, SUBORDER I.) ALCOHOLS.—Colorless and liquid, with Specific Gravity less than 0-90 at 20°/4°. Dimethylallylcarbinol, Me,.C(OH).C,H,.—Oxid. by Test 702 gives acetone (Test 711), formic ac., etc. Pinacoline Alc., Me,.C.CH(OH).Me.—M. p. 4°.—Silky ndl. w. camphorous odor. Methyldiethylcarbinol, Me.C(OH).Et,.—Test 702 gives acetic ac. (Test 311). Dimethylpropylcarbinol, Me,.(Pr).C.OH.—Test 702 gives acetic and propionic acids. Glycol Diethyl Eth., C,H,.(OEt),. Ethylisopropylcarbinol, Et.CH(OH).Pr. act. Amyl Alc., Me(Et)CH.CH,.OH.—Test 702 gives valerianic and acetic acids. Dimethylisobutylcarbinol, Me,.C(OH).C,H,. — V. d. s. aq. — Test 702 gives acetic and isobutyric acids (Test 311). {Isoamyl Alc., Me,.CH.(CH,),.0H.—Odor disagreeable, pro- voking coughing.—S. in 30-4 pt. aq. at 22°.—Burns w. smoky flame.—A few drops warmed w. x’s of CrO, mix- ture gives at first the sweetish and fruity odor of valerianic aldehyde, soon followed by the unpleasant odor of iso- valerianic ac.!—Warmed w. 14 pt. conc. H,SO, gives a red sol. Methylisobutylcarbinol, Me.CH(OH). Bu. 2,3, 3-Trimethylbutanol(2), Me,.C.CMe,.0H.—Odor camphor- ous.—M. p. 17°.—Hygroscopic, giving a hydrate, m. p. 83°. a-Ethylallyl Alc., Et.C;H,.OH.—Unsat. (Cf. Test 901.) Ethylpropylcarbinol, Et.CH(OH).Pr. Methylbutylcarbinol, Me.CH(OH).Bu.—Oxid. by Test 702 gives acetic and butyric ac. Hexenyl Alc., C,H,,0.—Odor pungent and peppermint-like. —HE. s. & aq. Amyl Alc., C,H,,OH.—I. aq.—Test 702 gives valerianic ac. (very unpleasant odor). Methylcrotylcarbinol, Me.CH(OH).C,H,—D. s. (Cf. Test 901.) Diisopropylcarbinol, (C,;H,),.CH.OH.—Oxid. by Test 702 gives diisopropylketone, isobutyric ac., and acetone. Methylethylpropylcarbinol, (Me)(Et)(Pr).C.OH.—Test 702 gives acetic and propionic acids. Triethylcarbinol, Et,.C.OH.—Test 702 gives acetic and pro- pionic acids and diethyl ketone. Methylpropylcarbincarbinol, (Me)(Pr).CH.CH,.OH.—Test 702 gives methylpropylacetic ac. and methyl propyl ketone. Ethylisobutylcarbinol Et (Bu).CH.OH.—Test 702 gives acetic and isovalerianic acids, etc. Methylisoamylcarbinol, (Me)(C,;H,,).CH.OH.—Odor like fusel oil.—Oxid. by Test 702 gives methyl isoamyl ketone, iso- valerianic ac., etc. Isohexyl Alc., Me,.CH.(CH,),.0H. Diallylcarbinol, (C,H,),.CH.OH.—Alm. i. aq.—Test 702 gives CO, and some formic ac. act. Hexyl Alc., Me.CH(Et),.(CH,),.0H (?).—Test 702 gives act. caproic ac. Dipropylcarbinol, Pr,.CcH.OH.—Test 702 gives propionic and butyric acids. aq.—Unsat. GENUSSVITE DIV. BOSEOT. ¥. 163 (ORDER I, SUBORDER I.) Oe Te Boiling-point (C.°). 157c. 157 158 -4c. 160 160-5c. 161-5c. 164-5 LBP BS 175-6 175-8 (th. i.) 179 179-5 190-5 195-5 (th. 1.) 194-8 sl. d. 210-11 211c. 214370 (tn, 1.) 214 sl. d. 215 (th. i.) 229-30 231c. Specific Gravity. 0-833(0) 0-8712°/, 0-864(0) 0-830(20) 0+838?°/, 0-825(20) 0-855(20) 0-878(0) 0-834(0) 0-81929/, 0-835(20) 0-870(20) 0-838(0) 0-868(20) 0-839(0) 0-849(0) 0-842°/, 0-880(15) 0-830(20) ALCOHOLS.—Colorless and liquid, with Specific Gravity less than 0-90 at 20°/4°. Hexyl Alc., C,H,,.0H. Diethylallylcarbinol, Et,(C,H,).C.OH.—Odor like camphor.— Test 702 gives diethyl ketone, etc. Methyldiallylcarbinol, Me(C,H,),.C.OH.—Test 702 gives acetic ac. (Test 311) and CO,. Diethylisopropylcarbinol, Et,(C,;H,).C.OH. Cyclohexanol, (CH,),: CH.OH.—M. p. 16°-17°.—Odor like cap- ryl ale.—S. in 28 vol. ag.—HNO, oxid. to adipic ac.—CrO, oxid. to cyclohexanone. Diethylpropylcarbinol, Et,(Pr).C.OH.—Test 702 gives propionic and butyric acids. Methyldipropylcarbinol, Me(Pr,).C.OH.—Test 702 gives pro- pionic and butyric acids. __ Methylamylcarbinol, (Me)(C,H,,).CH.OH.—Test 702 gives acetic and valerianic acids. 2-Methylheptene(2)-0l(6), C,H, .OH.—Adds Br directly.—Heat several hours w. dil. H,SO, to form the oxide, b. p. 127°-9°. Ethyldiallylcarbinol, (Et)(C;H;),.C.0H.—Oxid. by CrO, gives oxalic ac. { Heptyl Alc., C;H,..0H. { Methylhexylcarbinol, (Me)(C,H,,).CH.OH.—Test 702 gives acetic and caproic acids. | (Cf. foot-note on p. 147.)! Ethyldipropylcarbinol, (Et)(Pr,).C.OH.—Test 702 gives acetic, propionic, and butyric acids. [—] Linalol, C,,H,,O.—(1n origanum and other essential oils.) — Agreeable perfume odor!—Adds Br,—KMn0O, oxid. to citral, levulinic ac., and acetone. Octyl Alc., C,H,,.OH. Coriandrol, C,,H,,,.OH.—Fragrant odor!—Shaking w. 5% H,SO, gives terpine hydrate.—E. oxid. by KMnQ,. Propylhexylcarbinol, (Pr)(C,H,,).CH.OH. Diamyl Alc., C,,H,,.OH.—Odor faint. Nonyl Alc., C,H,,.OH. Anthemol, C,,H,,0.—(Occurs in Roman camomile oil.)—Thick liq. w. camphorous odor,—Oxid. by CrO, gives CO, and aq. ; by dil. HNO, p-toluic and terebhthalic acids. (Cf. Tests 905-3 and 318-8.) Methylbenzylcarbinol, (Me)(C,H,).CH.OH. Geraniol, Me,.C: CH.(CH,),.C(Me): CH.CH,.OH.—B. p. (15 mm.) 118-20°; still lig. at —15°.—Odor like the geranium and rose.—I. aq.; misc. ale. or eth.—Opt. inactive —Oxid. by KMn0O, gives acetone and levulinic ac.; by CrO, mixture, citral—For identification as its diphenylurethane, cf. Journ. f. prakt. Chem. II, 56, 28. Decyl Alc., C,,H,,.0H.—Viscous, highly refractive oil.—M. p. ete: COLORLESS COMPOUNDS CONTAINING ©, H, AND O [SUBORDER I OF ORDER I] GENUS VIII, ALCOHOLS. DIVISION B, SECTION 2,—LIQUID ALCOHOLS WITH SPECIFIC GRAVITY GREATER THAN 0-90 AT 20°/4°. Boiling-point (C.2). 67 102 114-5 135 138 160-1 161-2d. 168-70 171-2 176-8 183-4 184—5c. 187-5. 188-9 191 192 197-7 -5c. 202-4 203-5 Specific Gravity. 1-048(0) 0-972797, 0-926(13) 1-113(18) O °O15* 7. 1-165(0) 1-136(20) 1-145(0) 1 -003(20) 0-960(15) 0. 995(0} 1-040(19- 4) 0-920(21) 1-019(0) 1-125(0) 1-013 1-011 0-950(15) ALCOHOLS.—Colorless and liquid, with Specific Gravity greater than 0-90 at 20°/4°. Hydrofurane (cf. Genus IX, B, 3). Dioxyethylene, C,H.O,.—M. p. +9°. Propargyl Alc., CH :C.CH,.OH.—Odor agreeable.—S. aq. —-Un- sat. (cf. Test 901), and gives an explosive greenish-yellow ppt w. ammon. CuCl in Test 906.—Heated w solid KOH gives acetylene, CO,, and H. Ethyleneglycol Monoethyl Eth., HO.CH,.CH,.OEt. Erythrite Anhyd., C,H,O,.—Misc. w. aq.—Reduces h. emmon. AgNO, sol.—Ppt’s MgO fr. MgCl, sol. Trimethyleneglycol Ethyl Eth., Et.0.(CH,),.0H.—Odor pleasant. —V.s. aq. Glycid, C,H,0.CH,.OH.—B. p. (15 mm.) 74°-5°.—Misc. w. aq., alc., or eth.—Dist. under ordinary pressure gives acrolein (Test 112).—Reduces Tollen’s reagent in the cold (Test 101)! —Unites quickly w. aq., forming glycerine (Test 816). Furfuralcohol, C,H,O.CH,.OH.—D. s. aq.!; e. s. ale. or eth.— Very unstable towards mineral acids; becomes green when treated w. conc. HCl!—Heated w. solid KOH gives succinic ac. (Test 320), CO,, etc. Glycerine Eth., (C;H,)..0;.—Misc. w. aq., alc., or eth. !—At 100° unites w. aq. to form glycerine (Test 816)!—After being warmed w. dil. HCl gives ‘‘iodoform reaction”’ and reduces Fehling’s sol.—Br acts violently, giving dibromhydrine. 1, 2-Dihydroxy-2-methylpropane, C,H,,0,.—Heated w. aq. at 180°-200° gives isobutyric ald. 2, 3-Dihydroxy butane, C,H,.(OH),. Suberyl Alc., (CH,),:CH.OH.—Taste, burning, bitter.—PCl, gives suberyl chloride. 2, 3-Dihydroxypentane, C,H,,0,.—Oxid. by Br aq. gives acetyl- propionyl. Propylene Glycol, MeCH(OH).CH,.OH.— Taste sweetish: — Mise. w. aq.; s. in 12-13 pt. eth—Test 702 gives acetic ac. only.—Made into a paste w. ZnCl, and ignited as in Test 816 for glycerine gives propionic ald. s-Diethylglycerine Eth., C,H,,0;. 1, 2-Dihydroxybutane, C,H,.(OH),.—E. s. aq. + Ethylene Glycol, CH,(OH).CH,(OH).—Somewhat viscous liq. —Misc. w. aq.; v. 8s. alc.; d.s. eth.—Solidifies abt. — 20° and then melts at —17.4°.—Ignited w. KHSO, as in acrolein test for glycerine gives acetaldehyde. (Cf. Tests 816, 112, and 111.) Methylphenylcarbinol, (Me)(Ph).CH.OH. Butanediol (1, 4), C,H,.(OH),.—Viscous. ~ 164 Boiling-point Ory 204 204: 7c. 206-7 212 214 (th: i.) 217 218 221 220-5 235 225-30 240d. 246 - 6c. 247-5 250 254 290 290c. 327 Specific Gravity. 1-126 1-043?9/, 1-034(21) 1-053(18) 1-036(0) 0-936(20) 1-000(0) 1-008(18) 1-101(25) 0-978(15) 1-120(23) 1-132(0) 1-0442°/, 1-138 1-2607%/, 1-062(16-5) GENUS VIII, DIV. B, SECT. 2. 165 (ORDER 1, SUBORDER I.) ALCOHOLS.—Colorless and liquid, with Specific Gravity greater than 0:90 at 20°/4°. Butanediol(1, 3), C,H,.(OH),.—V. s. aq.; i. eth.—Oxid. gives oxalic and acetic acids and crotonic ald. Tt Benzyl Alc., Ph.CH,.OH.—Odor faintly aromatic.—S. in 25 pt. aq. at 17°.—Oxid. by Test 702 gives benzoic ac. (Test 312).—(Unless freshly prepared is likely to contain traces of benzaldehyde.)—Identify by Test 812! 2, 3-Dihydroxyhexane, C,H,,.(OH),. Benzylcarbinol, C;H,.CH,.OH. { Trimethylene Glycol, CH,(OH).CH,.CH,(OH).—Viscous; misc. w. aq.—f Distilled w. KHSO, as in acrolein test for glycer- ine (Tests 816 and 112) gives no color w. the fuchsine- aldehyde reagent. (Dif. fr. glycol and glycerine.) m-Tolylcarbinol, Me.C,H,.CH,.OH.—Remains liq. at —20°.— S. in 20 pt. c. aq. 1 Terpineol, C,,H,,O.—Separates fr. eth. sol. in transparent cryst. w. m. p. 35°. (The commercial product is always liq.)—I. aq.; v.s. alc. or eth.—Adds Br,, giving oily bromide. Gives a dihydrochloride, m. p. 50°.—The odor when suffi- ciently diluted resembles that of lilac flower! 1,4-Dihydroxypentane, C;H,,.(OH),.—Viscous.—Misc. w. aq. or ale, !; 1. lgr. s.-Dimethyl Dipropyl Glycol, [(Me)(Pr)C.OH},. Phenylpropyl Alc., Ph.(CH,),.0H.—Viscous, d. s. aq.; misc, w. alc. or eth.—May be oxid. by CrO, to hydrocinnamic ac. Ethyl Glyceryl Eth., CH,(OH).CH(OH).CH,.0.Et. Allyl Glyceryl Eth., C,H;.0;.C;H;—S. in 2 or 3 vol. aq.!— Unsat. (Cf. Test 901.) p-Cuminic Alc., Me,.CH.C,H,.CH,.OH.—Misc. w. alc. or eth.— Oxid. by KMnO, to terephthalic and oxypropylbenzoic acids.—Persistent boiling w. Zn dust gives cymene. Saligenin Methyl Eth., o-MeO.C,H,.CH,.OH. Diethylene Glycol, CH,(OH).CH,.0.CH,.CH,.OH.—S. aq. alc. or eth. Cinnamyl Alc., Ph.CH:CH.CH,.OH.—Aromatic odor like hy- acinths.—D. s. aq.; v.s. alc. or eth.—Gives Test 304 easily. Triethylene Glycol, C,H,,0,.—Misc. w. aq.; d.s. eth. { Glycerine, CH,(OH).CH(OH).CH,.OH.—Viscous sweet-tast- ing syrup.—Misc. w. aq. or alc.; i. abs. eth—Identify by Test 816!—(Commercial glycerine usually contains so much water that it may begin to boil 100° lower than the b. p. given. The temperature will rise nearly to the true b. p., however, if the distillation is continued.)— [N.B.—Several of the higher homologues of glycerine have been prepared. They are syrups, v. s. in water and almost insoluble in ether; but as they possess little interest, and can not be distilled without decomposition under the usual atmospheric pressure, their description is omitted.] Dibenzylcarbinol, (Ph.CH,),.CH.OH.—E. s. alc. or eth. NUMBERED SPECIFIC AND SEMI-SPECIFIC TESTS FOR THE ALCOHOLS. [TESTS 801-900.] 801. The Iodoform Test. The more or less ready formation of iodoform when certain aliphatic compounds are treated with iodine in dilute alkaline solution, furnishes a qualitative test that has found many applications in organic analysis. When the use of this reaction is directed in the tables for the purpose of distinguishing between some of the lower boiling liquid alcohols and ketones, proceed as follows: Prepare a cold aqueous solution containing one drop of the pure compound in each cubic centimeter of water. If the test is to be made with a single centimeter of the solu- tion, carry it out in a three-inch test-tube (‘‘weighing-tube”). For each centimeter of solution used, add two drops of sodium-hydroxide solution (1 : 10); then, drop by drop, from a medicine-dropper, a concentrated iodine solution,* until a barely perceptible tint of yellow, that persists after standing for several seconds, remains. If too much iodine should be inadvertently used, cautiously add just enough more soda to destroy the excess of color. Let the mixture stand at the temperature of the laboratory for two minutes. Then shake and notice whether any iodoform has separated. If no iodoform separates in the cold, immerse the bulb of a small thermometer in the solution; heat to 60°, and maintain this temperature for one minute. If the solution becomes entirely colorless during the heating, add just enough more iodine to restore the trace of yellow that was previously present. If no precipitate appears at once, set the tube aside for two minutes before making the final observation. In the first part of the test, 7 the cold, tsopropyl alcohol and acetone give none precipr- tates of todoform immediately; secondary butyl alcohol rather slowly. Methyl, ethyl, propyl, isobutyl, tertiary butyl, isoamyl, and allyl alcohols give no precipitates under the same conditions. After heating at 60°, ethyl alcohol gives a good precipitate, and allyl alcohol a very scanty one. The other compounds mentioned in the preceding paragraph which do not give iodoform in the cold, do not give any at 60° within the specified time limit. The interpretation here given to the results of the test will not hold for solutions that vary greatly from the prescribed concentration. It is applicable, however, in testing the saponification distillates obtained by the procedure of Generic Test V-2, B. Under other conditions, which were first carefully studied by Lieben,f the delicacy of the reac- tion when used for the detection of smaller quantities of ethyl alcohol, etc., may be greatly increased. According to Lieben, most compounds containing the CH,.CO.C and CH,.CHOH.C groups may be made to yield iodoform by appropriate treatment with iodine and alkali; some, like levulinic acid, giving it very readily in the cold. Hence * This iodine solution should be kept in stock, and is prepared by rubbing 1 part iodine in a mortar with 5 parts of potassium iodide and 15 parts of cold water. + Cf. Lieben, Liebig’s Annalen, Spl. 7, 221.—The lower alcohols and acetone, if in very weak solutions, are easily concentrated by distilling through a tower. The first runnings will contain nearly all of the organic compound so that the second half of the distillate may be safely rejected, The process of “salting out” with potassium carbonate may be combined with distillation, as is illustrated in paragraph (i) of Generic Test V-2, B. 166 SPECIFIC TESTS FOR THE ALCOHOLS. 167 while the test is more used than any other as a preliminary reaction for the detection of ethyl alcohol and acetone in aqueous solutions, the result requires confirmation by additional evidence. Iodoform is ordinarily recognized by its peculiar pervasive odor and pale-yellow color, though it is said that neither of these properties are characteristic of the chemically pure substance. Indeed, under the conditions of the test, the precipitate is at first often prac- tically white, and the odor is not always well developed at the moment of formation. An iodoform odor, unaccompanied by a precipitate, should never be accepted as satisfactory evidence of the presence of any of the compounds giving the reaction. An iodoform pre- cipitate, if washed with cold water, dissolved in a little warm and quite dilute alcohol, and then allowed to crystallize out very slowly, separates from the solvent in regular hexagonal plates of decidedly characteristic appearance, in which the opposite corners of the hexagon are connected by straight lines crossing its geometrical centre; or, sometimes, in regular six-rayed stars whose primary rays branch into a system of symmetrical subordinate rays after the manner seen in frost crystals. 811. Allyl Alcohol. (Properties tabulated on p. 161.) Support a 25 ce. distilling-flask with a long side-tube in a vertical position by a clamp. Cool the bulb by surrounding it with cold water. Introduce two drops of the alcohol, and then three drops of a solution made by dissolving 1 grm. of chromic anhydride in a mixture of 6 cc. of water and 0.8 cc. of concentrated sulphuric acid. The liquids should be dropped from a medicine-dropper in such a manner that they will not come in contact with the side walls of the flask in falling. Cork quickly. Loosen the clamp, and incline the flask so that the lower end of the side tube shall dip into 2 cc. of water contained in a test-tube standing in a beaker partly filled with cold water. Boil the solution in the flask over a very small flame until it has evaporated nearly to dryness. Loosen the stopper before taking away the lamp. Mix the aqueous solution in the test-tube with 5 cc. of the fuchsine-aldehyde reagent used in Test 112 (1). Allow to stand overnight and observe the color the next morning. Mix 2 cc. of the solution with 2 cc. of hydrochloric acid (sp. gr. 1.20), and again observe the color. Finally note the color of this acid mixture after it has been diluted with water to 100 cc. In this test allyl alcohol is oxidized to acrolein. The violet-red coloration which makes its appearance within a few seconds after adding the aldehyde reagent, and which within ten minutes renders the solution practically opaque, is not characteristic, very similar colors being obtained from many other alcohols when treated in the same manner. If, however, the color after standing overnight is a red-violet (RV), of such intensity as to appear opaque except in thin layers, and if this color upon addition of the hydrochloric acid changes to an impure dark yellow or dark yellow-green (about YS2 to YGS2, when viewed in very thin layers against a white background), and this color in turn, upon the dilution with water to 100 cc. gives a pure blue (BTI, occasionally approximating VBTI, the comparison being made in a six-inch test-tube against a white background), the compound, if it has the proper physical properties, must be allyl alcohol. 812. Benzyl Alcohol. (Properties tabulated on p. 165.) Place in a 25-50 ce. distilling-flask two drops of the chromic-acid mixture used in Test 811 for allyl alcohol, 10 cc. of water, and four drops of the alcohol. Heat over a small flame, while shaking, for two or three minutes, until the solution appears distinctly greenish; the temperature meanwhile being kept a little below boiling, so that no vapor shall escape through the side tube. Next distil, collecting about 2 cc. of distillate in a test-tube containing 1 cc. of cold water. Do not use a condenser, but let the extremity 168 SPECIFIC TESTS FOR THE ALCOHOLS. of the side-tube of the flask almost touch the surface of the water in the test-tube. The test-tube should stand in a beaker half filled with cold water. When the distillation is finished, wash down the sides of the test-tube with 3 cc. of water and 6 cc. of strong alcohol. Add one drop of pure phenylhydrazine and boil for half a minute. ‘From this point on, follow literally the directions given in part 1 of Test 113 for benzaldehyde. The oxidation with chromic acid gives benzaldehyde; and the treatment with phenylhy- drazine gives its phenylhydrazone, melting-point 156°. The hydrazone, being rather unstable in the light, will sometimes be found to melt one or two degrees below its true melting-point. (Benzyl alcohol oxidizes so readily, that specimens which have been ex- posed for some weeks to the air will be found to give aldehyde reactions.) 813. Butyl Alcohol (Normal).* (Properties tabulated on p. 161. Convert six drops of the alcohol into n-butyl 3, 5-dinitrobenzoate by the procedure given in the first paragraph of Test 814-1. To purify the ester, crush the reaction product when cold with a stirring-rod. Dissolve it in 10 ce. of ethyl alcohol (2:1). Filter hot if not clear. Cool well, shake persistently, and filter. Wash with 3 cc. of cold ethyl alcohol (2:1). Recrystallize from 8 ce. of the same alcohol and wash with 2 ce. Spread on a porous tile and allow to become air dry in a warm place. Determine the melting-point. The ester obtained in this test is distinctly crystalline, has a pearly lustre, and melts at 64° (uncor.). 814. Ethyl Alcohol. (Properties tabulated on p. 161.) The ready formation of iodoform at 50°-60°—but not in the cold—in Test 801 is the most convenient preliminary test for ethyl alcohol. The following very satisfactory confirmatory test is, of course, applicable only to a nearly pure alcohol containing not more than about 10 per cent of water. The same general procedure with slight modifica- tions may be used in the identification of many of the homologues of ethyl alcohol. 1. Heat together gently in a three-inch test-tube held over a small flame, 0.15 grm. of 3, 5-dinitrobenzoic acid | and 0.20 grm. of phosphorus pentachloride. When signs of chemical action are seen, remove the heat for a few seconds. Then heat again, boiling the liquefied mixture very gently for one minute. Pour out on a very small watch-glass, and allow to solidify. As soon as solidification occurs, remove the liquid phosphorus oxychloride with which the crystalline mass is impregnated by rubbing the latter between two small pieces of porous tile. Place the powder in a dry five- or six-inch test-tube. Allow four drops of the alcohol to fall upon it, and then stopper the tube tightly without delay.— | [When employing this procedure for the propyl and butyl alcohols, use six drops of the alcohol instead of four; for the alcohol must always be present in moderate excess.|— Immerse the lower part of the test-tube in water having a temperature of 75°-85°. Shake gently, and continue the heating for 10 minutes. To purify the ester produced in the reaction, crush any hard lumps that may form when the mixture cools with a stirring-rod, and boil gently with 15 cc. of methyl alcohol (2:1) until all is dissolved, or for a minute or two.—_{In testing for other alcohols than ethyl, all directions for the use of the solvent in this paragraph must be modified as else- where specified. Cf. tests for methyl, propyl, butyl, and isobutyl alcohols.]—Filter boiling hot if the solution is not clear. Cool. Shake, and filter. Wash with 3 cc. cold methyl alcohol (2:1). Recrystallize from 9 cc. of boiling methyl alcohol (2:1). Wash with * A preparation from Kahlbaum of Berlin. + This new reagent is listed by C. A. F. Kahlbaum of Berlin at 8 marks per 100 grams, and may be obtained in New York from Eimer & Amend. It may also be readily prepared in the laboratory from benzoic acid. SPECIFIC TESTS FOR THE ALCOHOLS. 169 2 cc. of the same solvent. Spread out the product on a piece of tile. Allow to become air dry, and determine the melting-point. Ethyl 3, 5-Dinitrobenzoate, the product in this test, crystallizes in white needles melting at 92°-93° (uncor.). 815. Ethylene Glycol. (Properties tabulated on p. 164.) Shake vigorously in a stoppered six-inch test-tube for five minutes, occasionally cooling with water, one drop of the alcohol, 0.4 cc. benzoyl chloride, and 5.0 ce. of a 10 pen cent aqueous solution of sodium hydroxide. Add 10 ce. of cold water. Shake again for a few seconds, and then filter. Wash the precipitate with 20 cc. of cold water. Dis- solve in 20 cc. of hot dilute alcohol (1 : 1), filtering hot if the solution is not clear. Cool and filter. Wash with 4 cc. of cold alcohol (1:1). Dry on a porous tile at the room temperature for an hour. The ethylene dibenzoate, as obtained in this test, melts at 70.5°-71° (uncor.). The melting-point may be slightly raised by repeated crystallization. 816. Glycerine. (Properties tabulated on p. 165.) Of the three tests for glycerine here described, color reaction 1 with pyrogallol has the advantage, as a preliminary test, of being rapid and directly applicable to rather dilute aqueous solutions, but results by procedures 2 and 3 are more conclusive. In testing for glycerine in the presence of other organic compounds, such for example as in the aqueous solution resulting from the saponification of an ester by the method of Generic Test V—2, the glycerine should first be isolated in a nearly pure state by evap- orating to dryness on a water-bath, and extracting the powdered saline residue with a mixture of equal volumes of nearly absolute alcohol and ether. Evaporation of the solvent will then give a syrup that will often be pure enough for identification by either one of the following methods. In the presence of sugars this purification will prove insufficient to permit the use of procedures 1 and 3; but method 2 may be safely used. , 1. Dissolve one drop of the glycerine in 2 cc. of cold water. Add five drops of a one per cent aqueous solution of pyrogallol, and 2 cc. of concentrated sulphuric acid. Shake. Heat quickly to boiling and boil for 20-25 seconds. Cool immediately with running water. Dilute to 20 cc. with strong alcohol in a six-inch test-tube. Without delay compare the coloration produced with the color standard, holding the tube in front of a white back- ground. Glycerine in this test gives a characteristic purplish-red coloration to the alcohol that matches VRT1-T2 of the standard. The color fades away after standing for some minutes. This procedure is directly applicable to quite dilute aqueous solutions if “2 ce. of the solution” is substituted for the “drop of glycerine, and 2 cc. of cold water” called for in the directions. The color from a one per cent solution will then be found to be as pure, and nearly as intense, as when a drop of pure glycerine is taken. The color given by solutions containing 0.1 per cent of glycerine is very pale indeed and fades rapidly, but it is still quite noticeable, and of the correct hue. Very weak solutions may require heating for thirty seconds or more. The presence of sugars, or of certain other polyatomic alcohols like erythrite, may obscure the reaction by giving rise to reddish- or yellowish-brown color- ations. 2. Stir up into a stiff uniform paste on a watch-glass, by means of a thin wire, one drop of the syrupy compound and 0.5 grm. of powdered acid potassium sulphate. Drop the mass into a dry six-inch test-tube supported by a clamp in a slightly inclined position on a lamp-stand. Fit the tube with a clean perforated cork stopper carrying a glass gas- delivery tube, 20-25 cm. long, and bent downward so that one end is barely immersed beneath the surface of 2 cc. of distilled water contained in a second test-tube that stands 170 _ SPECIFIC TESTS FOR THE ALCOHOLS. in a beaker partly filled with cold water. Ignite the sulphate mixture strongly with a gas-flame until frothing ceases and the mass is completely liquefied. Test the aqueous solution in the second test-tube for acrolein by observing its odor, and by color reaction 112-1. The vapors of acrolein, the dehydration product of glycerine in this test, are remark- able for their painfully irritating action on the mucous membranes of the nose and eyes. Their effect must not be confounded with that due to sulphur dioxide, which is usually formed during the ignition, even in the absence of glycerine. Little difficulty will be found in making the distinction by any one who has ever performed the experiment with pure glycerine. The phenomena of the color reaction between acrolein and the fuchsine-aldehyde reagent are fully discussed under the specific test for acrolein, and are very characteristic. Ethylene glycol gives acetic aldehyde, but like trimethylene glycol, erythrite, or man- nite, does not give an acrolein odor or interfering color reaction in the fuchsine test- This latter reaction is also not seriously interfered with by the small quantities of grape- or cane-sugar that remain with glycerine after the purification of a crude glycerine by the ether-alcohol extraction referred to in the introduction to this test. Sugars, if present in larger quantity, are likely to give confusing colorations, but never any acrolein odor. 3. Place in a six-inch test-tube one drop of glycerine, 0.4 cc. benzoyl chloride, and 5.0 ce. of a 10 per cent aqueous solution of sodium hydroxide. Stopper, and shake vigorously, occa= sionally cooling under cold water, until a solid separates. This requires from five to eight minutes. Add 10 cc. of cold water, and shake again for ten to twenty seconds. Filter. Wash with 20 cc. cold water; then with 10 ce. of a cold mixture of 2 ce. glacial acetic acid and 8 cc. water. Crystallize from 15 ce. of boiling dilute alcohol (2 vols. alcohol: 1 volume aq.). Filter hot if all does not dissolve on boiling. Cool and shake till a precipitate gathers. Filter. Wash with 3 cc. of dilute alcohol (2:1). Dry on a porous tile in the air. The product in this test is a white crystalline substance melting at 71°-72° (uncor.). It is presumably glycerine tribenzoate, for which several melting-points with the extreme values of 70° and 76° are to be found in the literature. This procedure is applicable with only slight modification, to not too dilute solutions of glycerinein water. Thus, a fair yield of benzoate is obtained when one drop of glycerine dissolved in 1 cc. of water is substituted for one drop of pure glycerine as prescribed in the directions. It is of course inapplicable in the presence of polyatomic alcohols or other substances giving.the Schotten-Baumann reaction. 817. Isobutyl Alcohol. (Properties tabulated on p. 161.) Convert six drops of the alcohol into O- O- O- O- Specific Gravity. -446(0) -535(0) -603(0) -60(0) -6281°7/, -634(15) -64979/, -751205/, 668(17-5) -677(0) 6772-5 /, -658(20- 9) ¢ 75071/, -790°/, -711(0) -682(17-5) -690(20) -75420/, -689(27) -689(14-9) -769(2°/,) 711"/, 759(7°/o) 809(20) 769(7°/,) HYDROCARBONS.—Colorless Liquids with Specific Gravity less than 0-85 at 20°/4° that do not give Tests 901 to 903. Methane, CH,. Ethane, C.H,. Propane, Me.CH,.Me. Trimethylmethane, Me,.CH. Butane, C,H,,.—S. in 18 vol. c. ale. Tetramethylmethane, Me,.C.—M. p. —20°. 2-Methylbutane, Me,.CH.CH,.Me. Pentane, C,H). Methylcyclobutane, Me.C,H,.—Does not add HI cold. Trimethyl-ethyl-methane, Me,.C.Et. Cyclopentane, C,H,,.—Br substitutes, but only at a high tem- perature.—Oxid. by HNO, gives glutaric ac., etc. Diisopropyl, Me,.CH.CH.Me,. 2-Methylpentane, Me.(CH,),.CH.Me,. Methyldiethylmethane, Me.(Et,).CH. {+ Hexane, C,H,,. jt No evidence whatever of chem. action in Tests 901-903. Methylcyclopentane, Me.C,H,.—Not easily attacked by warm HNO,+H,SO,.—Fuming HNO, oxid. to formic, acetic, and glutaric acids. ; Cyclohexane (Hexanaphthene), C,H,,.—M. p. 4-7°.—‘‘ Not at- tacked by cold mixture of equal vol. conc. H,SO, and fuming HNO,.” ‘‘ Attacked by Br at 100°-110°.” Dimethyldiethylmethane, Me,.C.Et,. 2-Methylhexane, Me,.CH.(CH,),.Me. 3-Methylhexane, Me.CH(Et).(CH,),.Me. 1, 3-Dimethylcyclopentane, Me,.C,H,. Triethylmethane, Et,.CH. Heptane, C,H,,. Hexahydrotoluene (Heptanaphthene), Me.C,H,,.—‘‘Not at- tacked by c. nitro-sulphuric” ac. W. Br and AIBr; gives pentabromtoluene, m. p. 282°. 2, 5-Dimethylhexane, Me,.CH.CH,.CH,.CH.Me.. Hexahydro-m-xylene (Octonaphthene), Me,.C,H,,.—Cf. p. 186, Section 2. Cycloheptane, C,H,,.—Heated w. Br in sealed tube gives pentae bromtoluene. Hexahydro-p-xylene, Me,.C,H,).—Cf. p. 186, Section 2. 182 EEE GENUS IX, DIV. B, SECT. 1. 183 (ORDER I, SUBORDER I.) Boiling-point Specific HY DROCAR BONS.—Colorless Liquids with Specific Gravity less (C.°). Gravity. than 0-85 at 20°/4° that do not give Tests 901 to 903. 124 Methylethylcyclopentane, Me.C,H,.Et. 125-5c. 0-719°/, } Octane, C,H,,. {No evidence whatever of chem. action in Tests 901-903 ! 129-5-31-5 0-725(24-7) | B-Nonane, C,H. 135-6 0-767(?°/,.) | Hexahydropseudocumene (Nonaphthene), Me,.C,H,(1, 3, 4). 135-8 Mesitylenehexahydride, Me,.C,H,(1, 3, 5)- 135-7 0-742(12-4) | a-Nonane, C,H.. 147-50 0-787(20) Hexahydrocumene, Pr.C,H,,. 149-7c. 0-7187°/, Nonane, C,H».—M. p. —51°. 159-5 0-736°°8/, + 2, 7-Dimethyloctane, Me,.CH(CH,),.CH.Me,.—S. in 12 pt. c. glacial Ac. 159-62 0-746(22) 3, 6-Dimethyloctane, Et.CHMe.(CH,),..CH(Me)Et.—Opt. active. 160-62 0-783 (18) Dekanaphthene, C,H». (Fr. petroleum.) 160-62 0-7887°/, a-Terpenetetrahydride, C,,H,,.—‘‘ Not attacked by conc. H,SO,. With fuming H,SO, heat is evolved, but the hydrocarbon is apparently not changed.” 164 0-793*/, f-Terpenetetrahydride, C,,H».—‘‘Br substitutes when hot.— Nitro-sulphuric ac. gives no cryst. nitro product.” abt. 170 0-80(15) Hexahydro-p-cymene (‘‘ Terpane,” “‘ Terpilenehydride ””), C, ,H.p. —‘"Is not attacked by cold fuming HNO,, fuming H,SO,, or Br, 173¢. 0-730(20) Decane, C,,H...—M. p. —30°-32°. 173-80 0-837(1°/,) | Naphthalenedecahydride, C,,H,,. abt. 190 abt. 0-805(20) | Undekanaphthene, C,,H,,. (Fr. petroleum.) 194-5ce. -7417°/, Undecane, C,,H,,.—M. p. —26-5°. 197 -801(20) Dodekanaphthene, C,,H,,. (Fr. petroleum.) 208-10 -813(20) Tridekanaphthene, C,,H,,. (Fr. petroleum.) 214-5c. tok /, Dodecane, C,,H,,.—M. p. —12°. 0 0 0 0 234 Oeigt %, Tridecane, C,,;H,,..—M. p. —6-2°. 240—46 0-819(17) Tetradekanaphthene, C,,H,,. (Fr. petroleum.) 246-8 0-829(17) Pentadekanaphthene, C,,H». (Fr. petroleum.) 252: 5c. On 6579); Tetradecane, C,,H, —M. p. +5-5°. 268c. 0-792(14) 7, 8-Dimethyltetradecane, C,,H,,.—Still liq. at —30°. 270° 5c. 0-7697°/, Pentadecane, C,;H;,.—M. p. 10° 287 - 5c. Oc4ip/, Hexadecane, C,,H;,.—M. p. 18°. 303 Genii? /, Heptadecane, C,;H;,.—Does not give Test 901-3. Slice. Meili, Octadecane, CisHss.—M. p. 28°.—Does not give Test 901-3. Ecc reac aac ara ee -asaicareniniir iiniiraiiniN rage nisin: COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER I]. GENUS IX, HYDROCARBONS. DIVISION B, SECTION 2,—LIQUID HYDROCARBONS AND LIQUID ALIPHATIC ETHERS WITH SPECIFIC GRAVITY LESS THAN 0-85 AT 20°/4° THAT ARE ATTACKED OR DISSOLVED EITHER IN TEST 901, 902, OR 903. Boiling-point (G22): —102-7 —85 —50-2 abt. —35 14-5 18-19 21-2 Specific Gravity. 0-610 0-451(0) 0-635(13-5) 0-691(20) 0-65( —20) 0-6607°/, 0-685(0) 0-670(0) 0-691°/, 0-685°/, 0-69420/, HYDROCARBONS, ETC. — Colorless Liquids with Specific Gravity less than 0-85 at 20°/4° that are attacked or dis- solved either in Test 901, 902, or 903. Ethylene, CH,:CH,.—} Easily absorbed by liq. Br, giving C,H,Br,, b. p. 180°, m. p. +9-5°. Acetylene, CH: CH.—V.d.s. aq.—t} Apply Test 906 w. ammon. CuCl sol.! (Dull-red ppt.)—Absorbed in Br gives liq. tetra- bromide, b. p. 124°-6° (15 mm.), Propylene, Me.CH:CH,.—} The gas is freely absorbed by ec. conc. H,SO, or liq. Br.—Dist. of the H,SO, sol. largely diluted w. aq. gives isopropyl alc. (cf. Test 818).—B. p. of dibromide 141-5° ¢.! Cyclopropane,(CH,),.—Absorbed slowly by conc. H,SO, or Br. —B. p. of dibromide 165°; G, 1-92317°°/,. Butadiéne(1, 3), CH,:CH.CH:CH.. cis- Butene(2), MeCH:MeCH.—B. p. of dibromide 158°.—Not absorbed by conc. H,SO,+4 vol. aq. trans-Butene(2), Me.CH: HC.Me.—M. p. of dibromide 161°. Methylcyclopropane, Me.C,H,. Caoutchene, C,H,.—M. p. —10°. Ethylacetylene, Et.C : CH.—Gives Test 906 w. ammon. CuCl.— Bromide, C,H,Br,, cryst. solid. Butadiéne(1, 2), CH,:C: CH.Me.—Odor like garlic. Isopropylethylene, Me,CH.CH:CH,.—I. at 0° in 2 vols. conc. H,SO, and 1 vol. aq. 1, 1-Dimethylcyclopropane, Me,C.(CH,),.—Easily attacked by Br, but ‘‘rather stable toward 1% KMnO,.’’—Soluble at 0° in 2 vols. conc. H,SO, and 1 vol. aq. Butine(2), MeC :CMe.—Strong odor.—B. p. of dibromide 147°-8°. —Shaking w. conc. HCl polymerizes to hexamethylbenzene. Isopropylacetylene, Me,.CH.C: CH.—Gives Test 906 w. ammon., CuCl. uns.-Methylethylethylene, MeCEt:CH.,. Isoprene, CH,: CH.CMe:CH,.—Very unstable.—Treated w. cone. HCl and distilled w. steam leaves rubber-like mass! s-Methylethylethylene, MeCH:CHEt.—HI gives methylpropyl- carbinol, b. p. 145° Trimethylethylene, Me,C: CHMe.—Polymerized by conc. H,SO, —S. in 2 vol, H,SO,+1 vol. aq. 3, 3-Dimethylbutine(1), Me,C.C: CH. Propylethylene, PrCH: CH,. 2-Methylbutadiéne(2, 3), Me,.C:C:CH.,. 184 Boiling-point (Ec): 42 42-5 45 48-9 50 55-5-6 59-5c. 60 65-7 68 68-70 69-71 abt. 70 70 69-5-71 70-1 70°3 71-2 71-2-5 70-74 72 72-4 72-4 73 75-80 77-8 78-80 78-80 78-83 82-5 83-4 83-4 85-6 Specific Gravity. ee) (=) G2) lea) =) -80519/, -690(20-7) -687(19). -670(0) -785(20) -858(18-2) -698(19) -731(0) -763(0) -750?"/, -732(0) -77629/, -714(12) -712(0) -719(21) -730(0) -751 -825(0) -714(0) -738(13) GENUS IX, DIV. B, SECT, 2. 185 (ORDER I, SUBORDER 1.) HYDROCARBONS, ETC. — Colorless Liquids with Specific Gravity less than 0-85 at 20°/4° that are attacked or dis- solved either in ‘lest 901, 902, or 903. Piperylene, CH,:CH.CH,.CH: CH,.—The tetrabromide cryst. fr. alc. in pearly ndl., m. p. 114-5°. Cyclopentadiéne(1, 3), C;H,.—Conc. H,SO, or HNO, attacks violently.—Reduces ammon, AgNO, sol.—Polymerizes easily to dicyclopentadiéne, m. p. 32-9°. Cyclopentene, C,H,. Propylacetylene, PrC :CH.—Gives Test 906 w. ammon. CuCl and AgNO. Valylene, C,H,.—Odor of garlic_—Test 906 gives yellow ppt.— Br gives cryst. hexabromide. Valerylene, C;H,.—Test 906 gives no ppt.—Heated w. dil. H,SO, gives methyl propyl ketone. Diallyl, (CH,:CH.CH,),.—Odor pungent.—H,SO, attacks w. violence.—Br gives cryst. tetrabromide, m. p. 63°. Pirylene, C,H,.—Peculiar odor.—Test 906 gives no ppt. Sty as RES A Me,C: CHEt.—Gives iodide w. HI, b. p. 42°, s-Methylpropylethylene, Pr.CH: CH.Me.—S. in 3 vol. c. H,SO,+ 1 vol. aq.; the sol. is ppt’d by aq. Butylethylene, Bu.CH:CH,. 1-Methylcyclopentene(2), Me.C,H,.—Oxid. by KMnO, gives a- methylglutaric ac. Butylacetylene, BuC : CH.—Gives Test 906. Diallylene, C,H,.CH,.C: CH(?).—Test 906 gives yellow-green ppt.—Alc. AgNO, gives ppt. of Ag compound. Methylethylpropylene, Me(Et)C:CH.Me. 3-Methylpentadiéne(1, 2), Et.C.Me:C:CH,. Methyl Butyl Eth., Me.O. Bu.—See Test 907! Methylcyclopentane, C,H,,.—Cf. IX, B, 1. 2-Methylpentine(3), Me,.CH.C: C.Me.—Adds HBr. Methyl Isocrotyl Eth., Me,.C: CH.O.Me.—Dec by 2-3 hrs. heat- ing at 140° w. 1% H,SO, giving methyl] alcohol and isobutyl aldehyde. 1-Methylcyclopentene(1), Me.C;H,. Hexadiéne(1, 3), Et.CH:CH.CH:CH,,. $-Ethyldivinyl, CH,: CEt.CH.CH,. Tetramethylethylene, Me,.C:C.Me,.—S in 2 vols. conc. H,SO,+ 1 vol. aq.—Acetone is among products of oxidation by ec. dil. CrO, sol. (cf. Tests 702 and 711). 2, 3-Dimethylpentene(2), Me,.C: C( Me) Et. 2-Methylpentadiéne(2, 3), Me,.C:C: CH.Me.—W. Br in C8, gives C,H,Br, Ethyl Isobutyl Eth., Et.0.C,H,.—See Test 907! 2, 2, 3-Trimethylbutene(3), Me,.C.CMe:CH,.—Odor of camphor and turpentine Hexadiine(1, 4), Me.C:C.CH,.C:CH.— Polymerizes readily — Gives Test 906. 1, 2-Dihydrobenzene, C,H,. 2, 5-Dimethylpentene(2), Me,.C:CH.CH.Me,.—Adds HI easily. Methylpropylacetylene, MeC? CPr.—CrO, mixture oxid to acetic and butyric ac. (cf. Test 702)-—Br reacts violently.—Pro- longed shaking w- 5 pt conc H,SO,+1 pt. aq. gives methyl butyl ketone. 1, 4-Dihydrobenzene, C,H,. 186 GENUS IX, DIV. B, SECT, 2. (ORDER I, SUBORDER I.) Boiling-point (Ci2)2 86-7 92 92-4 96-8 97-8 98 98-9 102 102-5c. 103-4 105 105-6 105-8 108-5 111-3 111-4 112 113-4 114-5 115 115-5 116-8 116-8 117-1 116-20 117-9 118-9 120.5-21 120 120-1 19929-5 122-3 123-5 124-6 131-2 O- O- 0: Specific Gravity. 819(0) -752(20) -7489/, 72515 /, -703(19-5) -751(0) 715(25) 803(20) -814°/, -760(0) -796(15) -763(0) -764(18) -841(0) -741(22) -777(0) -759(29/,) -769?/, -756(21) -762(15) -760(14) -799(0) -722(17) -770(0) HYDROCARS3B0NS, ETC. — Colorless Liquids with Specific Gravity less than 0-85 at 20°/4° that are attacked or dis- solved either in Test 901, 902, or 903. ee eee Hexadiine(1, 5), CH:C.CH,.CH,.C: CH.—Ammon. CuCl in Test 906 gives greenish-yellow ppt.—Alc. AgNO, gives white ppt. —Adds Br, violently. Ethyl Butyl Eth., Et.O. Buu—See Test 907! Ethyl Isocrotyl Eth., Me,.C: CH.O.Et.— Unsat.—Dec. by heating w. 1% H,SO, giving isobutyric ald. and C,H,OH. 3-Ethylpentadiéne(1, 2), Et,.C:C:CH,. 3-Ethylpentene(2), Et,C: CHMe. Heptene(2), Me.(CH,),.CH: CHMe.—CrO, mixture oxid. to va- lerianic and acetic acids. (Cf. Test'702.)—In the cold adds fuming HCl. Heptene(1), Me.(CH,),.CH:CH,.—Does not unite w. cold fum- ing HCl. CEnanthylidene, Me.(CH,),.C:CH.—Ammon. CuCl (Test 906) gives yellow ppt.; ammon. AgNO, also gives ppt.—Gives a liq. dibromide. Diisobutylene, Me,.C:CH.CMe,.—CrO, mixture, cold, oxid. to acetone, etc. (cf. Test 702).—Adds HCl or HI at 100°. Heptine, C,;H,,.—Odor peculiar.—Absorbs O.—HNO, attacks violently.—H,SO, polymerizes to diheptine, b. p. 247°.— Adds Br.—Does not give Test 906.—(FY. dist. of rosin.) Toluenetetrahydride, Me.C,H,.—Nitrated by nitrosulphuric ac. Ethylpropylacetylene, PrC: CEt.—H,SO, gives butyrone. Dihydrotoluene, Me.C,H,. I, I, 2-Trimethylcyclopentene, C,H,,.—Faint odor like camphor and turpentine. Methylbutylacetylene, Me.C:C.C,H,.—Alc. AgNO, gives no ppt. Ethyl Valeryl Eth., Me.C(Et):CH.O.Et.—Heated w. 1% H,SO, at 130°-40° gives methylethylacetaldehyde and C,H,OH. Ethyl Isoamyl Eth., Et.0.C,H,,.—See Test 907! 2, 5-Dimethylhexadiéne(1, 5), CH,:C(Me).CH,.CH,.C(Me) :CH.. Cycloheptene, C,H... Heptone, C,H, ,.—Gives oily hexabromide, C,H,,Br,. s-Dimethyldiethylethylene, Me,C: CEt,. -Hexeny]l Eth., (C,H,,),.0.—Oil w. very pungent odor; i. aq. 2-Methylheptadiéne (4, 6), C,H,,. Propyl Butyl Eth., Pr.O. Buu—See Test 907! s-Diisopropylethylene, Pr.CH:CH.Pr. Octadiéne(2, 6), C,H,,. Hexahydro-m-xylene, Me,.C,H,,.—Hot nitrosulphuric ac. gives trinitro-m-xylene, m. p 172°-4° Hexahydro-p-xylene, C,H,,(CH;),.—E. s. on warming in mix. of HNO, and H,SOQ,. Allyl Isoamyl Eth., C,H,.0.C,H,,. sec.- Butyl Eth., (Me(Et).CH).0. Isobutyl Eth., Bu,.0.—See Test 907! 4-Ethylhexadiéne(1, 4), CH,:CH.CH,.CEt: CHMe.—Absorbs O fr. air slowly.—CrO, mixture oxid. to Ac and propionic ac. (Tests 905-2 and 311) Glycol Diethyl Eth., C,H,.(OEt),.—See Test 907! Octene(1), C,H,;.CH: CH,. Octine(1), C,H,,.C :CH. GENUS IX, DIV. B, SECT, 2. 187 (ORDER I, SUBORDER I.) es 3 “40s HYDROCARBONS, ETC. — Colorless Liquids with Specific case cere Gravity less than 0-85 at 2U°/4° that are attacked or dis- solved either in Test 901, 902, or 903. 132-4 0-773(18) 2, 5-Dimethylhexadiéne(2, 4), Me,C: CH.CH: CMe,.—M. p. + 6°. —Very unstable, absorbing O rapidly fr. the air—Polymer- izes on keeping.—Gives liquid tetrabromide. 132-4 0-828(20) m-Dihydroxylene, Me,.C,H,.—Conc. HNO, gives nitro-m-xylene- 133-4 Octine(2), Me.(CH,),.C: C.Me.—The tetrabromide is oily. 133-5 Octone, C,H,,.—Absorbs O fr. air.—Br or HCl gives a resin. 134-5 o-Dihydroxylene, Me,.C,H,.—Odor like camphor.—Quickly oxid. in air to a resin.—Adds HCl in eth. sol. 134-5-5-5 p-Dihydroxylene, Me,.C,H,.—Odor like turpentine.—HBr gives cryst. addition product. 134-7 Ethyl Hexyl Eth., Et.0.C,H,,—See Test 907! abt. 135 0-803(20) Campholene, C,H,,.—Odor like turpentine.—Absorbs Br, in dil CHCl, sol. 138 0-798(22) Trimethylcyclohexene, C,H,,. 139-5ce. 0-7437°/, Merona C,H,,.—(Several isomers boiling between 140° and Om 141 0-769(20) Butyl Eth., Bu,O.—See Test 907! 140-1 0-8357°/,, Pe atts SA Diethyl Eth., (CH,);.(OEt),.—Fruity odor. —I. aq. 141-5 2-Methyloctene(1), Me.C(C,H,,) : CH,.— Odor aromatic. 142-3 0-757(20) 2, 6-Dimethylheptadiéne(2, 6), C,H,,. 145 0-831(15) Octylene Oxide, C,,H,,0. 145-50 Decone, C,,H,,.—Odor like turpentine.—Absorbs O rapidly. 147-5-9-5 Propylhexamethylene, Pr.C,H,,. 149-8 0-795(0) Methyl Heptyl Eth., Me.0.C,H, See Test 907! 150 Decenylene and Rutylene, C,,H,,. 150-2 1, 2-Methylethylcyclohexane, Me.C,H,,.Et. 153 1, 2-Dimethylcycloheptane, Me,.C,H,.. 154-6 0-772(20) Diamylene, C,)H.». 155-7 Nonone (Carpene), C,H,,.—Oxid. to a resin in the air. 156 -86(20) Pinene (Terebenthene), C,,H,,.—Cf. (IX, B, 3). 0 158 0-7667!/, 4-Propyl-3, 6-heptadiéne, C,,H,,.— Unstable oily tetrabromide. 166 0-795(0) Ethyl Heptyl Eth., Et.0.C,H,,.—Cf. Test 907! 0 167 - 4c. -806°/, Menthene, C,,H.,.—Opt. act —Easily oxid. by shaking with c 1% permanganate sol.—(Descriptions conflicting.) 167-70 3, 6-Dimethyloctadiéne(3, 5), C,)H,s. 171-2 0-856(10) Phellandrene, C,,H,,.—Cf. (IX, B. 3). 173 0-801(0) Methyl Octyl Eth., Me.0.C,H,,—Cf Test 907! 173c. 0 781(15) t Isoamyl Eth., (C;H,,),.0.—Cf Test 907! 175 (th. 1.) 0 853(25) Cymene, C,,H,,. 176-7 0-851(16) Sylvestrene, C,,H,,.—(In Swedish turpentine oil.) 176-5 0-853""/, [+ or —] Limonene, (Hesperidene, Citrene, Carvene), C,,H,..— ([+] variety in lemon oil, etc )—Cf IX, B, 3. 173-80 0-8371°/, Naphthalenedecahydride, C,,H,,.—Hot fuming HNO, attacks violently. 177-8 0-774(0) Triisobutylene, Me,.C:C.(CMe,),.—Oxid. slowly in air; Br acts w. violence. 180 Diallyl Eth., (C,H,,),.0. 179-82 Terpinene, C,,H,,.—Cf. IX, B, 3. 181-2 0-844(20) i-Limonene, C,,H,,.—Odor like oil of lemons —Cf. IX, B, 3. 183-5c. Terpinolene, C,,H,,.—Cf. IX, B, 3. 188 GENUS IX, DIV 75, 8hCig: (ORDER I, SUBORDER I.) ap ; ; HYDROCARBONS, ETC. — Colorless Liquids with Specific ea ean recipe Gravity less than 0-85 at 20°/4° that are attacked or dis- solved either in Test 901, 902, or 903. 189.2 0-801(0) Ethyl Octyl Eth., Et.0.C,H,,—Cf. Test 907! abt. 195 abt. 0:8 Undecylene, C,,H,,. 196-8c. 0-8397°/, Dodecon, C,,H».—Easily oxid.—Action of Br violent. abt. 210-15 Undecine, C,,H...—Ammon. AgNO, gives white ppt. 213-215 0-785(20) Duodecylene, C,,H,,.—(Fr. Canadian petroleum.) 2338¢. 0-845(0) Tridecylene, C,,H,,.—(Fr. Burmese petroleum.) 245-8 0-814 Triamylene, C,,H.—Turpentine odor.—Adds Br, cold. 261 0-815(0) Heptyl Eth., (C,H,,;),.0.—Cf. Test 907! 274 0-7841°/, Cetene, C,,H;..—Br gives dibromide.—M. p. 4°. 280-5 0-8047°/, Cetylene, C,,H5.—M. p. 20°. 291-7 0-820(0) Octyl Eth., (C,H,7),.0.—Cf. Test 907! 314-5 0-818(24) Eicosylene, CH;,. COLORLESS COMPOUNDS CONTAINING C, H, AND O [SUBORDER I OF ORDER J]. GENUS IX, HYDROCARBONS, ETC. DIVISION B, SECTION 3,—LIQUID HYDROCARBONS AND ETHERS WITH SPECIFIC GRAVITY GREATER THAN 0.85 AT 20°/4°. Boiling-point (Ce). 31-5 67 80-36 93 111 114 120-1 136-5 (th. i.) 138 139-2 141-6 (th. i.) 142c. 143-5 146 152-5-3 155 155 156 Specific Gravity. 0-944(15) 0-950(15) 0-879/, 0-90377/, 0-866?°/, 0 913°/, 0-893°/, 0-883(0) 0-880(0) 0-86629/, 0 -9307°/, 0-893(0) 0-890(0) 0-925(0) 0-859(25) 0-98871/, 0-86(20) 0-870%8/, 0-873(16) HYDROCARBONS, ETC. — Colorless Liquids with Specific Gravity greater than 0-85 at 20°/4°. Furfurane, C,H,O.—Peculiar odor.—I. aq.; e. s. ale. or eth.— Colors a pine splinter moistened w. conc. HCl emerald green! —Conc. HCl attacks vigorously giving a brown resinous body. Hydrofurfurane, C,H,O (?).—Adds Br, cold.—Not attacked by Na, KOH, or acetic anhyd.—PCl, gives furfurane. + Benzene, C,H,.—M. p. 5-42°.—Identify by Test 913! 2, 5(a)-Dimethylfurfurane, Me,.C,H,O.—I. aq.; misc. w. ale.— Conc. HCl changes to a resinous body.—Dil. HCl at 170° gives acetonylacetone. + Toluene, Me.C,H,.—Identify by Test 918! Tropilidene, C,H,.—CrO, mixture (cf. Test 905-2) gives benzoic ac. (cf. Test 312) and benzaldehyde.—Br gives an oily di- bromide. Cycloheptadiéne, C,;H,,.—Odor garlicky. { Ethylbenzene, Et.C,H,.—} Oxidize 1 grm. to benzoic ac. by Test 905-1! + p-Xylene, Me,.C,H,.—M. p. 15°.—Identify by Test 920! ; + m-Xylene, Me,.C,H,.—M. p. —54°.—Identify by Test 919! Phenylacetylene, PhC: CH.—Test 906 w. ammon. CuCl gives a yellow flocculent ppt. fr. alc. sol., which when dry detonates on heating.—HNO, or conc. H,SO, resinifies.—7} Heated w. dil. H,SO, gives acetophenone (Test 712). + o-Xylene, Me,.C,H,.—M. p. —28°.—Identify by Test 921! Crotonyl Eth., (Me.CH:CH.CH,),.0. Styrene, PhCH:CH,.—I. aq.; misc. with alc. or eth.—Slowly polymerizes to glassy mass;—conc. H,SO, polymerizes im- mediately.—Gives Test 903!—Odor aromatic and rather characteristic. Cumene, Ph.CH.Me,.—Test 905-1 gives benzoic ac. (Test 312). Benzylethylene, Ph.CH,.CH:CH,.—Unsat. (cf. Test 901).—Test 905-1 gives benzoic ac. (Test 312). Anisol, Me.0.Ph.—Aromatic odor !—I. aq.—W. conc. HI] at 130°- 40° gives phenol and methyl iodide. Pinene (Terebenthene), C,,H,,.—(The chief constituent of { oil of turpentine). The American or English, fr. Pinus Aus- tralis, is[+]; the French, fr. Pinus maritima, is [—].—Odor penetrating and characteristic.—Gives Test 901.—Fum- ing HNO, attacks w. almost explosive violence.—Well cooled and saturated w. dry HCl gas, gives hydrochloride (C,)H,,-HCl), stable volatile cryst. (m. p. 125°), fr. dil. alc., and of camphor-like odor (“‘ artificial camphor”’),. Propylbenzene, Pr.C,H,.—Test 905 gives benzoic ac. o-Methylethylbenzene, Me.C,H,.Et.—Oxid. by Test 905-3 gives phthalic ac. a“. 189 190 Boiling-point (C.°). 158-9 160-2 162 164 164-5 167-8 168-8 -5 169-8c. 170-72 171-1-5 171-3 171-2 170-5 172 173 174-5 170-80 175 (th. i.) 175 175-5 -5 175-6 176c. 176 176-5 Specific Gravity. 0-869(20) 0-788?°/, 0-865(21) 0-7939/, 0-869°8/, -938(18) co) iS -87929/, -873(16) -858(15) -996(0) -856(10) 2) je) == 0-982(0) 0-846(23) 0-918'5/,, 0-853(25) 0-987(0) 0 -862(20) 0-957(15) © -927(20) 0+85319/, GENUS IX, DIV. B, SECT. 3. (ORDER I, SUBORDER I.) HYDROCARBONS, ETC.—Colorless Liquids with Specific Grav- ity greater than 0-85 at 20°/4°. m-Methylethylbenzene, Me.C,H,.Et.—Test 905-1 gives iso- phthalic ac. a-Terpenetetrahydride, C,,H,,.—(Cf. IX, B, 1.) p-Methylethylbenzene, Me.C,H,.Et.—Test 905-1 gives tere- phthalic ac. (Test 318-3). 6-Terpenetetrahydride, C,,H,,.—(Cf. IX, B, 1.) t Mesitylene, C,H,.Me,(1:3:5).—Identify by Test 914! Methyl Benzyl Eth., C,H,.0.Me. tert.-Butylbenzene, Ph.C.Me,.—Oxidation (cf. Test 905) gives benzoic ac. t+ Pseudocumene, C,H;.Me,(1, 2, 4).—For coloration w. AICI, cf. Test 904.—Identify by Test 917! sec.- Butylbenzene, Me.CHEt.C,H,.—Test 905 gives benzoic ac, — Isobutylbenzene, Ph.CH,.CHMe,.—Test 905 gives benzoic ac. o-Cresyl Methyl Eth., Me.O.C,H,. [+] Phellandrene, C,,H,,.—(In fennel and other essential oils.) — I. ale.; s. eth.—Identify as nitrosite. (Cf. A, 246, 282; and 287, 374.) p-Methylstyrene, Me.C,H,.CH:CH,.—Unsat. (cf. Test 901).— Test 905-1 gives terephthalic ac. (Test 318). Phenetol, Et.O.Ph.—Odor aromatic.—I. aq.—At 400° gives phenol (Test 414) and ethylene. Amenylbenzene, Ph.CH(Et).CH:CH,.—Gives Test 901.—Con- tinued boiling gives diamenylbenzene, b. p. 208°-12°.—Test 905 gives benzoic ac. (Test 312). Allylbenzene, PhCH: CHMe.— Unsat. (cf. 901).—Dibromide, ndl. d.‘s..c.-alc.,;m..p2 00a Diamylene Oxide, C,,H,,0.—Reduces ammon. AgNO, sol. Cymene, p-Me.C,H,.CHMe,.—Test 905-2 gives terephthalic ac. (Test 318). p-Cresyl Methyl Eth., Me.0.C,H,. I, 2, 3-lrimethylbenzene, C,H,.Me,. m-Methylisopropylbenzene, Me.C,H,.Pr.—Br substitutes readily cold.—Test 905-2 gives isophthalic ac. (Test 318). 1, 2-Hydrindene, C,H,:C,H,:CH,.—Br substitutes. — Sulpho- nated by cold conc. H,SO,. M. p. sulphonamide 91°-2°, } Eucalyptol (Cineol), C,,H,,0.— Agreeable odor like car- damon and camphor!— M. p. —1°-3°.— Unsat.; dibro- mide very unstable-—Dry HCl conducted into mixture of equal vols. eucalyptol and lgr. gives cryst. ppt. of unstable (C,,H,,O),.HCl.—Shaken w. saturated sol. of I in saturated KI sol. gives ppt. of minute cryst. w. greenish lustre. [+ or —]Limonene (Hesperidene, Citrene, Carvene), C,,H,,. —({+] in oil of lemons.) —General behavior in Test 901-3 as with pinene.—Dilute w. 4 vol. glac. Ac, cool well, and drop in Br as long as color disappears. Allow to stand until crystals separate. Drain, and then recryst fr. acetic ether. The tetrabromide formed melts at 104-5°. (A, 239, 3)! Boiling-point TCLS). — 176-7 176-8 176-8 178 180 180c. 179-82 180-1 181 (th. i.) 181-2 181-2 182-3 183-4 183-4 183-5c. 185 185 185 185 186-7 186-8 185-90 185-90 189 189-5-91 0-851(16) om) O- O- Specific Gravity. -901(15-5) -873(21) -864(15) -040(15) 958 844(20) -860°/, -86218/, -878(20) -942(0) -86618/, -861(20) -892?2/, -966(0) -874(15) GENUS TX, DIV. B, SECT. 8, 191 (ORDER I, SUBORDER I.) HYDROCARBONS, ETC. — Colorless Liquids with Specific Gravity greater than 0-85 at 2u°/4°. [+] Sylvestrene, C,,H,,.—(In Russian and Swedish turpentine oils.) —The sol. in acetic anhyd. is colored intensely blue by | a drop of conc. H,SO, (a reac. that may be interfered with by the presence of some other terpenes).—Br in Ac sol. (pro- cedure as w. limonene above) gives tetrabromide, m. p. 135°-6°; but it is said to be preferable to identify as dihy- drochloride, m. p. 72° (cf. A, 230, 241; 239, 25), obtained by action of dry HCl gas. p-Butyltoluene, Bu.C,H,.Me.—Oxid. by dil. HNO, (Test 905-3), giving p-toluic ac. Phenylbutylene, Ph.C,H,,—Unsat. (cf. Test 901).—Test 905-1 gives benzoic ac. Diethylphenylmethane, Ph.CH.Et,.—Test 905-1 gives benzoic ac. Butylbenzene, C,H,.C,H;.—Test 905-1 gives benzoic ac. 1, 2-Indene, C,H,.—(In light coal-tar oils.)—Conc. H,SO, gives brown resin.—Adds Br.—Forms picrate.—Dil. HNO, gives phthalic ac. Terpinene, C,,H,,.—(In cardamon and other essential oils.)— Opt. inactive.—Resinifies on keeping, or by action of conc. H,SO,.— Unlike pinene is completely destroyed in the cold (except a few brown flocks) by a mixture of 6 pt. Na,Cr,O,, 5 pt. H,SO,+30 pt. aq.—For identification as nitrosite, see A, 239, 36! o-Cresyl Ethyl Eth., Et.0.C,H,. Isobutenylbenzene, Ph.CH: CMe,.—Test 905-2 gives benzoic and acetic acids.—Br gives liq. bromide. i-Limonene, C, ,H,,.—(Syn.-Dipentene, diisoprene, cinene, caout- chin, etc.)—Odor lemon-like.—Absorbs O fr. the air.—Pre- pare the tetrabromide, m. p. 124°-5°, by the procedure given under + or — limonene on p. 190! m-Diethylbenzene, C,H,.Et,.—Oxid. by Test 905-1 gives iso- phthalic ac. (Test 318). p-Diethylbenzene, C,H,.Et,.—Test 905-1 gives terephthalic ac. I, 3, 4-Dimethylethylbenzene, Me,.C,H,.Et.—May be oxidized to xylic ac. Pinol, C,,H,,0.—Odor like that of eucalyptol !—Unsat.—Dis- solved in 2 vols. glacial Ac and treated w. Br, gives stable dibromide which cryst. well fr. eth.-alc. w. m. p. 94°. Terpinolene, C,,H,,,. o-Diethylbenzene, Et,.C,H,.—Test 905-1 gives some phthalic ac. Ethyl Benzyl Eth., Et.0.C;,H,.—Treatment w. P,O, gives ethyl- ene and anthracene (Test 912). I, 3, 5-Dimethylethylbenzene, Me,.C,H;.Et.—Test 905-2 gives mesitylenic ac. Phenylallylene, Ph.C:C.Me.—Tetrabromide, lft. fr. alc., m. p.75°. 1’-Butenylbenzene, Ph.CH: CHEt.— Unsat. (cf. Test 901).—Test 905-1 gives benzoic ac. (Test 312). m-Pseudobutyltoluene, Me,C.C,H,.Me.—Test 905-2 gives iso- phthalic ac. (Test 318). Phenylcrotonylene, Ph.C,H,.—Unsat. (cf. Test 901).—Test 905-1 gives benzoic ac. (Test 312). Naphthaleneoctahydride, C,,H,,—Odor like turpentine.—Ab- sorbs O fr. air. p-Cresyl Ethyl Eth., C,H,.0.Et. Dimethylethylphenylmethane, Me,(Et)(Ph).C.—Br substitution product is oily. 192 Boiling-point (Coy: 190-2 193 194-5 195 195-7 198-200 199-200 201 201-3 200-5 204 (th. i.) 205 (th. i.) abt. 205 (th. i.) 205-6 205-6 206-7 206-10 208-8 -5 209 211-13c. 212 213 214-15 214-15 216-2 214-18 215-20 220-5-1-5 223-8 226-9 229-30 O- 0 O- 1 O- O-: O- 0. 0 GENUS IX, DIV. B, SECT. 3. (ORDER I, SUBORDER I.) Specific HYDROCARBONS, ETC. — Colorless Liquids with Specific Gravity. Gravity greater than 0-85 at 20°/4°. 1, 3-Ethylisopropylbenzene, Et.C,H,.Pr.—Test 905-1 gives iso- phthalic ac. (Test 318-2). -885(18) Isoamylbenzene, Ph.C,H,,.—Slowly oxid. by Test 905-2 to ben- zoic ac. (Test 312) eure in sunlight gives Br derivative, m p. 128°-9°. Isopropyl-m-xylene, Pr.C,H,.Me.. m-Tolylbutylene, C,H,.C,H,—Unsat. (cf. Test 901); the di- bromide is oily. -896°/, I, 2, 3, 5-Letramethylbenzene, Me,.C,H,.—Test 905-1 gives only mellophanic ac., m. p. 238° d. p-Tolylpropylene, C,H,.C,H,.—Unsat. (cf. Test 901). -879(20) (s), I, 3, 5-Diethyltoluene, Et,.C,H,.Me.—Test 905-3 gives uvitic ac., m. p. 287°-8°. -860(22) Amylbenzene, C,;H,,.C,H;.—Test 905-2 gives benzoic ac. (Test 312). -923(21) Ethylphenylacetylene, PhC : CEt.—Unsat. (cf. Test 901). Test 905-1 gives benzoic ac. (Test 312). Ethylbutylbenzene, C,,H,,. 1,2; 3) 4-Tetramethylbenzene, Me,.C,H, sae cryst., p. ’"4°.—Test 905-3 gives prehnitic ac. (TIT, Ai mas 2375), 981(12-5) | Naphthalenetetrahydride, C,,H,,— Feeble odor. Tea 905 gives phthalic ac.—Conc. HNO, gives picric ac.—Oxid. on stand- ing in air.—Br gives unstable substitution product. -93473/, Naphthalenehexahydride, C,,H,,.—Absorbs O fr. air.—HNO, or cold Br attacks w. violence .—Fuming H,SO, sulphonates. 96877 /, y-Methylindene, C,,H,,.—Naphthalene odor.—Absorbs O fr. air. —Conc. H, So, or HCl resinifies—Forms very unstable pic- rate, m. p. "75° Gu, -086(15) Veratrol, o-C,H,.(OMe),.—Solid at 15°.—Heated w. HI gives pyrocatechin and methyl iodide. Propyl-p-xylene, Pr.C,H,;.Me,. s-Dimethylpropylbenzene, Me,.C,H,.Pr(3:5:1). — Test 905-3 gives mesitylenic ac. (III, A, 2, m. p. 166°). Propyl-m-xylene, Pr.C,H,.Me,(4, 3, 1). Propyl-o-xylene, Pr.C,H,.Me,(4, 2, 1). 871(0) p-Propylisopropylbenzene, Pr.C,H,.Pr.—Test 905-3 gives tere- phthalic ac. and Poe ac. Naphthalenedihydride, C,,H,,.—Frozen at +15-5°.—Adds Br, in the cold; m. p. of unstable dibromide 74° .—Fuming H,SO, sulphonates. -864(9) p-Isoamyltoluene, Me.C,H,.C,H,,.—Test 905-2 gives terephthalic ac. (Test 318-3). 857(16) Isohexylbenzene, Ph.(CH,),.CHMe,. -080°/, Dimethyl Resorcinyl Eth., m-(MeO),.C,H,.—-Vol. w. st. 953(0) Methyl Thymy] Eth., Me. 0. C, His s-Triethylbenzene, C, A, .Et,.—Test 905-2 gives trimesic ac. (IIT, A, 1, m. p. 345°-5 50°). 920747; Issey) Phenyl Eth., C,H,,.0.Ph. Ny Ba a Dre C,H,.—Test 905--3 gives p-propylbenzoic en( Lil A, 2,miap. 140°). -911(0) Beaticass C,H... eee (cf. Test 901). -933(0) Ethyl Thymyl Eth., Et.0.C,,H,;.—At 360°—400° splits to thymol and ethylene. -890(15) Allylisopropylbenzene, Me.CH: CH.C,H, C,H, .—Adds Br, to form dibromide, v. s. h. alc., m. p. 59°. Boiling-point (Ex): 233 233c. 233 230-40 240-2 (th. i.) 242 (th. i.) 244 250 (th. i.) 251 258 sl. d. 258-60 261-2 261-3 262-4 263-7 265 250-80 265 269c. 270-5 272-7 275 (th. i.) abt. 275 275-5 (th. i.) 277 (th. i.) Specific Gravity. 1-108(15°) 0-989(28) 1-001(19) 1-008(0) 1-018'°/,, 1-0017°/, 0-849(15) 1-020(12) 1-015(27) 0-990(0) 0-904-0- 927 0-887(0) 1-096'4/, 0-933(20) 1-031(0) 0-929(0) 0-997(17-5) 0-899(19) GENUS IX, DIV, By, SECT.3, 193 (ORDER I, SUBORDER I.) HYDROCARBONS, ETC. — Colorless Liquids with Specific Gravity greater than 0-85 at 20°/4°. Safrol, C,H;.(C,;H,;)(O,CH,)[1:(3, 4)]—Strong sassafras odor! M. p. after solidification by cold+11°; N,=1-53836.— Quickly reduces a 1% neutral KMnOQ, sol. upon shaking. Is violently attacked and completely carbonized in Test 907 with conc. H,SO,. Anethol, Me.0.C,H,.—Cf. IX, A, m. p. 21-6°. ‘Heptylbenzene, C,H,,.C,H,.—(Several compounds isomeric w. this substance w. b. p.’s between 225°-48° have been de- scribed.) Diisobutylbenzene, (C,H,),.C,H,. a-Methylnaphthalene, C,,H,,.—Freezes at —22°.—Long boiling w. conc. HNO, gives isonaphthoic acid, C,,H,O,.—Picrate fr. alc. forms yellow ndl., m. p. 116°. (-Methylnaphthalene, C,,H,,.—M. p. 32-5°.—The picrate forms yellow ndl. w. m. p. 115°. Dimethyl Orcinyl Eth., (MeO),.C,H,.Me.—Alm. i. aq. I, 2, 4, 5-letraethylbenzene, Et,.C,H,—M. p. 13°.—Oxid. gives pyromellitic ac. (III, A, 1, m. p. 264°). -Ethylnaphthalene, Et.C,,H;.—The picrate cryst. fr. h. alc. in fine yellow ndl. w. m. p. 69°-71°. a-Ethylnaphthalene, Et.C,,H;— Forms a picrate, lemon-yellow nd!., m. p. 98°. ; Phenyltolyl, Ph.C,H,. Diphenylmethane, Ph,.CH,.—Ndl. m. p. 26°-7°.—Cf. Div. A of this genus. Octylbenzene, C.H,,.C,H;.—M. p. —7°.—Test 905-2 gives ben- zoic ac. w. difficulty.—(Isomeric hydrocarbons exist w. b. p.’s between 230°-260°.) 1, 4-(a)Dimethylnaphthalene, Me,.C,,H,. — Remains liq. at —18°.—Picrate forms orange ndl., m. p. 139°; s. h. alc.; v. s. eth. p-Phenyltolyl, Ph.C,H,.Me.—Freezes at —2°-3°. $-Propylnaphthalene, C,,H,;.Pr.—Picrate lemon-yellow ndl., m. p. 89°. Sesquiterpenes, C,,H,,.—(Important constituents of many essen- tial oils, like oils of cedar, calamus, cubebs, patchouli, etc.) —D. s. ale.; somewhat viscous.—Give solid hydrochlorides when HCl gas is passed into the cooled ethereal sol. Diisoamylbenzene, (C,H,,),.C,H,.— Liq. at — 20°. Methyl a-Naphthyl Eth., Me.0.C,,H;.—Gives red cryst. comp. w picric ac.—Split by conc. HCl at 150°. Phenanthreneperhydride, C,,H,,.—M. p. —3°.—Not attacked cold by fuming HNO,, by H,SO,, or Br, and by CrQ, only w. difficulty. m-Phenyltolyl, Ph.C,H,.—‘‘ Not attacked by KMnO,.” Cadinene, C,;H,,.—(A sesquiterpene present in cubeb, patchouli, and some other essential oils.)—D. s. ale-—Resinifies easily. —Gives a solid dihydrochloride, m. p. 117°-18°.—When slightly resinified and dissolved in much glacial Ac becomes green and then indigo-blue on addition of small successive portions of conc. H,SQ,. o-o and o-p-Ditolyl, (Me.C,H,),. m-Benzyltoluene, Ph.CH,.C;H,—Much conc. HNO, at 90° gives nitro-compound, cryst. fr. h. glacial Ac, m. p. 141°. Pentaethylbenzene, C,H.Et;.—Dec. by fuming H,SQ, to tetra- ethvl- and hexaethyl-benzene. a jl a a ee SS ee 194 GENUS IX, DIV. B, SECT. 3. (ORDER I, SUBORDER I.) -_ Boiling-point Specific. HYDROCARBONS, ETC.—Colorless Liquids with Specific (C.°). Gravity. Gravity greater than 0-85 at 20°/4°. 277 a-Diphenylethylene, C,,H,,.—CrO, mixture oxid. to benzophe- none. (Unsat.—Br addition product unstable.) 277-90c. 0-996(0) a?-Diphenylpropane, Me.CHPh.CH,.Ph. 280 $-Isobutylnaphthalene, C,H,.C,,H;—The picrate forms yellow ndl., e. s. alc., m. p. 96°. 280-1 3-Bitolyl, C;H,.C;H:.—CrO, oxid. to isophthalic ac. (cf. Tests 905-2 and 318). 28 1c. 1-075°/, Ethyl a-Naphthyl Eth., Et.0.C,,H,. 281-2 Dimethyldiphenylmethane, Me,.C.Ph,. 283-4 1-043 m-Ethylbiphenyl, Et.C,H,.Ph.—CrO, oxid. to m-phenylbenzoic ac CLLL AS 23m 1607), 286 0-98 p-Phenyltolylethane, Ph.C,H,.C;H;.—M. p. 27°. 286 Ditolylmethane, CH,.(C,H,Me),.—M. p. 22°-3°.—Slowly_sul- phonated by fuming H,SO,—CrO, oxid. to dimethylben- zophenone. 288 0-999'°/, o-m-Bitolyl, C;H,;.C;H-.—CrO, oxid. to isophthalic ac. (Test 318). 293-4 0-987(15) s-Benzyltolylethane, C,H,.C,H,.C,H,.Me. 293-5 p-Ethyldibenzyl, Ph.CH,.CH,.C,H,.Et.—_Shows bluish fluores- cence. 294 Benzyl-p-xylene, Ph.CH,.C,H,.Me,. 294-5 (th. 0-985(18-9) | Ethylbenzylbenzene, Et.C,H,.CH,.Ph.—H. s. alc., eth., or CHCl,. 295-8 0-9747/, p.-Ditolylethane, Me.CH.(C,H,)..—Test 905-2 gives dimethyl phenyl ketone and tolylbenzoic ac. 295-8 (th. i.) 1-036(16) Benzyl Eth., (Ph.CH,),.0.—Heated above 315° yields benzal- dehyde, toluene, and resinous matter. 304-5 Ditolylethylene, (Me.C,H,),.C : CH,.—Test 905-2 gives ditolyl ketone, m. p. 94°.—Dibromide v. unstable, losing HBr. 308 0-969(15) Benzylcymene, C,H,.C,H;.(Me)Pr. 310 (th. i.) 1-067(10-2) | Phenanthrenetetrahydride, C,,H,,.—Oxid. by CrO, in Ac sol. to anthraquinone (Test 1011). a. 300 0-939 Diterpenes, C,,H,,.—(In copaiva balsam, etc.)—Very viscous; Lalc: ; 323-5 0-9667°/, m-Dixylyl-ethane, (C,H;.Me,),.CH.Me.—Exhibits a blue fluo- rescence. 324c. a, §-Phenylxylylpropane, Ph,(C,H,.Me,).C,H,. , 324-5 a-Phenylnaphthalene, Ph.C,,H,,—Shows a feeble blue fluores- cence.—Oxid. to o-benzoylbenzoic ac. in alkaline sol. 343-6 0-969(18) Diterebenthyl, C,.H.—Absorbs O fr. air.—Is easily oxid. by oxid. agents.—Not attacked by cold H,SO,.—_Fuming HNO, nitrates.—Br substitutes. 350 Cuminyl Eth., (C,)H,;)..0.—Dist. w. partial dec. to cymene and cuminic aldehyde. 392-6 1-049 Dibenzyltoluene, Me.C,H;.(CH,Ph),. 392-6 Dixylylbenzene, C,H,.(CH,.C,H,.Me),.—E. s. alc., eth., or Ac. 390-400 0-871(0) Tetramylene, CH,). 396-400 s-Triphenylethane, Ph.CH,.CH.Ph,.—Shows a violet fluorescence. —_—_—___- SS NUMBERED SPECIFIC AND SEMI-SPECIFIC TESTS FOR SPECIES OF GENUS IX. [TESTS 901-1000] go1. Bromine Test for Unsaturation. This test for unsaturation finds many applications, but is most frequently employed in connection with the species of Genera IX and III. Dissolve or suspend 0.1 grm. of the pure compound—finely powdered, if it is an in- soluble solid—in 2 cc. of dry carbon tetrachloride in a three-inch test-tube. Add three drops of a bromine solution * prepared by dissolving 2.0 cc. of bromine in 50 cc. of carbon tetrachloride. If decolorization does not take place at once, stopper the tube loosely, and allow to stand for three minutes in the cold, shaking occasionally if the body is insoluble. If the solution becomes colorless before the end of two minutes, drop in more bromine solution until a color that is permanent for a minute or two is produced. Then blow sharply across the mouth of the tube, and notice whether a white cloud (hydrated hydro- bromic acid) makes its appearance. If no signs of action in the cold are observed, hold the tube high above a small flame and boil very gently for two minutes. If decolorization results, drop in more bromine until the coloration remains permanent for nearly a minute when the solution is again boiled. Test for hydrobromic acid as before by blowing across the mouth of the tube. Complete decolorization in either part of this test (either in the cold or after heating), if unaccompanied by evolution of hydrobromic-acid gas, shows that the compound under exami- nation 1s unsaturated; that rs, that it can add bromine. The presence of double or triple bondings in hydrocarbons may in the great majority of cases be detected by use of the test in the cold only; but there are a few unsaturated hydrocarbons like stilbene which require short heating, and in tetraphenylethylene we have one which remains unchanged even when heated. Among the unsaturated acids, maleic and fumaric acids} also show an exceptional behavior in not decolorizing the tetrachloride solution after two minutes’ boiling. Some other unsaturated acids, like aconitic, do not decolorize the solution until it has been heated, but the number of such species is not large. Decolorization in either part of the test when accompanied by a copious evolution of hydro= bromic acid always indicates substitution; but since addition may, or may not, have taken place at the same time, satisfactory inferences as to the existence of unsaturation in such cases can * Carbon tetrachloride is given the preference as the solvent, because bromine solutions pre- pared by its use may be kept for weeks without spoiling; because such solutions do not entirely lose their orange-yellow color on heating unless boiled for more than twice the time prescribed in the test procedure; and because the tetrachloride is such a poor solvent for hydrobromic acid that the gas escapes as soon as formed, and thus is easily detected by the fumes + Fumaric or maleic acids will, however, decolorize hot bromine water. (Bromine water is as a rule a very unsatisfactory substitute for the carbon tetrachloride reagent, since it is fre- quently decolorized by acting as an oxidizing agent, holds back hydrobromic acid, and loses its color rather quickly on boiling.) 195 196 SEMI-SPECIFIC TESTS FOR SPECIES OF GENUS IX. not be drawn. The appearance of scanty traces of hydrobromic acid towards the end of an experiment in which a considerable quantity of bromine has been consumed, may, however, be due to minor secondary reactions and may be disregarded. In the heat, the number of compounds in Order 1 that are attacked by the treatment with bromine is greatly increased. The saturated hydrocarbons of the marsh-gas series, (CrnHn+,), with unbranched carbon skeletons, and the members of the acetic-acid series, (CrH2»O,), are conspicuous examples of compounds unaffected under these circumstances. Some paraffin hydrocarbons like diisoamyl with branched carbon skeletons are, on the contrary, quite readily attacked in the heat, although not in the cold. Many of the aromatic hydrocarbons like mesitylene and anthracene are so easily substituted that decolorization occurs within a fraction of a minute in the cold; but pure benzene is so comparatively unreactive that it does not cause decolorization within the two minutes’ limit on boiling. Most phenols, and many aldehydes and ketones, cause decolorization cold within a few seconds. Whenever decolorization takes place readily in consequence of addition or substitution in a homogeneous compound, if the experiment is continued after the first disappearance of color, it will be found that the quantity of bromine eventually consumed will be at least several times greater than what was added at the beginning of the experiment. go2. Action of Fuming Sulphuric Acid. Support a three-inch test-tube containing 1 cc. of fuming sulphuric acid (sp. gr. 1.89) by means of a small clamp in a nearly vertical position, but so that it shall be slightly inclined away from the operator. Drop in slowly from a medicine-dropper about five drops of the compound. If there are no immediate signs of solution or chemical action, shake the mixture cautiously for about one minute. Then allow to stand for a short time, and notice whether the compound added separates apparently unchanged as an upper layer. If the substance does not dissolve, if heat is not evolved, and if the mixture does not be- come strongly discolored, the compound, if a liquid species of Genus IX, with a specific grav- ity less than 0.85 at 20°,/4°, may belong to Section 1 (the paraffin section) of Division B. 903. Action of Fuming Nitric Acid. [This test is dangerous unless performed cautiously as directed !] In a three-inch test-tube, supported as in Test 902, place 1 cc. of fuming nitric acid of specific gravity 1.48. Then add from a medicine-dropper, held at arm’s length, a single drop of the compound to be tested. A violent reaction often ensues, and there may be a slight explosion, or the substance may even ignite. If there are no signs of action, cautiously add a few more drops of the substance, and shake gently. If the substance is a liquid species of Genus IX with a specific gravity at 20°,74° less than 0.85, and does not dissolve in the acid, and is not attacked by it (as will be in- dicated by absence of sputtering and evolution of heat, and by the non-appearance of a copious disengagement of red nitrous fumes), it is to be sought for in Section 1 (the paraffin section) of Division B.* It is improbable that any of the Species of Section 2 remains entirely unchanged after such treatment. The liquid paraffins, although they are unattacked, and do not dissolve, always dissolve oxides of nitrogen so as to acquire a color much like that of the nitric acid. The presence of two layers after shaking may, therefore, be easily overlooked in a hasty observation. 904. Colorations with Aluminium Chloride. Drop a hard lump of sublimed aluminium chloride weighing about 0.2-0.3 grm. into a clean 6-8-inch test-tube that has just been taken from a hot drying oven. Stopper the tube loosely. Hold it in a nearly horizontal position, and by means of a small flame placed * The tertiary paraffin diisopropyl is said to be violently attacked by cold nitric acid of specific gravity 1.52. : : | E j SEMI-SPECIFIC TESTS FOR SPECIES OF GENUS IX. 197 under one end slowly sublime the chloride until it forms a thin light-yellow coating cov- ering a considerable portion of the glass surface. Allow to cool. Drop in 0.5jcc. of a solution containing 0.05 grm. of the hydrocarbon dissolved in 2.5 cc. of chloroform. Stopper the tube tightly. Lay it on its side upon a sheet of white paper that rests upon and partly covers the color standard. Then roll it back and forth so that the solution shall flow over and wet all parts of the sublimate. Observe the color after a few seconds, and again after 15-20 minutes. Most aromatic hydrocarbons give colorations when thus treated. The colors are often very intense, and sometimes admit of employment as minor preliminary or confirmatory tests; but since the hue may be much modified by the presence of small quantities of impuri- ties, too great importance ought not to be attached to the indications obtained by their use. The initial colorations given by the liquid homologues of benzene approximate orange; e.g. pseudocumene, RO; m-xylene, O; benzene, OY (after five minutes). After standing fifteen minutes these colors will either remain unchanged, or will change by about one hue of the standard in the direction of the red end of the spectrum. The initial coloration with diphenylmethane and triphenylmethane is YO, darkening within a few minutes to YOT1; with anthracene it is OYS2-YS2. Initial colorations of great intensity which persist unchanged for more than twenty minutes and approximate blue, are given by several important solid hydrocarbons; e.g. blue (B), by diphenyl; blue to green-blue (GB-B), by phenanthrene; and blue-green (BG), by naphthalene. 905. Oxidation of Side Chains. The oxidation of the side chains in aromatic hydrocarbons to carboxyl groups by hot aqueous solutions of potassium permanganate, chromic acid, or nitric acid, has been em- ployed in determining the constitution of many species of Genus IX. The most serious difficulty encountered in adapting these methods for use as practical specific tests arises from the extreme insolubility of all hydrocarbons in aqueous solutions. This renders the oxidations very slow. During the oxidation period—which is seldom less than several hours—the oxidation product, which is itself never entirely stable, is exposed to the de- structive action of the oxidant. Hence the yield, which even under favorable circum- stances falls much under the theoretical, is often very poor indeed. Hydrocarbons which are themselves stable, but give unstable oxidation products, are therefore the most difficult to treat successfully. Whenever it is suggested in the tables that some particular oxidant may be used in the identification of a hydrocarbon, it does not always follow that the oxidant mentioned is the best that could have been selected for the purpose, or that the yield will be good, but merely that the product named has been obtained by its use. It should also be understood that the following general directions are given as suggestions rather than mandatory procedures; and that what is said refers more especially to aro- matic hydrocarbons having one or two side chains. 1. (Oxidations with Potassium Permanganate.)—The oxidation with permanganate, when applicable, will usually be preferred to either of the other methods. The reagent is a neutral aqueous solution containing 61.6 grms. of potassium permanganate to the liter. In organic oxidations it is said to be reduced according to the equation 2KMn0, +2H,0=2Mn0,.cAq. +2KOH +30. 1 cc. of the solution accordingly contains 0.01 grm. of “available oxygen,” and the alkali liberated is sufficient to combine with the full quantity of organic acid and carbon dioxide that will be produced in any ordinary oxidation. The iatter fact makes it possible to perform these oxidations in closed vessels, and thus avoid the violent bumping that is one of the greatest objections to the use of permanganate when the oxidation is performed by boiling in flasks. 198 SEMI-SPECIFIC TESTS FOR SPECIES OF GENUS IX. Calculate by aid of the equation given above how much permanganate solution will be theoretically needed to produce the desired effect, and place it in a strong wide flask or bottle of about one-liter capacity. If, as will sometimes happen, the hydrocarbon is lighter than water, and a liquid, the extended contact surface presented by the permanganate solution, which will be spread out in rather a thin layer, will do much to accelerate the reaction. When the oxidation product expected is benzoic, isophthalic, or terephthalic acid, about 1 grm. of the hydrocarbon should be enough for an experiment. Suspend the bottle by a wire, so that the lower part will be immersed in a boiling water-bath; and, as soon as the air within has been expanded by the heat, and the hydro- carbon introduced, stopper tightly to prevent loss of substance by volatilization. Then heat until the red color of the permanganate is seen to have completely disappeared. This may require from two to eight hours, and some of the hydrocarbon will always remain unattacked. Separate the colorless alkaline solution from the bulky brown precipitate of hydrated manganese oxide by filtration. LEvaporate to a small volume. Filter if neces- sary,and cool. Acidify the solution with a moderate excess of hydrochloric acid, and shake vigorously. Benzoic, isophthalic, and terephthalic acid will precipitate at this point. The two former may then be identified by their melting-points and specific tests, after a single crystallization from boiling water; the latter after being well washed with water. Phthalic acid being comparatively easily oxidized by hot permanganate, will not be detected, unless the hydrocarbon is one that oxidizes quite rapidly. The loss of benzoic acid in long-continued oxidations is also large, though less serious. In an oxidation of 1 grm. of ethylbenzene requiring six hours, the yield of pure benzoic acid was 0.20 erm. Benzoic acid is easily separated from any of the phthalic acids by treatment with chloroform, in which it is very soluble. 2. (Oxidations with Chromic-acid Mixture.)\—Boil the hydrocarbon in a round-bot- tomed flask containing ebullator tubes (cf. p. 223) with the quantity of chromic-acid mixture theoretically required to produce the desired effect, until the chromic acid is completely reduced. The apparatus, chromic-acid mixture, and general procedure for the oxidation are the same as have been more fully described in Test 702 for the oxidation of ketones and alcohols, except that longer heating will be necessary. As the action of hot chromic acid on most of the aromatic acidsis even more destructive than that of permanga- nate, it is advisable to use at least 2 grms. of the hydrocarbon for each experiment, and even larger quantities may sometimes be found necessary. Collect the insoluble residue of oxidation products, and unchanged hydrocarbon that separates from the well-cooled solu- tion, on a small filter. Wash with a little cold water. Dissolve out the aromatic acids by boiling with a slight excess of sodium-carbonate solution. Reprecipitate with an excess of hydrochloric acid, and identify them by appropriate tests. 3. (Oxidations with Dilute Nitric Acid.)—Although nitric acid, being a milder oxidant than either permanganate or chromic acid, may be successfully employed in some cases in which the latter are inapplicable, and is occasionally mentioned in the tables, it has the disadvantage of being exceedingly slow in its action, and of giving products which sometimes consist largely of nitrosubstitution derivatives whose removal is troublesome. The proper procedure depends so much on the properties of the particular hydrocarbon. to be oxidized, that in the few instances in which this method is referred to in the tables, it will always be best to consult the original literature relating to the subject before pro- ceeding to the experiment. The following general statement and suggestions may, how- ever, be of some assistance. It is best to oxidize at least 2 grms. of the hydrocarbon with a large excess of acid. The nitric acid is usually a mixture of one part of concentrated commercial nitric acid with three parts of water, though in some cases a stronger acid can be used, shortening the SEMI-SPECIFIC TESTS FOR SPECIES OF GENUS IX, 199 time without causing much substitution.* The time of boiling varies from six to forty- eight hours. In general it is best to boil at least eight hours. If it is expected that a solid aromatic acid, not volatile with steam, will be formed, the excess of nitric acid should be removed by evaporation on a water-bath. The residue is next extracted with boiling sodium-carbonate solution, the solution filtered, and the organic acids precipitated from the filtrate by a moderate excess of hydrochloric acid. Nitro-acids may then be reduced by warming with tin and hydrochloric acid, so as to form soluble hydrochlorides of the corresponding amino-acids, which, upon filtration, will pass into the filtrate. Or, if the acid sought should also be soluble in dilute hydrochloric acid, it may be separated from the amino-acid by crystallization, after precipitating the tin with sulphuretted hydrogen. 906. Test for Triple-bonding in Compounds Containing the (~C = CH) Group. Dilute 1 cc. of ammoniacal cuprous chloride solution,t in a test-tube, with 5 ce. of cold water. Add a few drops of the hydrocarbon, if a liquid, and shake. If the hydro- carbon is a gas, conduct it directly into the copper solution. Collect the precipitate on a filter. Wash with cold water and observe the color. The hydrogen atoms in compounds containing the =CH group are usually replace- able by copper when thus treated. These copper compounds appear as insoluble floccu- lent precipitates, varying in color, according to the body from which they are obtained, from a dark brick-red to a greenish yellow. When washed with alcohol and ether and dried with proper precautions, they often explode violently when struck a sharp blow or when strongly heated. 907. Saturated Ethers of Division B. Drop 1 cc. of the compound slowly into 2 ec. of ice-cold sulphuric acid (sp. gr. 1.84) contained in a five-inch test-tube standing in a beaker of ice-water. Without removing the test-tube from the ice-water, shake briskly for half a minute or more. Then, after allowing to stand for a minute or two, observe whether the compound has dissolved completely to a colorless or nearly colorless solution. In case such a solution has been formed, pour it slowly into a second test-tube containing 3 cc. of cold water, shaking and cooling mean- while, Just as was done during the preparation of the acid solution. If the mixture on standing separates into two layers, remove and reject the lower layer, which will consist of dilute sulphuric acid, with the aid of along capillary-pointed medicine-dropper. Wash the upper layer by shaking with 2 cc. of sodium-carbonate solution. If an emulsion forms, hasten the separation into layers by warming. Remove the carbonate solution as before by the aid of the dropper, and transfer the organic liquid to a dry three-inch test-tube. Add a small fragment of solid potassium carbonate, and heat nearly to boiling to hasten the drying action. Then after a few minutes, in order to ascertain whether the product obtained is identical with the original substance, determine the boiling-point of the clear dried * Thus Fileti (G. 21, I, 5 and 22) used one part of acid to one of water in oxidizing p-propyl- isopropylbenzene, obtaining terephthalic acid with only a trace of a nitro-acid. + Ammoniacal Cuprous Chloride Reagent.—This is the reagent used in gas analysis for the absorption of carbon monoxide.—It is prepared from an acid cuprous chloride solution as re- quired for use. To prepare the acid solution, cover the bottom of a bottle with a layer of pow- dered copper oxide 1 cm. deep. Place in the bottle a number of pieces of rather stout copper wire, reaching from top to bottom, sufficient to make a bundle an inch in diameter, and fill the bottle with common hydrochloric acid of 1.10 sp. gr. Stopper, and allow to stand with occa- sional shaking for some days, or until the solution becomes nearly or quite colorless. When about to make a test, decant a little of the clear acid solution, and add ammonia to it until present in slight excess, i.e., until the mixture has a distinctly ammoniacal odor. The space left in the stock bottle after every withdrawal of solution should be immediately filled with more bydrochloric acid (1.10 sp. gr.), and the bottle always be kept tightly stoppered to pre- vent absorption of oxygen from the air. 200 SPECIFIC TESTS FOR SPECIES OF GENUS IX. liquid by Siwoloboff’s method. For a more detailed description of the manipulations involved in the washing and drying, and in the boiling-point determination, read the latter half of paragraph 7. on the identification of soluble alcohols obtained in saponification tests (cf. p. 115). Any species of Genus IX, Division B, that dissolves in sulphuric acid in this test to a clear, nearly colorless solution, which, upon dilution, gives a liquid identical in boiling- point with the original substance, is probably the oxide of a saturated hydrocarbon radi- cal or, possibly, an ‘‘ unsaponifiable ester.’ Unsaturated ethers and unsaturated hydro- carbons may also dissolve completely in the cold acid, or may be entirely decomposed by the reagent; but when a clear solution does result, dilution with water can not be expected to yield the original substance. Saturated hydrocarbons, even the aromatic ones, do not dissolve in the cold acid to any considerable extent. giz. Acenaphthene. (Properties tabulated on p. 177.) Dissolve 0.05 grm. of the hydrocarbon and 0.10 grm. of picric acid in 2.5 ec. of boiling 95 per cent alcohol in a dry test-tube. Allow the solution to cool down to the temperature of the laboratory gradually. Acenaphthene under these conditions yields a beautifully crystallized orange-colored picric-acid compound, C,,H,,.C,H,(NO,),0, whose slender flat needles shoot from the bottom of the tube to the surface of the solution. Collect on a small filter, and wash with 3 cc. of cold alcohol. Dry for fifteen minutes on a piece of porous tile at 100°, and determine the melting-point. The color of the dry crystals is nearly the orange of the color standard (O-YO). They melt at 161°-162° (uncor.). g12. Anthracene. (Properties tabulated on p. 180.) Place in a six-inch test-tube 0.05 grm. of the hydrocarbon, 1.5 grms. of chromic acid (CrO,), 4 cc. of glacial acetic acid, and 1 cc.of water. Support the tube by a clamp so that its lower end shall rest in a circular perforation in a piece of asbestos board arranged as in Test 312-2, and boil for ten minutes over a small flame, so gently that the vapors shall all condense on the sides of the tube. Pour into 20 cc. of cold water. Collect the floc- culent precipitate on a filter. Wash thoroughly with much water, and finally with 5 ce. of cold alcohol. Transfer the precipitate to a dry test-tube and boil with 10 ce. of strong alcohol. Cool. Collect the nearly white precipitate on a small filter. Wash with 5 cc. of cold alcohol. Boil up a second time with 10 cc. of strong alcohol, and again cool. Filter, and wash with 5 cc. of cold alcohol. Dry the residue fifteen minutes at 100° on a piece of porous tile, and determine the melting-point. Anthraquinone, the product obtained in this test, is a pale yellowish compound, crys- tallizing from alcohol in minute needles which melt at 279°-280° (uncor.). For other characteristic properties of anthraquinone see Test 1011. 913. Benzene. (Properties tabulated on p. 189.) Mix in a dry test-tube three drops of the hydrocarbon, 1 ce. of nitric acid (sp. gr. 1.42), and 1 cc. of sulphuric acid (sp. gr. 1.84). Heat the mixture until it begins to boil, and maintain it at this temperature for half a minute. Then pour slowly into 10 cc. of cold water. Cool quickly. Shake. Collect the bulky flocculent precipitate on a small filter, and wash until the washings are no longer colored. Dissolve in 8 cc. of boiling dilute alcohol (1:1). Allow to stand until the solution has assumed the room temperature. The liquid will become filled with long, fine, nearly white needles of m-dinitrobenzene. Collect on a small filter. Wash with 5 cc. of cold dilute alcohol (1:1). Drain on a piece of porous tile and dry fifteen minutes at 50°. The dinitrobenzene formed in this test melts at 89°-89.5° (uncor.). SPECIFIC TESTS FOR SPECIES OF GENUS IX. 201 914. Mesitylene. (Properties tabulated on p. 190.) Allow one drop of the hydrocarbon to fall into a mixture of 2 cc. of sulphuric acid (sp. gr. 1.84) and 1 cc. of fuming nitric acid (sp. gr. 1.48) contained in a dry test-tube. Shake, and then boil very gently for one minute over a small flame. Break up any hard lumps that may form with a stirring-rod, and pour into 10-12 cc. of cold water. Collect the solid nitro-compound on a very small filter and wash well with cold water. Then wash once with 5 cc. of cold strong alcohol. Transfer to a test-tube and boil gently with 15 ce. of 95 per cent alcohol (*) until all dissolves. (The compound dissolves quite slowly.) Allow to cool. Shake vigorously. Collect the crystalline precipitate in the point of a very small filter. Wash with 5 cc. of cold 95 per cent alcohol (**). Drain on a piece of porous tile; dry for fifteen minutes at 100°, and determine the melting-point. The product in this test, trinitromesitylene, is obtained in the form of minute colorless needles melting at 235° (uncor.). 915. Naphthalene. (Properties tabulated on p. 176.) Dissolve 0.05 grm. of the hydrocarbon and 0.10 grm. of picric acid in 2 cc. of boiling 95 per cent alcohol. Allow the solution to cool gradually. Collect the long, hair-like yellow (Y-YT1) needles of the picric-acid compound, C,,H,.C,H,(NO,),0, on a small filter, and wash with 1 cc. of strong alcohol. After draining, transfer to a piece of porous tile, and press out adhering mother-liquor. Form the crystals into a little mound on a dry part of the tile; rinse them off with 5-10 drops of strong alcohol. Repeat the washing with alcohol twice more in the same manner, pressing out the adhering alcohol on a dry part of the tile each time with a small spatula. Spread out the crystals on a bit of dry tile and dry for 15-20 minutes at 50°. Then determine the melting-point. The picric-acid compound of naphthalene, thus purified, melts at 150.5° (uncor.). (Long-continued drying at a high temperature is inadmissible since it causes a gradual loss of naphthalene.) 916. Phenanthrene. (Properties tabulated on p. 177.) Dissolve 0.10 grm. of the hydrocarbon and 0.20 grm. of picric acid in 5.0 ce. of boil- ing 95 per cent alcohol. Allow to stand until quite cold. The picric-acid derivative of phenanthrene that forms separates in crystals. Collect on a filter, and allow to drain well without washing. Transfer to a piece of porous tile to absorb the last of the mother- liquor. Redissolve in 1 ce. of boiling alcohol. Allow to cool slowly as before. Collect the crystals on a piece of tile to absorb the mother-liquor, and wash with five drops of strong alcohol. When the alcohol has nearly all disappeared, place on a fresh piece of tile; dry fifteen minutes at 100°, and determine the melting-point. The picric-acid compound of phenanthrene, C,,H,).C,H;(NO,),.0, obtained in this test, forms long, hair-like needles which are orange-yellow (OY) when dry, and melt at 143° (uncor.). 917. Pseudocumene. (Properties tabulated on p. 190.) Nitrate two drops of the hydrocarbon by the procedure of Test 914 for mesitylene. Do not increase the quantities of acids and solvents prescribed, but follow the directions given literally, except that more than usual care must be taken not to overheat during nitration. During the operation the test-tube should be held at some distance above the flame, and the heating should be interrupted before the expiration of the minute if the mixture show signs of darkening, or if a sublimate should begin to appear on the sides of the tube. _ The trinitro-pseudocumene formed in this test is a nearly white crystalline compound melting at 184° (uncor. . 202 SPECIFIC TESTS FOR SPECIES OF GENUS IX, 918. Toluene. (Properties tabulated on p. 189.) Dissolve three drops of the hydrocarbon in 1.5 ec. of the strongest fuming nitric acid. Then add at once, without cooling, 1.5 ce. of fuming sulphuric acid (concentrated sulphuric acid containing in solution about 10 per cent of sulphuric anhydride—the same reagent that is used for Test 902). After half a minute pour the mixture into 10 ce. of cold water in a test-tube. Cool well with running water. Close the tube with the thumb and shake vigorously and persistently until the nitro-compound separates in yellowish-white flocks, leaving the solution clear. Collect the precipitate on a very small filter and wash with cold water. Dissolve in 8 ec. of boiling 50 per cent alcohol. Cool in running water. Shake vigorously. Filter. Wash the precipitate with 5 cc. of cold 50 per cent alcohol. Redissolve the washed pre- cipitate a second time in 8 cc. of boiling 50 per cent alcohol. Cool. Shake. Wash with 5 ce. of 50 per cent alcohol. Dry, and determine the melting-point. 2, 4-Dinitrotoluene, the product in this test, is a nearly white precipitate of crystal- line structure melting at 70°-71° (uncor.). (If the solution, in making the last crystalliza- tion, is allowed to cool slowly, the compound will separate out in the form of delicate white needles.) gI9. m-Xylene. (Properties tabulated on p. 189.) Nitrate two drops of the hydrocarbon by the procedure of Test 914 for mesitylene Do not increase the quantities of acids or solvents prescribed, but follow the directions given literally in every detail, except that the precipitate referred to at the point marked by the double asterisk (**) should receive one additional crystallization from 10 ce. of boiling 95 per cent alcohol before being dried. The trinitro-m-aylene formed in this test is a nearly white crystalline compound melt- ing at 181°-181.5° (uncor.). 920. p-Xylene. (Properties tabulated on p. 189.) Nitrate two drops of the hydrocarbon by the procedure of Test 914 for mesitylene. Do not increase the quantities of acids or solvents prescribed, but follow the directions given literally in every detail, except that the quantity of 95 per cent alcohol used in erystal- lizing at the point marked by the single asterisk (*) should be reduced from 15 ce. to 5 ee. The trinitro-p-xylene formed in this test is a nearly white crystalline compound melt- ing at 138.5°-139° (uncor.). 921. o-Xylene. (Properties tabulated on p. 189.) This hydrocarbon is easily distinguished from the meta and para compounds by the fact that when nitrated by the procedure prescribed in Tests 919 and 920, it gives an oily instead of a solid high-melting nitro-derivative. The following test may also be applied. Sulphonate 0.25 ce. of the hydrocarbon by persistently shaking in a test-tube with 1 cc. of sulphuric acid (sp. gr. 1.84). During the shaking the tube should be gently warmed from time to time by dipping it for a second or two into boiling water. When the hydro- carbon has all dissolved (this will require 3-5 minutes), cool, and pour slowly into 10 cc. of a saturated solution of common salt. Cool well, and shake vigorously. The mixture will soon become pasty from the separation of a heavy precipitate of sodium o-xylenesulphonate. Filter, and wash with 10 cc. of a cold saturated salt solution. Press on a tile, and dry 10 minutes at 125°. Crush. Mix 4 parts by weight of phosphorus pentachloride with 3 parts of the dry sulpho- nate in a test-tube, and heat for 10 minutes at about 100°. Cool, and pour in 5 ce. of ice-cold water. Shake. Allow to settle. Decant the water through a wet filter. Wash again SPECIFIC TESTS FOR SPECIES OF GENUS IX. 203 by shaking with 5 cc. of cold water, followed by decantation. Return any precipitate that may have collected on the filter to the test-tube. Add 2 cc. of the most concentrated ammonia. Boil gently until the ammonia odor has almost disappeared. Dilute with 10 ce. of water. Heat to boiling. Filter hot. Cool the filtrate well with ice water. Shake vigorously, and collect the precipitate of the sulphonamide on a small filter. Wash with 5 ce. of cold water. Redissolve in 5 ce. of boiling water, and cool. Shake, filter, and wash as before. Repeat these operations twice more. Then dry for 15 minutes at 110° and determine the melting-point. o-X ylenesulphonamide, the product of this test, crystallizes in pearly-white scales which melt at 143.5°-144°, CHAPTER XII. S.U'B'O RD Ee Rael THE COLORED COMPOUNDS OF ORDER I. (Containing Carbon, Hydrogen, and Oxygen.) THE CONTENTS OF SUBORDER II ARE INDICATED BY THE TITLE ‘‘ COLORED COM- POUNDS.” ANY CAREFULLY PURIFIED SOLID SPECIES OF ORDER I WHOSE COLOR EXCEEDS TINT 3 OF THE COLOR STANDARD (CF. PAGE 281) IN SATU- RATION, OR ANY YELLOW LIQUID SPECIES WHOSE COLOR WHEN VIEWED IN A LAYER 1 CM. THICK AGAINST A WHITE BACKGROUND IS MORE SATURATED THAN YT1 OF THE STANDARD, WILL BE CONSIDERED COLORED. A very faint tinge of straw-yellow, caused by traces of impurities or decom- position products so small as to have no appreciable effect on the general chemical behavior of the substance, is often observed in specimens of compounds belonging to Suborder I. In doubtful cases the attempt should be made to decolorize such substances by boiling their solutions with purified bone-black. Compounds with colors less saturated than the tints of Series 3 of the color standard are described in Suborder I with the colorless compounds, but also sometimes receive mention in Suborder II. Subdivisions of Suborder II.—The species described in Suborder II are arranged in two divisions, A for solids, and B for liquids; but are not numerous enough to yequire further subdivision into genera. They are all either ketones, quinones, or phenols. The solid species are grouped in two sections. The arrangement in Section 1 is based upon melting-point, as 1s customary for solids in other parts of the work. Section 2 is virtually an appendix to Section 1, added to provide for the partial identification of certain important bodies, dyes, and acidimetric indicators, which have the common property of giving intensely colored solutions in alkali, but which fuse with so much decomposition, or at such high temperatures, or which are so difficult to isolate in a state of perfect purity, that their melting-points are unknown or have little practical significance. Some of these bodies are not met with except in the form of moist pastes and amorphous powders of rather variable compo- sition, and are only admitted to the tables as compounds by courtesy because of the interest attaching to them as colors. The arrangement of species in Section 2 is dependent on the color of the solution of the substance in dilute aqueous alkali, as is more fully explained on page 212. To make the color comparison, dissolve a few milligrams of the finely powdered sub- stance by shaking in a test-tube with 5 cc. of 1 per cent cold sodium-hydroxide solution; and then dilute, if necessary, with water, until the mixture when held before a white background shows a depth of color that approaches either the normal tone, or the first tint of that hue of the standard which the color of the solution most closely resembles. The comparison should be made quickly, as many of the solutions absorb oxygen from the air, or change rapidly in both hue and tone on standing. 204 SUBORDER II, COMPOUNDS CONTAINING C, H, AND O [ORDER I]. COLORED COMPOUNDS. DIVISION A, SECTION 1,—SOLID SPECIES OF DETERMINED MELTING-POINT. Melting-point CORDE 28 41 45-5 55 57-8 59-60 68 68-9 69-70 ral 72-3 83 -5-4 90 ee ch Pa ee ee eee ena COLORED COMPOUNDS.—Solid Species of Determined Melting-point. + Phoron, C,H,,0.—B. p. 198-5°.—Pale-yellow cryst.—Cf. VII, A, p. 136. Benzfuril, Ph.CO.CO.C,H,0.—Fine yellow ndl. fr. h. dil. ale-—Volatile undec.— S. alkalies giving benzfurilic ac. (dec. 108°).—25 pt. c. Br give tetrabromide, yellow ndl. fr. alc., m. p. 127°-8°. t+ Thymoquinone, (Me).(Me,CH).0O..C,H.(1, 4, 2,5).—B. p. 232°.—Orange-yel- low (OY) tbl. v. d. s. aq.; e. s. ale. or eth.—Odor sharp like quinone, but also like thymol!—S. without decomposition in c. cone. H,SO, or HNO,.-— For characteristic color reactions cf. B. 18, 3196.—Heat 0-1 grm w. 5 cc. aq. and 0-2 grm. Br for $ hr. on boiling water-bath. Wash the red oil with c. aq. until it is yellow and crystalline. Recryst. twice fr. 2 cc. h. alc. (add- ing a little eth. if oil should not crystallize readily). Gives dibromide, yel- low lfts., m. p. 73°. 1, 2-Dimethylquinone(3, 6), Me,.C,H,.0,.— Sbl. in yellow ndl., d. s. aq.; as alc. or eth. tT Benzylideneacetophenone.— Pale yellowish pr.—Cf. VII, A, p. 137. Dioxybenzophenone, (C,H,.0H),.CO.—B. p. 330°—-40° d.—Light-yellow ndl. fr. lgr.—Alm. i. aq.; v. s. alc. or eth.; s. K,CO,; but ppt’d by CO,.—Sol. in dil. alc. colored brown-red by FeCl,.—Warming w. conc. H,SO, or boiling w KOH sol. gives o-benzophenone oxide, ndl. fr. alc., m. p. 173°-4°, v. d.s. c. aq, Methyl Cinnamenylvinyl Ketone, C,,H,,O.—Cf. VI, A, p. 137. Toluquinone(2, 5), Me.C,H;.0,,—Sbl. in rhombic-yellow lft., d. s. c. aq.; v.s. alc. or eth.—Odor pungent, quinone-like !—Aq. sol. is colored brown-red by alkalies —Reduced by SO, to hydrotoluquinone, v. s. aq.; pearly lft. fr. bz.; m. p. 124°. Diphenylpropanetrione, (PhCO),.CO.—B. p. 247° (60 mm.).—Golden-yellow ndl. fr. lgr.; e. s. ale—Very hygroscopic.—Sapon. by NaOH gives benzoic and mandelic acids, benzoin, and CO,.—2 pt. boiled w. 5 pt. aniline and 10 pt. alc. give a dianil, yellow pyramids fr. bz., m. p. 148°. Phenoquinone, C,H,0,.2C,H,O.—Fine red ndl. w. green reflections !—S. c. aq. ; e. s. alc. or eth.; s. lgr. (dif. fr. quinone and quinhydrone).—The red crystals become blue-black upon addition of alkali.—Reduced to hydroquinone (Test 411) by SO. 1, 3-Dimethylquinone(2, 5), Me,.C,H,.0,,—Yellow ndl. Diphenylene Ketone, (C,H,)..CO.—B. p. 341-5°.—Large yellow tbl. fr. B16.5 1: aq.; v. s. ale. or eth.—Slowly oxid. by alkaline KMnO, to phthalic ac.— Oxime, m. p. 195°.—Well-cooled, fuming HNO, gives yellow nitro-comp. which sbl. easily, is d. s. c. alc., and melts at 220°.—Fusion w. KOH gives phenylbenzoic ac. Pseudodiphenylene Ketone, C,,H,0.—Dark-red cryst. fr. eth.—C. fuming HN Os . gives dinitro-comp., ndl. fr. h. glacial Ac; i. ale.; m. p. 310°.—Boiled w. dil. ale. quickly gives diphenylene ketone (cf. above). Acetonephenanthrenequinone, C,,H,,0;.—Thin pale-yellow tbl. fr. eth.; i. aq.— Phenanthrenequinone separates upon boiling w. KOH sol. Retene Ketone, C,,H,,0.—Vitreous sulphur-yellow cryst. ; vol. w. st.; e. s. ale. or eth.; i. NaHSO,.—Combines w. phenylhydrazine, but not w. hydroxyl- amine.—Ignition w. Zn dust gives retenefluorene. — 205 206 Melting-point (C8), 92-3 95 98 102-3 103 103 103-4 104 106 109-10 111 112-2-5 115-7 d. 115-20 120-5 125 125 SUBORDER II, DIV. A, SECT. 1, (ORDER I.) COLORED COMPOUNDS.—Solid Species of Determined Melting-point Acenaphthylene, C,,H,.—Golden-yellow cryst.—Cf. LX, A. + Benzil, Ph.cO.CO.Ph.—B. p. 346°-8° c.—Fine pale-yellow (YT2) ndl., i. aq.; e. s. alc. or eth.—Dissolve 4 pt. in x’s abs. alc.; add 1 pt. solid KOH and boil down in porcelain dish. An intense violet color (VR) appears, but disappears on continued boiling !—Sapon. w. NaOH gives benzilic ac. (quan- titative).—Gives oximes. Benzocotoin, (OH)(COPh)(OMe),.C,H,.—Pale-yellow pr. fr. alc.; e. s. eth.; s. dil., but i. conc. NaOH.—PbAc, gives yellow ppt. w. NH,OH sol.—Sol. gives dark-brown color w. FeCl,. Cinnamyleneacetophenone, C,,H,,0.—Golden ndl. fr. ale-—Colored cherry-red by conc, H,SO,.—Oxime, m. p. 131°. Oxy-m-xyloquinone, Me,.C,H.(OH),.0,.—Orange-red ndl., v. vol. w. st.—Sbl. in yellow ndl.—Odor like benzoquinone !—S. h. aq.; sol. colored red-violet by alkalies, even by CaCO,! Methyl Oxynaphthyl Ketone, Me.CO.C,,H,.OH.—B. p. 325° sl. d.—Pale-green 6-sided pr. fr. bz. !—I. aq.; d.s. alc.; s. alkalies, but ppt’d by CO,.—Oxime, m. p. 168°-9°. . Pipitzahoic Ac., (Perezon), C,;H.,0,.—Golden lft. fr. ale-—Sbl. undec.—S. in KOH w. intense purple color.—Ba salt purple and v. d. s. aq.—CO, sepa- rates ac. fr. salts. Santalin, C,,H,,0,(?).—-Mic. red cryst. or red mass; misc. w. abs. alc. w. blood- red color; s. eth.—A weak acid, s. alkalies w. violet color—Ammon. sol. gives dark-violet cryst. ppt. w. BaCl,—KOH fusion gives Ac and resorcin (cf. Test 418). Cinnamylenebenzylideneacetone, C,,H,,0.—Yellow pr. fr ale-——Oxime, yellow Ifts., m. p. 127°-8°. Phenylnaphthoquinone, Ph.C,,H,;0,.—Golden-yellow ndl. fr. ale.; s. eth.; d. s. lgr.—Polymerized quickly by sunlight.—An alc. sol. sat. w. NH, separates a comp. (red ndl. s. eth.) on standing, m. p. 174°.—Gives aniline derivative fr. h. ale. sol. w. aniline, dark-red ndl., m. p. 158°. I, 2, 4, 5-letramethylquinone, Me,.C,.0,.—Sbl. at 100° in golden ndl., d. s. ¢e. ler.; v.s. alc. or eth.—Very volatile with steam. | Dibenzylideneacetone, (Ph.CH:CH),.CO.— Gives Test VII-1.— Yellow Ift., d.s. alc.; s. eth.—S. in conc. H,SO, w. deep orange-red color.—Colored dark vermilion by conc. HCl without being dissolved.—Adds Br, in CHCl, sol. to form comp. of m., p. 208°-11° d., ndl., v. d. s. ale. or eth. + Benzoquinone, p-C,H,.0,.—Peculiar, sharp irritating odor slightly suggesting that of chlorine !—Golden-yellow monoclinic pr. fr. h. aq.; d.s. ¢. aq.; e. 8. alc. or eth.; s. h. lgr.—Sbl. easily in golden ndl.—Sol. in alkalies absorbs oxygen rapidly, becoming dark-colored.—Identify by Test 1012! I, 2-()-Naphthoquinone, C,,H,O,.—Small odorless red ndl. fr. eth., or orange lft. fr. bz.—Not vol. w. st. —-Unstable.—Sol. in dil. NaOH is yellow and absorbs O rapidly.—Add 14 pt. aniline to a cone. sol. of 1 pt. of the quinone in h. alc.; anilinonaphthoquinone separates as red ndl. w. golden to greenish reflections, i. aq.; d.s. alc.,m. p 240° (differs from aniline a-naphthoqui- none in being s. in cold alkalies) —KMn0O, oxidizes to phthalic ac.—Reduced by SO, to corresponding hydroquinone. + Absinthin, C,,H,.0,+ 4H,0.—(Fr. Artemesia absinthium.)—Yellowish (OYT2) mic. cryst. fr. alc. w. bitter taste and wormwood odor (sample fr. Merck) !— Alm. i. c. aq.; e. s. ale or eth.—Sol. in NaOH is brown-red.—Sol. in H,SO, is brownish and then green-blue liq.—Reduces ammon. AgNO,, but not Fehling’s sol.—Ale. sol. gives ppt. w. tannic ac. Benzohydroquinone, Ph.CO.C,H;.(OH),.—Long yellow ndl. fr. dil. ale.; e. s, ale. or eth. 1, 4-Dimethylquinone(2, 5), (Phloron), Me,.C,H,.0,.—Long golden-yellow ndl. fr.alc.; d.s. h. aq. or c. ale-—Sbl. undec.—Reduced by SO, to hydrophloron, —Br aq. gives dibrom-derivative, golden lft. fr. h. ale., m. p. 184°.—Aniline derivative yellow-green ndl., m. p. 264° (A, 255, 171). SUBORDER II, DIV. A, SECT. 1. 207 (ORDER I.) Melting-point CGE 125 127 129 abt. 130 130-1 132-5 133-4 135 140 140 140-1 142 142 143-4 143-4 146-7 146-8 COLORED COMPOUNDS.—Solid Species of Determined Melting-point. 1 1, 4-(a)-Naphthoquinone, C,,H,O,.— Yellow (Y) ndl. w. pungent quinene like odor, which is, however, much less intense than that of benzoquinone.—E. vol. w. st. (dif. fr. -comp.).—S. ale.; e. s. eth.; d.s. aq.—Sol. in alkali is red-brown.—Identify by Test 1013! Oxylapachol(a), C,,H,,0,.— Yellow ndl. e. s. alc., eth., or alkalies—AgA + H,O, chestnut-brown cryst. ppt. | af-Dibenzoylstyrene, Ph.CO.CPh: CH.CO.Ph.—Pale-yellow ndl. (YT2) fr. alc., v. d. s. c. alc. or eth.; e. s. h. alc —Odor faint aromatic.—M. p. of nitro deriv. 155°. Oxypipitzahoic Ac., C,,H,,0,.—Reddish-yellow lft.—Sol. in KOH is violet-red. + Cotoin, MeO.C,H,(OH),.CO.Ph.—(In coto bark.)—Pale-yellow pr. fr. h. aq.— Sulphur-yellow (sample fr. Schuchardt YT2) tbl. fr. ale-—Taste sharp and biting; dust provokes sneezing.—V. d. s. c. aq.; e. 8. alc., eth., NaOH, or Na,CO,, but ppt’d by CO,.—Reduces ammon. AgNO, sol. cold and Fehling’s sol. on heating.—In conc. aq. sol. FeCl, gives brown-black ppt. and in alec. sol. brown-red color.—Warming w. conc. H,SO, gives benzoic ac. and phloro- glucin.—Sol. in ammonia gives yellow amorphous ppt. w. PbAc,.—Yields a cryst. oxime. Chrysoketone, C,,H,,O.—Silky yellow ndl. or orange-red pr. Salicyloresorcin, HO.C,H,.CO.C,H;.(OH),.— Yellow lft. fr. h. ale.—S, h. Na,CO, sol., but ppt’d by CO,.—Fusion w. KOH gives resorcin and salicylic ac. + Furoin.— When pure, slightly yellowish; usually buff colored. Sol. in NaOH violet-red.—Cf. Genus IV, A. + Hematoxylin, C,,H,,0,+ 3H,0.—Melts w. loss of aq.—Taste sweet !—Colorless tetragonal pr. when pure and freshly prepared, but soon changed by sunlight to dark red-brown.—D. s. c. aq.; e. s. alc., eth., or h. aq.; s. alkalies and alkali carbonates w. intense beautiful purple-red color, changed by acids to a clear orange-yellow (OY).—Thin layers of the very intensely colored alkaline sol. are V; largely diluted VR and R.—Gives dark color w. FeCl, and finally a ppt.—W. alum sol. gives rich RV color, which largely diluted gives VR.— Reduces ammon. AgNO; sol. in the cold. Lapachol, C,,H,,0;—Small yellow pr. fr. eth. or bz—Sbl. w. much difficulty.— S. NaOH or Na,CO, w. red color.—Dissolved by shaking w. 5 pt. conc. H,SO, and ppt’d by aq. gives §-lapachon, which cryst. fr. alc. in flat orange-red ndl., m. p. 155°-6°.— Readily oxid. to phthalic ac. by HNO, (sp. gr. 1-38). j Alizarin Yellow A (Trioxybenzophenone), (HO),.C,H,.CO.Ph.—(Cryst. w. 1 aq.).—Yellow ndl., d.s. h. aq.; e. s. alc. or eth.; ppt’d fr. Na,CO, sol. by CO,.—Sol. in conc. H,SO, yellow.— Warming w. conc. H,SO, gives benzoic ac. Pyrene Ketone, C,,H,0.—Golden-yellow tbl. fr. ale—Gives NaHSO, comp.— Fuming HNO, dissolves w. deep purple-red color—KMn0O, oxid. to naph- thalic ac. + Dicinnamenyl Vinyl Ketone, C,,H,,0.—Golden-yellow ndl. fr. abs. ale.; d. s. c. alc. or eth. Perezinon, C,,H,,0,.—Pale-yellow ndl. s. ale. or eth—Garnet-red on warming with Millon’s reagent. 2, 4’-Dioxybenzuphenone, (C,H,.0OH),.CO.—Pale-yellow Ift. fr. h. aq.; e. s. ale. or eth.; s. alkalies, but ppt’d by CO,.—Fusion w. KOH gives phenol and p- oxybenzoic ac. 1-Oxyxanthone, C,,H,O,.—Clear-yellow ndl. fr. alc.; d.s. h. aq.—Fusion w. KOH gives resorcin and salicylic ac.—W. Br in Ac sol. gives dibrom-derivative, yellow ndl., m. p. 222°. + Barbaloin, C,,H,,0, (dried at 100°).—(Before drying, yellow ndl., w. xH,O, m. p. 70°-80°).—Taste sweetish and then very bitter.—S. 60 pt. aq., 20 pt. alc., or 470 pt. eth.; v. s. NaOH to deep orange-red sol.; e. s. acids.—A trace of FeCl, gives fine red-violet color w. aq. sol.; more FeCl, gives a green- ish black !—Br water added drop by drop w. a pause of 4 min. between each addition gives a fine VRT2 color. An x’s of Br immediately changes the color to yellow, and then gives a vellow ppt. of tribromaloin.—A little of the powder stirred into a drop of HNO, (sp. gr. 1-2) gives a deep carmine-red, soon changing to orange. (The carmine color w. nataloin is permanent, but is not given at all by socraloin ) SUBORDER II, DIV, A, SECT. 1, (ORDER I.) Melting-point (Cosh 148 149 152 151-4 156-8d. Ay All 171-2 170-78 177 177 178 178(?) or 190 COLORED COMPOUNDS.—Solid Species of Determined Melting-point. Vulpic Ac., C,yH,,0,.—(In Cetraria vulpina.)—Yellow monoclinic lft. fr. ale., v. d. s. alc.; e. s. eth.—Heated above 200° gives MeOH and pulvic anhyd.— Sapon. by boiling Ba(OH), gives MeOH, oxalic, and a-toluic ac. 2, 3, 4, 2’-Tetraoxybenzophenone, (OH),.C,H,.CO.C,H,.OH.—Cryst. w. 1H,O in greenish-yellow Ift.; e. s. alc. or eth.—W. warm conc. H,SOQ, splits to sali- Cylic acs. ete. Paracotoin, C,,H,O,.—Pale-yellow lft., d. s. h. aq.; e. s. eth. or h. ale.—S. in alkalies, sapon. giving a yellow i. ac., m. p. 108°.—Fusion w. KOH gives piperonylic ac.—Br substitutes in c. CHCl, sol. giving comp. cryst. fr. alc., m. p. 200°-1°. 5-a-Oxynaphthoquinone (Juglon), HO.C,,H,;.0,.—Yellowish to brick-red ndl. fr. CHCl,.— Begins to darken on heating to abt. 125°.—Somewhat vol. w. st.—I. aq.; e. s. ale.; s. conc. H,SO, w. intense blood-red color, s. in very dil. NaOH w. purple color, changing to brown.—Boiling w. aq. gives i. green- ish-brown powder, s. in alkalies w. deep-violet color.—CuAc, added to ale. sol. gives dark-violet mic. pr. w. metallic lustre. Euxanthic Ac., C,,H,,O,,.—Straw-yellow ndl., anhydrous when fr. ale.—D. s. ¢. alc.; e. s. eth.—PbAe,, yellow gelatinous ppt.—Dist. w. HCl gives furfurol (Test 115). Furil, C,H,0.CO.CO.C,H,0.—Golden-yellow ndl. alm. i. aq.; d.s. eth. or c. alc.; e. s. CHCl,.—Sapon. gives furilic ac. (v. unstable).—E. dec. by conc. HCl.— Reduced to furoin by Na amalgam. {+ Anthranol.—Cf. Genus IV, A.—Color YT2-YT3. D. s. in alkali w. bright- yellow color. Diphenylbutanoltrion, Ph.CO.CH(OH).CO.CO.Ph.—Yellow pr.; e. s. alc. or eth. Dioxydimethyltriphenylmethane, (Me.C,H,.0H),.CH.Ph.—Pale-yellow ndl. fr. dil. alc.; d.s.aq.; e. s. alc. or eth.; e. s. dil. NaOH.—Gradually turns red on exposure to air, especially if warmed. Diacetate by boiling w. x’s acetic anhyd., yellow ndl. fr. ale., m. p. 94°. t+ Quinhydrone, C,H,.0,.C,H,.(OH),.—Dark-green pr. w. metallic lustre, red- brown by transmitted light !—Sbl. w. slight dec.—S. h. aq.; e. s. ale. or eth. w. yellow color; i. lgr.—Boiled w. aq. splits to quinone and hydroquinone.— Reduces ammon. AgNO, sol.—Reduced by SO, to hydroquinone (Test 411), 6-Phenyl-3-benzoylpyronon, C,,H,,0,— Yellow ndl. fr. ale.; d.s. c. alc., e. s. eth.—Boiled w. ale. KOH gives acetophenone, benzoic, and acetic ac.— FeCl, gives orange-red color w. alc. sol.—Sol. of NH, salt gives a scarlet-red ppt. w. FeCl,—Sol. in conc. H,SO, is olive-green, becoming violet when warmed. + Chrysarobin, C,,H,,0,.— Yellow nd. or lft. fr. acetic ac. (sample fr. Merck YS1 powd.).—Sbl. w. dec. in yellow Ift.—I. aq. or NH,OH; s. in not too dil. KOH w. yellow color and green fluorescence.—Air passed through sol. oxid. to chrysophanic ac., m. p. 162°.—Ignition w. Zn dust gives methylanthra- cene.—Sol. in conc. H,SO, is yellow. 2-Methylanthraquinone, Me.C,,H,.0,.—Pale-yellow lustrous ndl., s. eth.; v. d. s. alce.; s. conc. H,SO, w. blood-red color, changing to violet on heating !— Ignition w. Zn dust gives 2-methylanthracene. 2-Naphthyl-1, 4-Naphthoquinone, C,,H;.C,,H,.0,.—E. s. alc. or bz.; s. conc. H,SO, w. indigo-blue color! Curcumin, C,,H,,0,.— Yellow or orange-yellow pr.; i. aq.; d. s. ale.—Sol. in eth. fluoresces green.—S. alkalies w. intense red-brown color.—Sol. in cone. ° H,SO, is fine reddish purple.—Alc. sol. gives bright-red ppt. w. PbAc, sol.— Place piece of filter-paper in alc. sol. and evaporate to dryness at 100°. Saturate paper w. boracic ac. sol. A red color appears at once or cn evap- orating. A drop of NaOH sol. will give series of fine colors, green and pur- ple most prominent; HCl will give a red color changed to green and tas by x’s of alkali. Dioxymethylanthraquinone (Chrysophanic Ac.), C,,H,,0,.—6-sided tbl. fr. bz.; golden yellow ndl. fr. ale.; s. eth. or h. ale.; v. d. s. NH,OH or alkaline car- bonates; v.s. NaOH; in each case w. deep-red color.—Salts dec. by CO;.— Ignition w. Zn dust gives methyl anthracene. "a a SUBORDER II, DIV. A, SECT. 1, 209 (ORDER I.) eo aa COLORED COMPOUNDS.—Solid Species of Determined Melting-point. 181-2 Fluorenequinone, C,,H,O,.—Yellowish granules fr. bz.—Hot KOH sol. gives brown product w. odor like diphenyl. 185-5 Picylene Ketone, C,,H,,0.—Golden-yellow cryst. powder, e. s. h. bz.—Fusion w KXOH gives picenic ac. 188 Fluoranthenequinone, C,,H,O,.—Small red ndl.; s. ale. or NaHSO, sol.—Quickly oxidized to CO, by CrO, mixture (dif. fr. fluorenequinone).—Ignition w. soda- lime gives diphenyl. 187-92c. Sinapic Ac., C,,H,,0,.—Pale-yellow ndl., e. s. h. alc.; i. eth.—Na salt gives red ppt. w. FeCl, a. 190 Rutin, C,,;H;,0,,+2H,0.—(In leaves of rue: Ruta graveolens.)—Clear yellow silky ndl. fr aq.—Loses 2H,O at 150°-60°.—E. s. h. aq.; 1. eth.; s. alkalies, —Sol. colored dark green by FeCl,!—Hydrolyzed by boiling w. dil. ac. to quercetin and rhamnose. 191-2 o-Diphenyleneketonecarbonic Ac., C,,H,O;.—Orange-red ndl. fr. dil. alc., alm. i. aq.; e. s. eth.—Ignition w. Zn dust gives fluorene. Warmed w. fuming HNO, gives nitro ac., m. p. 245°-6°. 195 Caffeic Ac., C,H;.(OH),.CH: CH.CO,H.—(Cryst. w. $H,O.)—Straw-yellow pr. fr. aq.; e. s. ale.—Aq. sol. becomes grass-green w. FeCl, changing to blue or violet upon addition of Na,CO,.—Alkaline sols. brown in the air.—Aq. sol. reduces h. AgNO, and gives a yellow ppt. w. PbAc,.—Dist. gives pyrocatechin, Test 416. 195-6 a-Usnic Ac., C,,H,,0;,—(Fr. various lichens.)—Sulphur-yellow pr. fr. h. alc.; d.s. c. alc. or eth.—Very weak acid.—Salts are yellow.—FeCl, gives a dark brownish-red color w. alc. sol. 197-7-5 Retenequinone, C,,H,,0,.—Flat orange ndl.; s. h. alc.; d.s. h. eth. or lgr.; i. c. NaOH; s. conc. H,SO, w. green color !—A drop of ale. KOH added to an alc. sol. gives dark Bordeaux-red color which disappears on shaking w. air! Upon warming w. exclusion of air, color reappears.—Ignition w. Zn dust gives retene, m. p. 94°. 199-201 Carbousnic Ac., C,,H,,0,—(In lichens.)—Yellow pr. similar in properties to a-usnic ac. (cf. m. p. 195°-6°). 200d. Eupittonic Ac., (MeO),.C,,H.O,.—Hair-like orange ndl. fr. ethyl ale.—Dibasic.— The blue solution in NaOH gives blue ppt. of Na salt with x’s alkali which changes to green cryst. after 24 hrs. 200-1 Bithymoquinone, C.,H,,0,.—Long clear yellow silky ndl., not vol. w. st.—V. d. s. solvents; i. abs. eth.; s. undec. in h. fuming HNO;.—Dist. gives much thymoquinone (cf. p. 205) !—Not reduced by SO,, but gives hydrothymo- quinone when dist. fr. Zn dust. 200-2 Euxanthonic Ac., [C,H;.(OH),],.CO.— Yellow warts or cryst. fr. h. aq., s in KOH w. yellow color which darkens rapidly in the air——Red-yellow ppt. w. PbAc, sol.—Fusion splits to euxanthone and H,O.—FeCl, gives red color. 202 Quinacetophenone, Me.CO.C,H,(OH),.—Pale yellow-green cryst.; v. d.s. c¢. aq. —Reduces Fehling’s sol.—IeCl, gives transient deep-blue color w. aq. sol. 202 + Phenanthrenequinone, C,H,.CO.CO.C,H,.—B. p. a. 360°.— Yellow-orange (YO) ndl.; sbl. in cryst.; d.s. h. aq.; d. s. alc. or eth.; e. s. h. Ac; e. s. warm NaHSO, sol. !—Ignition w. Zn dust gives phenanthrene; w. soda-lime, di- phenyl.—Identify by Test 1014! 206d. a-Anthracenecarbonic Ac., C,,H,,O,.—Cf. III, A, 2. 202-19d. Scoparin, MeO.C,H;.(OH).C,,;H,O;.(OH) 5+5H,0.—(In Spartium scoparium.)— Small clear yellow cryst. fr. 70% ale.; v. d. 8. ¢. aq.; e. s. h. aq.; i. eth.; e. s. NaOH or Na,CO, giving greenish-yellow sol.—Bleaching powder colors dark red —HNO, gives picric ac.—Fusion w. KOH gives phloroglucin, va- nillic, protocatechuic, and acetic acids. 211-12 Isoanthraquinone, C,,H,O,.—Pale-yellow ndl.—Fusion w. KOH gives blue mass. —More s. in H,SO, than anthraquinone. 214-15 Pulvic Ac., C,,.H,,0,.—Orange pr. fr. ale. which effloresce to orange powder’ s. aq., eth., CHCl,, or bz.—Adds Br, and is oxid. by alkaline KMnO,. ee 210 SUBORDER II, DIV, A, SECT. 1. (ORDER I.) Melting-point (CON), 240c. abt. 250 253-6d. 256 261 262-3 COLORED COMPOUNDS.—Solid Species of Determined Melting-point. { Piperic Ac., CH,.0,.C,H,;.CH: C,H,: CH.CO,H(3, 4, 1).—Pale-yellow (YT2) ndl., alm. i. aq.; s.h. ale. or eth.—f The sol. in dil. Na,CO, when gently oxid. by warming on a watch-glass w. a few drops of KMnO, sol. emits the delicate heliotrope aroma of piperonal !—BaaA,, i. ¢. aq. Purpurin-1-carbonic Ac., C,,H,(OH),0,.CO,H.—Red Ift., i. c. aq. or ale.; d. s, h. CHCl,.—Sol. in Na,CO, is orange-colored.—Boiling w. aq. or alc. gives CO, and purpurin. a-Dioxyanthracene, C,,H,,0,.—Yellow lft. or ndl., v. s. ale; the yellow sol, fluoresces strongly blue.—FeCl, or Br gives blue-green color w. alc. sol. Oxylepidene (‘‘ Needle-shaped”’), C,,H,,0,.—Yellow ndl., i. aq.; d.s. h. ale; alm, i. eth. Diphenyleneketonecarbonic Ac., CO.C,,H;.CO,H.—Yellow ndl. fr. ale.; i. aq.; s. conc. H,SO, w. yellow color.—Gives oxime, m. p. 263°.—AgaA yellow ppt. Purpurinxanthinecarbonic Ac., C,,H,(OH),O,.CO,H.—Golden Ift. fr. glacial Ac, s. eth. or h. aq.; s. in NaOH w. red color, or in conc. H,SO, w. intense yellow color.—Dec. above m. p. 2-Oxyxanthone, C,,H,0,.— Yellowish ndl. fr. dil. ale-—Acetyl deriv., m. p. 161°, Oxylepidene (‘‘ Octahedral’’), C,,H,,O,.— Yellowish octahedra fr. h. Ac, alm. i. alc.; i. h. alcoholic KOH.—Heated nearly to boiling gives isomer, s. alc., w. Miipelso., Chrysoquinone, C,H,.CO.CO.C,,H,.—Orange-red ndl.; s. h. ale.; v. d. s. eth.; s. in cold H,SO, w. corn-flower-blue color, ppt’d by aq. (delicate). Sbl. in red ndl. Oxid. by KMnO, to phthalic ac.—Ignition w. Zn dust gives chrysene. } Euxanthone, C,,H,O,.—Pale-yellow (YT1) Ift. or ndl.; sbl. w. dee.—I. aq.; e. s. h. alc.; d.s. eth.; s. NaOH or conc. NH,OH w. yellow color.—Green color w. FeCl,—PbAc, gives ppt. w. alc. sol—Gives no oxime or phenyl- hydrazone. + Brazilin. — Cf. Gen. IV, A!— Cryst. red-brown after exposure to air and light. Sol. in NaOH intense red! Taste sweet! {+ Daphnetin, C,H,O,.(OH),.—When strongly heated on a watch-glass has a faint coumarin-like odor.—Pale yellowish ndl. fr. dil. ale. (preparation fr. Schuchardt YT3); s. h. aq.; v. d. s. eth.—FeCl, added to a 1:4000 aq. sol. gives a permanent green (G) color, changing to red (RS2) when Na,CO, is added (cf. Test 401) —Reduces ammon. AgNO; or Fehling’s sol. instantly — Gives a yellow gelatinous ppt. w. PbAc,. } Purpurin, 1, 2, 4-Trioxyanthraquinone, C,H,.(CO),.C,H.(OH),.—Deep-red ndl. fr. abs. ale.-—Long orange ndl. (+H,O) fr. dil. ale.-—S. aq. w. deep-yellow color (no absorption bands).—Sol. in eth. shows absorption bands at E and F.—Sol. in NaOH or Na,CO, is bright red w. two absorption bands in the green.—Sol. in cone. H,SO, is cherry-red.—Oxid. by HNO, (cf. Test 905-3) gives phthalic ac.—W. alumina mordant dyes scarlet. Acenaphthenequinone, C,,H,O,.—Sbl. in yellow ndl.—V. d. s. ale. or ec. Ac.— Dissolved to an acid by boiling w. KOH.—Reduction w. Zn dust in boiling Ac sol. gives acenaphthenon. Xanthopurpurin, C,H,.(CO),.C,H,.(OH),.— Yellow ndl. fr. Ac.—Sbl. in orange ndl.—S. in Ba(OH), sol. (dif. fr. alizarin and anthrachryson).—S. in NaOH is red.—Boiled w. KOH in air gives purpurin (cf. spectrum above).—Igni- tion w. Zn dust gives anthracene.—Does not color fibre mordanted w. alumina. Resorcinphenylacetein, C,,H,,0,.—Mic. brown plates, green by reflected light, fr. alc.+Ac.; i. eth. or bz.—Dil. sol. in NaOH shows intense-green fluores- cence.—Diacetate, silky ndl. fr. Ac., m. p. 150° d. Gentianine, C,,H,O,.Me.—Pale-yellow silky ndl., d. s. h. aq., ale., or eth.; e. s. alkalies w. golden-yellow color, reprecipitated by CO,. Diacetate (boiling w. acetyl chloride), hair-like ndl. fr. alc., m. p. 196°.—Reduces Tollen’s reagent. Melting-point ‘CCA ————=> 275 (284 - 5c.) 275 276 280 282d. 283 289-90 SUBORDER II, DIV. A, SECT. 1. 211 (ORDER I.) emcees COLORED COMPOUNDS.—Solid Species of Determined Melting-point. 7 Anthraquinone, C,H,.CO.C,H,.CO.—B. p. 380° ¢.—Sbl. in pale-yellow ndl.— S. 44 pt. h. ale.; v. d.s. c. ale. or eth—_V. stable, not attacked by boiling NaOH or oxid. agents.—Ignition w. Zn dust gives anthracene.—Identify by Test 1011! 1, 3-Dioxyflavone, C,,H,,0,.—Thin pale-yellow tbl.—Sbl. in ndl.—Alm. i. aq.; s. h. Ac.; e. s. alkalies w. intense-yellow color.—Ale. sol. is dirty violet w. FeCl,.—Split by boiling KOH to acetophenone, phloroglucin, etc. 2, 3-a-Dioxynaphthoquinone, (HO),.C,,H,.O,.—Orange-red Ift., green by re- flected light !—Sbl. in ndl. w. metallic lustre—D. s. h. aq.; v.d_s. ale. or eth.—Sol. in NaOH is corn-flower blue; in Na,CO, violet-blue.—E. oxid. to phthalic ac. by Test 905-3. 1, 5-Dioxyanthraquinone (Anthrarufin), C,,H,O..(0H),.—Sbl. in light-yellow TooLued lft., alm 1. -ad.s d. 6, aic.- sa eth, aims, NH.OH? Na.CO,,, or Ba(OH),; e. s. KOH w. violet-red color.—sS. conc. H,SO, w. very intense- red color and fluorescence, distinct even at dilution of 1: 10,000,000 !—Con- tinued fusion w. KOH gives salicylic ac., etec.—Ba salt is carmine-red. Pyrenequinone, C,,H,O,.—Sbl. w. slight dec. in light purple-red ndl., v. d. s. alc., eth., or CS,; s. NaHSO,; s. conc. H,SO, w. brown color.—Ale. sol. +1 drop NaOH is dark wine-red, unchanged upon shaking w. air.—Ignition w. Zn dust in H gives pyrene. G-Anthraquinonecarbonic Ac., C,H,:(CO),:C,H;.CO,H.—Yellowish pr. fr. alc., v. d. s. alc. or eth.—Sbl.— Boiled w. Zn dust and KOH gives intense-red color. + Alizarin, C;H,.(CO),..(CsH».(OH):.—B. p. 430°.—T.t. partly immersed in oil- bath at 200° sbl. slowly in OR and O. ndl.—I. aq., v. d. s., alc. or eth. —S. in v. dil. NaOH; sol. has red-violet (RV) color. More conce.: sols. intensify the color, but the hue remains the same.—NaOH sol. is ppt’d by CO, (dif. fr. isopurpurin), Alkaline sol. is ppt’d by BaCl,; not soluble in Ba(OH),.—Sol. in conc. H,SO, is purple-red.—Ignition w. Zn dust gives anthracene. 1, 7 (m-)Benzdioxyanthraquinone, C,,H,O,.—Sbl. w. dec. in yellow ndL., s. eth. or ale.; s. NaOH w. deep-yellow color. Diacenaphthylidendione, C,,H,,0,.—Sbl. brownish-red ndl., v. d. s. bz.—Adds Br, (comp. i. alc., lft. fr. CHCl, and lIgr.) m. p. 237°.— Phenylhydrazone, brown-red cryst. powder, m. p. 105°-10°. 2-(m)-Oxyanthraquinone, C,H,.(CO),.C,H;.OH.— Yellow lft. or ndl. fr. ale.—Sbl. —Alm. i. aq.; e. s. alc. or eth.; e. s. ammonia giving red-yellow sol.; s. Ba(OH), sol., and K salt s. alc. (dif. fr. alizarin).—Ignition w. Zn dust gives anthracene (Test 912). Alizarin-(-carbonic Ac., (HO),.C,H,:C,0,:C,H,.CO,H.—SbIl. in red ndl., s. ale.— The sol. in alkalies is blue. Naphthalfluorescein, C,,H,,O;. — Large yellow rhombic pr. fr. eth.—Sol. in dil. NaOH is reddish yellow w. green fluorescence.—Acetyl derivative (fr. acetic enya... ps 191% Anthragallol, C,,H,0,.(OH);—Sbl. at 290° in orange-red ndl.—Brown sol. in alc. or eth. —S. alkalies w. green color. — Spectrum, cf. B. 19, 2331. — Igni- tion w. Zn dust gives anthracene.—Pb salt, violet-brown ppt. fr. alc. w. PbAc,. 2, 3-Anthraquinonedicarbonic Ac., C, ,H,0,.—Yellow ndl., e. s. ale.—Salts red- dish, alm. i. ag.—Warmed w. Zn dust and NH,OH is easily reduced to an- thracenedicarbonic ac. SSS COMPOUNDS CONTAINING ©, H, AND O [ORDER [I]. SUBORDER IJ, COLORED COMPOUNDS. DIVISION A, (SUPPLEMENTARY) SECTION 2—SOLID SPECIES, MOSTLY OF HIGH OR ILL-DEFINED MELTING-POINT, GIVING INTENSELY COLORED SOLUTIONS IN DILUTE ALKALI [The arrangement of species in this section of the tables is such, that compounds follow one another in the order that the hues obtained by dissolving them in dilute caustic soda occupy in the spectrum or color standard, beginning with red, and proceeding through orange, yellow, green, blue, and violet.—Since the hue as well as the intensity of these colors devends very much on the concentration, the colors should be produced and observed under the conditions pre- scribed on page 204. The exact order of succession is reasonably well established only for those compounds whose color reactions have actually been examined by the author with the aid of the color standard. The colors thus determined are distinguished from those based on the verbal description of other authorities by being followed by a color symbol (e.g., red=R). The preparations used in most of the writer’s experiments on the species of this supplementary sec- tion were commercial products—sometimes pastes—from reliable manufacturers. The best preparations of this class are, of course, liable to slight differences in composition, and are never absolutely homogeneous. ] COLORED COMPOUNDS.—Solid Species, giving intensely Color of Solution in very ) , ‘ L colored solutions in dilute Alkali. dilute NaOH. R-RV. Hematoxylin, C,,H,,O,+3H,0.—Brown cryst. (colorless when Intense VB in conc. NaOH. pure).—Taste sweet.—Sol. in conc. NaOH, deep violet (V or BV), becoming (R) on acidification w. HCl.—Sol in conc. H,SO, orange (O).—Cf. Sec. 1, m. p. 140°. Red (R). Brazilin.—Red-brown cryst (colorless when pure).—Taste sweet.—Cf. Gen. IV, A,m. p. abt. 250°. Red (R) Flavopurpurin, C,,H,0,.(0H),.—Yellow ndl. or YOS1 paste.— (slightly RV). “Deep red.” ‘“Vine red.” Red (R). Fuchsine red. Intense red to brown (yellow-green fluorescence). Red (w. green-yellow fluorescence). Red. Carmine-red. D. s. h. aq.; e. s. h. ale.-—Sol. in conc. H,SO, is red. 2, 7-Dioxyanthraquinone, C,,H,O,.(O0H),+H,0O, [Isoanthraflavic. Ac.].—Yellow cryst.; m. p. a. 330° after losing cryst. aq. at 150°.—Sbl.—Sol. in conc. H,SO,, deep red.—s. ce. Ba(OH),. sol ; s. alc.; alm. 1. eth. Trioxyaurine, C,,H,O.(OH),.—Dark-red lft. fr. eth.-ale. Purpurin, C,H,.(CO),.C,H.(OH),._{Cf. Sec. 1, m. p. 256°.}— Orange-red (ORS1) paste or ndl.—Sol.in cone. H,50,, R-OR, changing to YO on dilution w. aq. Cresolaurine, C,.H,,O.(OH),.—Amorph. red powder; i. aq.; d. s. eth.—Sol. in Ac, yellow. Resorcinoxalein, C,,H,O,.(OH),;.—Red powder.—S. in cone, H.SO, w. emerald-green color.—The alkaline sol. diluted to a pale-yellow shows moss-green fluorescence, Beep C,.H,,0,(OH),. — Red-brown grains, v. d. s. alc. Carminic Ac., C,,H,,0,).—Red pr. fr. alc., or red-brown powder. E. s. aq.; sol. yellowish red.—Aq. sol. gives purple ppt. w. baryta sol.—Alc. sol. heated w. aniline gives ruby-red cryst.. anilide, m. p. 190° d. Brazilein, C,,H,,0;.—Cryst. w. 1H,O. Powder reddish-brown. D. s. aq.; sol. rose-red w. orange fluorescence.—Alkaline sol. browns in air.—Triacetyl deriv., yellow lft. fr. ale., m. p. 203°-7°. 212 SUBORDER II, DIV. A, (SUPPLEMENTARY) SECT, 2. 213 Color of Solution in very dilute NaOH. Brownish red (fluorescent). Orange-red (OR) (not fluorescent). Yellow-red (not fluorescent). Orange. Red to yellow (according to dilution). Intense yellow-green (YG) fluorescence. Yellow-orange (YO). Yellowish brown. Yellowish brown. Orange-yellow. Orange-yellow (OY). Orange-yellow. Yellow. Deep yellow. Green. (ORDER I.) COLORED COMPOUNDS.—Solid Species, giving intensely colored solutions in dilute Alkali. Fisetin, C,,H,,0,+4H,O.—Cryst. in lemon-yellow ndl. w. 4 aq. (lost at 110°). M. p. a. 360° d.—S. ale. ; alm. i. aq.—PbAc, gives orange-yellow ppt. in alc. sol.— Reduces Fehling’s sol. hot.—Tetraacetate, ndl. fr. ale., m. p. 200°-1°. Auvine, C,,H,.0.(OH), and Rosolic Ac., Me.C,,H,,0.(OH),.— Commercial article a mixture w. very variable m. p (some- times as low as 90° or 100°), and w. strong odor of phenol.— Color of powder RO. Lumps show conchoidal fracture and greenish metallic reflections.—Sol. in cone. H,SO, yellow (OY-Y).—A (1:5000) sol. in very dil. NaOH shows absorp- tion band at D4E to b. More conc. sol. shows one-sided absorption fr, violet to D line.—Sol. in alc. orange (QO). Resaurine, C,,H,,O.(OH),.—Amorph. light brick-red powder; é. 8. alc.; alm. i. eth. 2, 6-Dioxyanthraquinone (Anthraflavic Ac.), C,,H,O.(OH),.— Sbl. in yellow Ift., m. p. a. 330°.—Sol. in conc. H,SO, yellow, showing broad absorption band between blue and green.— DSC nalecnl seri. Fluorescein, C.,.H,,0,.(0H),.—Yellow-orange (YOS1) powder. —Sol. in conc. H,SO, (Y) w. slight greenish fluorescence. — I. c. aq.; d.s. alc. or eth.—Paper stained a pale yellow by dil. sol. in Ac becomes pink when held in steam from boiling Br water.—The very dil. sol. in dil. NaOH shows a distinct absorption band from a little to right of EK to just beyond F. Phenacetolin (Phenacetein), C,,H,,0O,.—Chocolate or red-brown powder. M. p. a. 330°. Sol. in conc H,SO, (YOS1-2) — I. aq.; sol. in alc. orange; in dil. HCl yellow; in dil. am- monia violet-red (VR). (Colors as given by a sample pur- chased from Merck.) Resorcinbenzeine, C,,H,.0.(OH),.—Pr. or Ift., violet- or brown- ish-red; yellow by transmitted light. E s_ h. ale. when freshly precipitated, otherwise v. d. s.—Loses aq. at 130°.— Dil. ammon., sol. red-violet and fluorescent. Galloflavin, C,,H,O,(?).—Greenish-yellow lft. Sol. in cone. H,SO, orange.—D. s. h. alc.; sol. clear yellow w. faint-green fluorescence. Alizarin Yellow “ C,”” CH,.CO.C,H,(OH),.— Yellowish paste, e. s. h. aq.—Sol. in conc. H,SO, yellowish.—Cf. Gallacetophenone (lV, Aymp. 168°) Alizarin Yellow ‘‘A,” Ph.CO.C.H,.(OH);.—Paste, gray yellow (light YA). EH. s. h. aq.—sSol. in conc. H,SO, clear yellow (Y). Quercetin, C,,H,,0O,+7H,0.—Lemon-yellow cryst. powder. Loses H,O at 130°.—S. 280 pt. h aq. or 229 pt. c. ale.—M. p. a. 250° (r. h.).—Ale. sol. dark green w. FeCl,, turning dark red on warming; gives brick-red ppt. w. PbAc,. Croconic Ac., CO:C:C:(CO,H),+3H,0.—Pale sulphur-yellow ndl. or grains, e. s. aq.; s. ale.-—Sbl. after losing aq. at 100°. —DaCl, gives lemon-yellow ppt. of BaA+14H,O0.—Ag salt, orange-red ppt. Luteolin, C,,H,,0,-+2H,0(?).—Yellow ndl., m. p. a. 320° d— Sbl.—S. 14,000 pt. ¢. aq., 37 pt. ale., or 625 pt eth.—Taste, bitter-astringent.—Sol. green w. little FeCl,, brown-red w. larger quantity.—Sol. in conc. H,SO, yellowish green giving violet ppt. on dilution.—CaCl, gives orange ppt., which becomes red and cryst. on boiling. a-Naphtholbenzeine, C;,H,,(O0H),.0.—Brown powder, i aq.; s. ale., eth., or bz. w. yellow-red color.—The green sol. in alka- lies is turned reddish yellow by acids. SUBORDER II, DIV. A, (SUPPLEMENTARY) SECT. 2. (ORDER I.) Color of Solution in very dilute NaOH. Intense G-YG. Blue. Cornflower-blue. Cornflower-blue. Intense blue. Intense blue (B). Intense Blue to VRT2 (according to concentration). Impure Violet. Blue (B) w. conc. NaOH. Blue-violet. Red-violet (RV). Violet-red. Violet-red. Violet-red (VR). RV (Intense VB-V w. conc. NaOH). COLORED COMPOUNDS.—Solid Species, giving intensely colored solutions in dilute Alkali. Coeruleine, C,,H,O,.— Black powd. or paste, i. aq. or ale.—Sol. in cone. H,SO, ‘‘dirty yellow-brown” (broken OY much darker than dark OY - 68-80 0-00 i Cane-sugar Crystals (melts with decomposition) .... 153-8 (?) 8-8 (2) (3).—[Sharpness Test for Liquids.] Distil 5-8 cc. of the liquid from a 10-15 ce. (or larger) distilling-flask, with all the precautions mentioned in the directions given for boiling-point determinations on page 221, recording thermometer readings at intervals of one minute. The readings must be made through a narrow horizontal tube, mounted and used as in the determination of the fusion-interval (cf. Fig. 8, page 225). The “‘boiling- interval” will be the difference between the mean values of the first two and the last two significant readings. Results by this method are of the same order of reliability as those for the fusion-interval by procedure 2, but are so much more easily obtained that pro- cedure 3 is of far greater practical importance. The significance that may be safely attached to boiling-intervals in special cases will be best understood from an inspection of the following table, in which a considerable number of such data obtained from typical pure and commercial preparations and mixtures have been collected. * The results in this table, as well as those on the boiling-interval on page 227, were obtained by Mr. Arthur Davis in the author’s laboratory, by the use of a 360° thermometer, the length of whose degree was slightly less than one millimeter. The last significant figure in all these results was secured by the process of averaging, and has a probable error of about three units. Substances 1 and 3 had been brought to a condition of exceptional purity by distillation and repeated recrystallization from alcohol. Their behavior is that of the typical, pure stable compound. 2 and 4 illustrate the effect of slight impurity in the case of the same substances. 2, 5, and 6 are good examples of what may be expected from high-grade commercial prepara- tions of good stability. 11 shows the uselessness of sharpness tests for pure compounds that decompose noticeably in melting. Numbers 7-10 show the progressive changes in the inter- val that occur in the crystallization of an impure substance by a suitable method. SPECIAL METHODS, APPARATUS, AND REAGENTS. 227. TABLE OF BOILING-INTERVALS OF TYPICAL COMPOUNDS AND MIXTURES ILLUSTRATING PROCEDURE (3). Boiling- Substance. interval deny a _ rm Meee eres pecially DPUTIfied . . 5...) e eens cece cceccdvecwevccecndiesesecses Bempemtemere emt o biiophene, ““frozen’”’. .......5.-00ccccancceccescceuvecevas MR COILIDANIN'S. oe ec ce cee ccc ccuccauvceccuutessesven REPO ETS ADL AUIN Ss... oo. oc ace vp wee hac tleuweelcdalecccteaecencncncs Meee commeuewmerck < from cryst. Benzene... .......0..cseccceucucscceccceces 8 : PUMUpercialt rade steag nicer ewe hh ete ai ee ag a acs iimiecnysamiuine, MMerck’s, free from mono compound ............-ss«sesseceress ; COCUIREr CIAL STOUG. ba. Wat, femme, eee Mea: A eS EES i Se ge en ae oy ee re eee rad ene Disulphite compound .... cc. s ses ce cere ede cc ececwcvcecacs Ei Bee omenciucally pure,” Merck’s.... <2 5 scence cov hatha sc cantseaen boc NO yo en otic hee ba cele pg be mau cubnaeannwes Bete eatin s intermediate grade.. .... 22... lec ee ces enc cuccccuceuvceness SMES VGICHIC oo ye ol cet ee nee dec sade ewgeeececnsunacectusen MMMM TUTE ALUT Sos a hed ele ee cate nv Viable ve dwsnveucenuvaees RR SIRLOIN Sous. ke a ne gale avis ee wuss o Ue cad v omens eravnadecs benzildenyde, originally “C. P.,” but slightly oxidized. ...........cenenevceess Piemmeacede sicic, containing about 2% water. .............ccerecccecvceeces Acetoacetic Ether, Kahlbaum’s (boiled with some decomposition) ............... Pennemenncia, Merck’s (boiled with decomposition)...............-cccvcccnes Piavenceraie, Kahlbaum’s, a mixture of isomers... ...0...... 00 0c veces cece aeas 70 Ethyl Ether, commercial, US. P., containing much alcohol and water........... 40-85 Semen eeatrnrry 7 LOWENC. |... oe ee a gi da vee cnc cdo w eile sccceansues 32 Nimovenzene conwmining 57%, o-Nitrotoluene.... 0.0... ccc cece cnc c ence ncccees eee eee enuaraine 57, Methyl Alcohol... 2... 2.0.06. ce cn cn eee ccd weeweneeedes emer oman contaming 5% o-Toluidine... ........2-2.ece ee eccees Loe bates ‘*Constant-boiling Mixture” of Methyl Alcohol and Benzene *................... CAOONOCWWWNFRRrRooOoococoocoocococooc°ce oe one (Je) SPECIFIC GRAVITIES. The specific gravity of solid organic compounds has been determined for com- paratively few species, and is consequently not at present a property of great analytical importance. The specific gravity of liquid compounds, on the con- trary, has been determined with almost the same regularity as the boiling-point, and sometimes affords the simplest possible means for the arrangement of such species into “‘Sections.”’ The recorded values for the specific gravities of organic liquids are usually reliable in the second decimal place, often in the third, but very rarely in the fourth. As the analyst willoften have too little of a pure compound to enable the deter- mination of its specific gravity by the Westphal balance or hydrometer, two other methods for the determination, which are also rapid and usually sufficiently accu- rate for his purpose, will now be described in detail. . * Ryland, Am. 22, 384 [1899].—This mixture is an example of many known cases of two miscible liquids, that, when once brought together in certain proportions, boil like a pure com- pound, and can not be separated by the usual method of fractional distillation. The analyst is not very likely to meet such mixtures ready formed in commercial preparations, the chances all favoring .the presence in excess of some one constituent. He may, however, somtimes pre- pare such mixtures for himself, while attempting to resolve a mixture into its constituents by fractional distillation. Such mixtures have a constant boiling-point only under the atmos- pheric pressure at which they were prepared, so that the absence of homogeneity may be detected by distilling over one half im vacuo and then determining the boiling-interval under the ordi- nary pressure of what remains in the flask—provided both constituents do not nave the same vapor-tension at all temperatures, which is a coincidence that is very unlikely to occur. 228 SPECIAL METHODS, APPARATUS, AND REAGENTS. Determination of the Specific Gravity of Small Quantities of Liquids. (1).—[Method for 0.20 cc. of Substance.] Prepare a pycnometer for this purpose by bending a piece of thick-walled glass tubing 28-30 cm. in length, into the form shown in Fig. 9. The tubing should be of the kind used in gas analysis for transferring gases from one container to another, and have an internal diameter of 1 mm. and an external diameter of about 5mm. The part between A and B should be drawn out to form a narrow-bored but thick-walled capillary,8 cm.long. The zero- point of the instrument is a short, thin hori- ’ gontal scratch made at C. To calibrate the pycnometer begin by attaching a few centimeters of clean rubber tubing at D. Slip the point of an ordinary medicine-dropper M into the open end of mas Os the rubber tube, and then a light brass burette-clip over the latter, so that it may be quickly clamped off at any time at D. Next incline the instrument as shown in the figure, so as to immerse the point of the capillary in cold water contained in a 3-inch test-tube. The manipulation will be facilitated by having the test-tube held in a clamp. Open the clip at D. Compress the rubber bulb of the dropper to expel air. Then allow the bulb to expand slowly again, so as to suck water into the pycnometer. When the latter has filled to the horizontal arm above the zero-mark, close the clamp. Separate the dropper from the rubber tube. Then take off the clamp and separate the rubber tube from the pycnometer. Next suspend the pycnometer for some time in the air from the hook of the analytical balance, or for five minutes in a beaker containing cold water having the desired temperature. When the instrument and its contents have acquired the temperature of their surroundings, touch the edge of a bit of dry filter-paper to the tip of the capillary A, which must be filled by the water. As the water is absorbed by the paper, its level in the longer arm of the pycnometer will gradually fall. Bring this level exactly to the zero-mark. {If care is taken in subsequent operations not to incline the capillary AB much below a horizontal position, no water will flow out.|—The pycnometer is now ready to be weighed, unless it has been suspended in water, in which case it must first be carefully wiped dry. To determine a specific gravity by this method, fill the pyenometer with the organic liquid by the manipulations described above in connection with the cali- bration. If we then represent the weight of water required to fill the instrument to the reference-mark by w, and the weight of the same volume of the organic compound by 0, the specific gravity, uncorrected for temperature, will be —. The result should not differ from the true gravity by a full unit in the second decimal place. After use, the pycnometer should be washed out at once with alcohol or ether, and thoroughly dried by an aspirated current of dry air. When not in use, it SPECIAL METHODS, APPARATUS, AND REAGENTS. 229 should be kept in a clean box along with a carefully adjusted counterpoise made from thick sheet lead, and a card giving the weight of water which it contains at the room temperature. As long as the counterpoise continues to balance the dry piknometer, its capacity may be assumed to have undergone no change. (2).—[Method with 1 cc. Pipette.] This very rapid method has an accuracy limit of about a unit in the third deci- mal place. Calibrate a pipette (A in Fig. 10), to contain (not deliver) one cubic centi- meter when filled to the reference-mark. If the determinations are to be made at about 20°, scratch the reference-mark on the pipette stem at the level of the lowest point of the meniscus seen when the pipette contains 0.9982 grm.* of distilled water at that temperature. Then the weight in grams of any liquid having the same volume at 20° will be the number express- ing its specific gravity at 20°/4°. The pipette is to be manipulated as follows: Suck in the liquid until it stands about half a centimeter above the reference-mark. Wipe off any traces of the liquid adher- ing to the outside of the stem. Then allow it to run out until the meniscus just touches the reference-mark. Wipe off the fraction of the last drop that hangs from the nar- row outlet of the pipette, by touching it with the finger. Stand the pipette in the recipient tube B. Support the apparatus by the aid of the attached platinum wire on the balance-pan, as shown in the cut, and weigh at once. If an accurately adjusted lead counterpoise for the entire apparatus is kept in readiness and placed upon the oppo- site pan of the balance, the weights that have to be added to produce equilibrium give the desired gravity directly without any calculation. * The correct location for this mark is most easily ascertained (as suggested in Ostwald’s ‘“Physico-chemical Measurements”) by gumming a strip of millimeter-paper to the stem of the pipette and determining the weight of water corresponding to two points on the scale, one on each side of the true position and 10 mm. apart. ‘‘Then, on the justifiable assumption that the stem is cylindrical throughout this short piece, we can calculate the proper position of the mark from these two weighings.’’ If, for instance, one weighing is 1-0222, the other 0-9930, and the desired weight 0-9982, then the reference-mark should lie sae cake aS x10=8-3 mm. 1-0222—0-9930 below the upper mark on the paper scale. If it is desired to calibrate the pipette for use in comparing the density of a liquid at some other temperature than 20° with that of water at 4°, the proper weight of water to be used may be taken from the accompanying table of the density of water at various temperatures. DENSITY OF WATER BETWEEN 15° AND 30°. a Tempera- Densities. Tempera- Densities. Tempera- Densities. ture (C.°). ture (C.°). ture (C.°). 15 0-9991 21 0-9980 26 0-9968 16 0-9990 22 0-9978 va 0-9965 ‘a 0-9988 20 0-9976 28 ‘| 00-9963 18 0-9986 24 0-9973 29 0-9960 19 0-9984 25 _ 0:-9971 30 0-9957 230 SPECIAL METHODS, APPARATUS AND REAGENTS. COLOR. According to Aubert there are at least one thousand hues in the solar spectrum which may be distinguished by the human eye as different. Each of these hues “may again be varied many times by changes in luminosity and admixture with white light, giving in the aggregate, it 1s estimated, as many as two million color differences that are recognizable under favorable circumstances. Yet, although the color of a chemical compound is often its most salient physical property, and the changes which this color experiences when treated with reagents may furnish the simplest test that can be applied for its identification, careful analysts have always very properly refused to attach the same importance to verbal descriptions of subjective color phenomena as a means for specific characterization, that they willingly grant to the recorded values of melting-points, boiling-points, specific gravities, and other physical constants whose determination requires the use of comparatively slow and elaborate methods of measurement. The chief causes for the disrepute into which color tests have fallen are: the customary failure, except in spectroscopic work, to refer colors to any well-defined standard; the loose use made of the terms constituting the popular nomenclature of color; the imperfect development of the color memory; and, finally, the fre- quent omission of minor but essential experimental details from the directions given for the performance of color reactions. To minimize these defects in the original color descriptions and tests of this work, it has been considered desirable, whenever possible, to consistently adhere to a more definite color terminology than has before been used for chemical purposes. It has been necessary, how- ever, to leave all copied color descriptions recorded in terms of the crude popular standard in which they were found; i.e.a standard in which red might signify any- thing from violet-red to orange, or from pink to russet. The Terminology of Color.—To prevent possible misunderstandings, before proceeding to the subject of color comparisons, it will be necessary to define the sense in which certain common color terms will be used. It should be remarked that the restricted meanings that will be accepted for the terms have the sanction of good authority, though they are sometimes used popularly, and by artists, with very different meanings. A Pure, Full, or Saturated Color is the most intense expression of that color without admixture of white, black, or gray. No pigmentary color is absolutely pure. A surface painted with artificial ultramarine blue, for example, reflects with the blue about 25 per cent of white light, the effect of which is to soften the color and reduce its action on the eye. In the color-standard cards A and B in the back of this volume, the third hori- zontal series of color rectangles, counting from the top of the sheet, approach most nearly to the corresponding colors of the spectrum; and, as the pigmentary types of the pure colors, will sometimes be referred to as the ‘“‘pure”’ or “‘full-color series”’ of the standard. The Luminosity of a color is that constant of it which is dependent on the quantity of light which it transmits to the eye, and is nearly equivalent to bright- ness. Two colors may be equal in purity, each reflecting, we will say, 75 per cent SPECIAL METHODS, APPARATUS, AND REAGENTS. 231 of blue and 25 per cent of white light, but can not be made to match except by exposing the brighter surface to a feebler illumination than the other. The Hue of a color is in some respects its most fundamental quality. It is dependent entirely on the refrangibility, or wave length, of the kinds of light pro- ducing the sensation. The purity and luminosity of colors may be absolutely equal, but one may appear red and the other yellow. The difference is one of hue. Each color in the standard, in going from red to violet, is a distinct hue. A Tint of a color is the result obtained by reducing a pure or full color by the addition of white light. In the standard, the two color rectangles immediately over each full color are its ‘‘tints.”” Tint 1 contains less white than Tint 2. Tint 3, which is sometimes referred to in descriptions, is not a tint actually represented in the standard, but is to be imagined as a tint of about half the saturation of Tint 2. A Shade of a color is the result obtained upon viewing a full color in shadow. With pigments, shades of most colors are obtained by adding black. The two shades corresponding to each full color of the standard are placed vertically under it. Each of the upper five colors in the same vertical column of the standard— two tints, two shades, and one full color—is called a tone of that particular color scale. The full color of the scale is sometimes called the ‘‘normal tone”’ of the color. A Broken Color is the subdued effect obtained by mixing a full color with neutral gray (black and white), viewing the tint of a color in a shadow, or a shade of a color in strong sunlight. The lowest horizontal series of colors in each of the sheets of the standard contains ‘‘medium”’ tones of the broken colors. Tints and shades of these ‘‘medium tones’’ will sometimes be referred to in the text as “light” or “dark” broken colors, respectively. It has not been considered necessary to represent them on the color sheets. The russets, browns, citrenes, and olives, are typical broken colors. All pigmentary colors, including the so-called full-color series of the standard, are somewhat broken; and in many color reactions, partic- ularly where intense violets are under observation, it will be found that the colors to be compared are distinctly more saturated than the purest corresponding color of the standard. This will not often prevent the recognition of the fundamental hue of the color, however. The Use of Pigmentary Color Standards.—Every colored substance illumi- nated by ordinary daylight owes its color to its selective absorption of rays of certain definite wave lengths from the white light that penetrates its surface. The light that escapes absorption and is transmitted to the eye is, almost without exception, a mixture of rays of many different wave lengths together with more or less unchanged white light. The subjective effect is, however, the perception of a simple color. Red and yellowish-green lights, for instance, give an orange which looks in all respects like the orange of the spectrum. Unaided by the spec- troscope, it is impossible for the eye to detect in it the presence of either red or yellowish green. In the same way the original ingredients of every subjective color entirely elude visual analysis, and it is therefore theoretically possible, by the use of a suitable mixture of pigments, to prepare a systematically graduated scale of apparently homogeneous colors, that may be used as a color standard, and with which all other subjective colors, however simple or complex the light 232 SPECIAL METHODS, APPARATUS, AND REAGENTS. rays producing them may be, can be compared. As the colors of all natural objects are somewhat “‘broken,” the fact that the colors of pigmentary standards are less “‘saturated”’ than the corresponding hues of the spectrum, is often an advantage rather than otherwise, and in other cases merely limits, but does not destroy, their usefulness. The exact color descriptions of this work are all expressed in terms of the Bradley Color Standard. This standard, mounted in a special compact form, to facilitate its use in the laboratory, will be found on the two cards,* A and B, in a pocket in the back cover of this volume. It contains eighteen pure colors; and of derived tones, thirty-six tints, thirty-six shades, and twelve medium broken colors. | Color Symbols are only used in the tables for describing such colors as have been actually compared with the Bradley Standard in the author’s laboratory. These symbols are as follows: R=RED; OR=ORANGE-RED; RO=RED-ORANGE; O= ORANGE; YO=YELLOW-ORANGE; OY=ORANGE-YELLOW; Y=YELLOW; GY=GREEN-YELLOW; YG=YELLOW-GREEN; G=GREEN; BG= BLUE-GREEN; GB=GREEN-BLUE; B= BLUE; VB=VIOLET-BLUE; BV=BLUE-VIOLET; V=VIOLET; RV=RED-VIOLET; VR=VIOLET-RED. The Tints of any color are represented by the symbol of the normal tone of the color followed by the symbol T1, T2, or T3; in which the numeral stands for the number of the tint, Tint 1 coming next to the normal tone of the color in satu- ration. The Shades of a color are in like manner represented by adding S1, or $2, to the symbol of the normal tone. The following examples will illustrate the use of these color symbols: YS2= the second shade of yellow; YT1=the first tint of yellow; OT1I-OYT1=a color between the first tint of orange and the first tint of orange-yellow. Comparisons with the Color Standard.—All comparisons with the Standard should be made near an unscreened window through which light reflected from the sky—not direct sunlight—falls upon the colored object and standard from behind the observer. * The colors used on these sheets are those of the Bradley Standard, as described in Milton Bradley’s “‘Elementary Color”, (Springfield, Mass.). The fundamental colors, red, orange, yellow, green, blue, and violet are claimed to be careful pigmentary imitations of the hues seen at certain definite points in the solar spectrum. The wave lengths of the light emitted by the portions of the spectrum selected for imitation are, according to the measurements of Prof. A. H. Pillsbury: 6571 for red; 6085 for orange; 5793 for yellow; 5164 for green; 4695 for blue; and 4210 for violet. This series of six fundamental normal hues is increased to eighteen, by introducing twelve additional colors in such a way as to bring two new hues, separated by equal chromatic intervals, between each of the original colors. The values for these inter- mediate hues were determined, by blending the adjacent hues of the original series of six in pairs, by Maxwell’s method, on a rotating color-wheel on which the areas of the two colored sectors were in the ratio of two to one. Yellow-orange, for example, is the subjective color resulting from the blending in the eye of the light from two superficial units of the funda- mental orange and one of the yellow; orange-yellow, of two parts of the yellow and one of the orange. Two “tints” and two “shades” were then derived for each of the eighteen ‘‘ normal tones” by dilution with white or black. Additional copies of these color sheets, to replace the originals as they become soiled or injured, can be procured at any time from Messrs. John Wiley & Sons, the publishers of this volume. A comparison of the new color sheets with well-preserved samples of the Bradley colored papers prepared at different times during the last dozen years, indicates that the colors used are stable, and that much care has always been taken by the manufacturers to faithfully reproduce the colors of their first standard. SPECIAL METHODS, APPARATUS, AND REAGENTS. 233 If the substance is a solid, it should be placed upon a piece of white paper, and laid upon the perforated shield accompanying the Standard, close to the rect- angular window. ‘The object of the screen is, partly to protect the Standard from accidental injury, and partly to prevent the confusion that is apt to arise from presenting many kinds of colored light to the eye at the same time. It is impor- tant to remember in color descriptions, that the color of a solid substance in masses is often different from its “streak,” or color of its fine powder; and that the color of a moist precipitate is usually different from that of the same substance after drying. It is only occasionally that a color is met with which exactly matches one of the color squares of the Standard. The statement in descriptions, that a compound has a light orange-yellow color (YOT1), is therefore to be understood to mean nothing more than that its color more closely resembles this color of the Standard than any other. If the color to be described obviously lies between two colors of the Standard, the fact is, however, often indicated by the symbol; e.g. YOT-OYT1. To examine a solution, lay the perforated screen upon the Standard so as to expose to view one or two color patches that resemble the color to be described, and hold or support it in an upright position, so that diffused sky light, coming from behind the observer, will fall upon it. Then hold the test-tube containing the solution vertically in front of the shield at a distance of about twice or thrice its diameter, and just above or to one side of the perforation. The comparison will thus be made by transmitted white light reflected through the solution from the screen. In observing the color of a fluorescence, replace the white screen by one coated with lamp-black. The light reaching the eye is in this case reflected back from the solution and not from the screen. The color of a solution depends not only upon the nature of the substances dissolved, but also upon its concentration, the thickness of the colored layer, and sometimes upon the temperature. No description of an unfamiliar color reac- tion in a solution is entirely satisfactory unless all these conditions are given. In the greater number of cases, it is true, the result of dilution is chiefly to reduce the saturation of the original color; i.e., to produce a lighter tint of the original hue. But some change in hue is of very common occurrence, and in tests, like that for acrolein (Test 112), where the change in hue upon continued dilution with water is from orange-yellow to violet-blue, it is the most striking and essential feature of the test. The temperature is sometimes a very important condition, as in Test 401 for phenols with ferric chloride, where a pronounced yellow color is communicated to the solution in blank experiments by the reagent alone, unless the test is made cold. Unless otherwise indicated by the context, all color comparisons with solu- tions which are referred to the color standard in this work relate to solutions of approximately definite concentration, the colors being observed, as above stated, in three- to six-inch test-tubes at the temperature of the laboratory. Many color reactions, especially among those with ferric chloride for the phenols, and for the Species of Suborder II, Division A, Section 2, give colors which change rapidly on standing. In the absence of directions to the contrary, such colors should always be observed as soon as possible after their appearance. 234 SPECIAL METHODS, APPARATUS, AND REAGENTS. It is more difficult to match the colors of solutions with a pigmentary stand- ard than those of solids; for the colors in the Standard often appear distinctly “broken”? and muddy by contrast, particularly if the solution happens to be a brilliant purple. But the fundamental hue, which is the most important color element, will still usually be distinguishable. Such comparisons are sometimes facilitated by using a solution of the colored substance so dilute that it will approxi- mately match the first ‘‘ tint” of a hue, rather than the ‘“‘full”’ or “‘normal”’ color of the scale. THE MANIPULATION OF SMALL QUANTITIES. As has been stated on page 2, most of the specific tests in this volume depend- ing upon the isolation of a pure derivative of a compound, are made with only a decigram or less of substance. The use of these small quantities not only saves valuable material, but also greatly shortens the time required to complete an experiment; so that,in many instances, a derivative may be prepared, filtered off, washed, recrystallized, and dried ready for a melting-point determination within half an hour. Some of the conditions and expedients that have been found conducive to success in such preparations in the small way deserve special mention. Solid Precipitates.—In making the selection of a characteristic solid deriva- tive suitable for preparation on the small scale in specific tests, it is desirable to choose one that will separate in a bulky but crystalline condition from the solvents used; and which may be recrystallized quickly by cooling its hot saturated solu- tions. Precipitates that are both crystalline and voluminous may be removed from glass surfaces and filters, and washed, recrystallized, dried, and handled with much less loss than those that are either too compact, slimy, or gelatinous. Precipitates that are very soluble in the cold, and which form only after evap- oration of a considerable portion of the solvent, are poorly adapted for these tests; evaporation being a slow operation, and the difficulty in separating crystals that are uncontaminated by by-products from the small mother-liquor being usually greater than in the method by cooling. Among the numbered specific tests are many examples of derivatives that combine all the good qualities just mentioned in a high degree. A single decigram of some of the aromatic nitro-derivatives, for example, upon separating from a hot saturated solution in dilute alcohol, is sufficient to fill entirely a five-inch test-tube with a mass of hard interlacing crystals. Some sticky resinous precipitates of equal weight would be entirely lost as inconspicuous adhesive smears on the test-tubes or filters. If no precipitate should appear upon cooling what is supposed to be a hot saturated solution of a solid derivative, always close the mouth of the test-tube firmly with the thumb, and shake vigorously and persistently. Many compounds whose preparation is directed in the numbered specific tests, tend to form super- saturated solutions; but upon being thus treated, give bulky crystalline precipi- tates. This final precautionary shaking should never be omitted. Small precipitates should be collected on correspondingly small filters and funnels. A large filter retains so much mother-liquor as to require excessive wash- ing; and the precipitate, if at all adhesive, will be very difficult to separate from the large paper surface. A supply of cut filters, 5 cm. in diameter, and a SPECIAL METHODS, APPARATUS, AND REAGENTS. 235 few very small funnels are therefore indispensable for the performance of the specific tests. When hot filtration of a saturated solution is necessary, the funnel and filter are most easily and effectively heated by first pouring through them some of the boiling liquid that is to be used as the solvent in the experiment. Clogging of the funnel-tube by separation of solid matter may be prevented by cutting off its lower end so that only about 1 cm. remains. If the solid begins to crystallize out at a temperature very little below the boiling-point of the solvent, a com- paratively large filter and funnel are to be preferred to a small one, as they will give more rapid filtration. On a very small filter there is greater danger that the free passage of the solution may become obstructed by the deposition of solid matter in the pores of the paper. In filtering from one test-tube into another, hang a short piece of thick bent copper wire over the lip of the test-tube in which the funnel is placed, so as to leave a passage for the escape of air from the tube. For mixtures that filter slowly, fit the recipient test-tube with a doubly perforated rubber stopper and use it as a filter-bottle, placing a small filter-cone in the funnel and applying gentle suction with the filter-pump. In washing small precipitates with a liquid in which they are rather soluble, the danger of using an unnecessarily large volume of solvent has been provided against in the more important procedures by the specification of some definite volume. These directions should be closely followed. The solvent should be dropped upon the precipitate in such a manner as to detach it from the sides of the filter and wash it down into the point, so as to facilitate its subsequent separa- tion from the paper. Very small precipitates which do not require much washing, and which it is thought undesirable to bring upon a filter, may be separated from most of the supernatant solution by decantation, and then shaken out upon a piece of porous tile. When the adhering solution has disappeared in the tile, 1t may be sprayed or moistened as many times as desired with the solvent, waiting after each treatment until the liquid disappears before adding more. If it becomes necessary to redissolve a precipitate that is very small and firmly. attached to the filter, open the filter, tear off the sector to which the solid adheres, and boil it with the solvent. Do not boil up the whole filter, or the pulpy mass formed may cause explosive boiling and loss of the substance. Precipitates whose melting-points are not too low are directed to be dried in a drying-oven at some definite temperature and for a definite time. Solids of very low melting-point are air-dried at the ordinary temperature, or supported in a warm place over a drying-oven, on a piece of porous tile or filter-paper. Drying in the oven should always be preceded by rubbing the moist substance over the surface of a porous tile with a small spatula, or pressing it between filter-paper to remove all the mother-liquor. Liquids.—The preparation of liquid derivatives is not often recommended in specific tests, because the purification of such compounds on the small scale gen- erally presents special difficulties. The procedure for the isolation and identifica- tion of liquid alcohols from the saponification of a gram or two of an ester (p. 114), the Siwoloboff boiling-point method for two or three drops of liquid (p. 222), and ¢ 236 SPECIAL METHODS, APPARATUS, AND REAGENTS. the method of page 228 for the determination of the specific gravity of liquids having a volume of only 0.2 cc., are, however, examples which show that the difficulties connected with the manipulation of small quantities of liquids may sometimes be satisfactorily overcome. ‘Test-tube experiments with less than a centimeter of a liquid must be made in very narrow tubes. With a tube of 5 mm. internal diam- eter, five drops of a substance are all that is required to enable a satisfactory obser- vation of the action of sodium on alcohols in Test VIII-2. The separation of very small volumes of two liquids of different specific gravi- ties is best made with a pipette. The mixture is placed in a narrow test-tube, and all but a few drops of the substance that is present in the greater quantity are removed by a large pipette and rejected. The remainder of the liquid, meas- uring perhaps 1 cc., is then sucked up into a small pipette made from a piece of glass tubing that has been drawn out so as to have an average internal diameter of only about 2 mm. in the long tapering portion. The suction is most easily controlled if applied by the rubber nipple of a medicine- dropper. When both liquids have been brought into the pipette, and appear in two layers after standing, they may be separated to a fraction of a drop by slowly ejecting them, successively, into separate tubes. The most perfect control over the rate of flow in careful experi- ments is gained by the employment of the safety pipette shown in Fig. 11. This pipette is provided with a regulator A, 3 cm. in length, made by drawing out a piece of thermometer tubing at the blast-lamp until the capillary at B and C is narrowed almost to complete closure; and then cementing it with melted wax, D, into a short section of glass tube of the same diameter as the upper part of the pipette stem. The capillary, if sufficiently constricted, offers so much resistance to the passage of gas from the air-space, E to H, that the contents of the pipette can not be discharged in less than several seconds, even when the bulb is suddenly and forcibly compressed. By the use of this device the transfer of a small measured volume of a valuable or corro- sive liquid in work at the balance (as in weighing out acetic anhydride for Test VIII-3) is made a safe and simple operation. Fig. 11. SPECIAL REAGENTS. The following is a complete list of the less common chemicals and solutions required for the performance of the. ordinal, generic, sectional, and numbered specific tests of this volume. All these reagents can be purchased, or easily pre- pared by following the directions given in these pages. Most of them are already used in analytical laboratories. [For Ordinal Tests.] Metallic Sodium. The best commercial sodium, free from particles of salt. Sodium Nitroprusside. In small crystals or powdered. Nitrosylsulphuric Acid. Preparation described on page 13. Fluorescein Paper. Preparation described on page 14. SPECIAL METHODS, APPARATUS, AND REAGENTS. 237 [For Generic Tests.] Fuchsine Aldehyde Reagent. Preparation described on page 15. a-Naphthol Solution. A 10 per cent solution in chloroform. See page 26. Decinormal Sodium Hydroxide (aqueous) Decinormal Hydrochloric Acid (aqueous) Carefully standardized. Normal Sodium Hydroxide (aqueous) Normal Sulphuric Acid (aqueous) Approximately Normal Sodium Hydroxide (alcoholic). Unless the alcohol is very free from aldehyde it will become colored on keeping, and hence should not be prepared in large iii quantities. Phenolphthalein. A 1 : 300 solution in 50 per cent alcohol. Ferric-Chloride Solution, A 10 per cent aqueous solution made from the sublimed chloride. Hydroxylamine-hydrochloride Solution. Prepared as described on page 133. Alcoholic Sodium-hydroxide Solution for Test VII, A. Prepared as described on page 133. Phenylhydrazine. Redistilled if the color is not very light. Acetic Anhydride. [For Sectional Tests.] Phenylhydrazine Hydrochloride. Prepared as described on page 32. Fehling’s Solution. Prepared as described on page 33. Bromine Solution. 2 cc. bromine in 50 cc. dry carbon tetrachloride. See page 195. Fuming Sulphuric Acid. An acid of sp. gr. 1.89, which may be prepared by dissolving sulphur trioxide or a solid Nordhausen acid in oil of vitriol. Fuming Nitric Acid. Specific gravity 1.48. [For Occasional Use in Numbered Specific Tests.] Acetyl Chloride. Aluminium Chloride. Dry, sublimed. Ammoniacal Silver-nitrate Solution. Prepared as described on page 22. Si amaan Cuprous-chloride Solution. Prepared as described on page 197. ine. Benzaldehyde. Benzoyl Chloride. Bromine. Chromic Anhydride. 3, 5-Dinitrobenzoic Acid. Prepared by Kahlbaum, and for sale by dealers. Iodine Solution. Prepared as described on page 166. Mercuric Oxide. 6-Naphthol. Phosphorus Pentachloride. Phlorogiucin Solution. Prepared as described on page 33. Resorcin. Para-toluidine. SPECIAL APPARATUS. Ignition-tubes of Hard Glass or Iron. Description and cut on page 10. Asbestos-board Screens. Size 4”x4”. Thickness 36”. Used in the sodium fusion (page 10, Fig. 1); the determination of boiling-points (page 221, Fig. 6); and in specific tests (e.g., Test 311-2). “*Medicine-droppers.”? As shown in Fig. 1, page 10. Lipped Test-tubes. In addition to the usual assortment of test-tubes of the larger sizes, a good supply of tubes with a height of 3 inches and diameter of 4 inch, with cork stoppers to fit, and a few with a height of 3 inches and diameter of 3, inch, should always be kept in readiness. (Cf. page 112, Fig. 3, and page 152, Fig. 4.) Mounted Burettes for Decinormal and Normal Alkali and Acid. Mounting shown in Fig. 2, page 78. Pipettes with Bulbs and Long Stems. Of the usual pattern and calibrated to deliver 2 cc., 25 ec., and 50 cc., respectively. I-cc. Pipette Graduated to Hundredths. Straight, without bulb; graduated by the manufacturer. 1-cc. Pipette for Specific Gravities. Page 229, Fig. 10. 1o-cc. Graduated Cylinders. With lip and foot for general use in rough measurements. Gradu- ation to half centimeter. Capillary Piknometer. Page 228, Fig. 9. Safety Pipette. Description on page 236, Fig. 11. : ‘ Covered Heating-bath. Page 152, Fig. 4. Recommended for use in several generic tests. Bath for Melting-point Determinations. Page 218, Fig. 5. Melting-point and Ebullator Capillaries. Pages 219 and 222, Fig. 7. xe Apparatus for Determination of True Melting-point and Fusion Intervals. Page 225, Fig. 8. Glass Funnels. Diameter 2 cm. Cut Paper Filters. Diameters 3 cm. and 5 cm. a ALPHABETICAL INDEX. The alphabeticai index relates primarily to classification, analytical methods, numbered tests, reagents, and apparatus, but also contains the names of such compounds—about 15 per cent of the total number described—as will be most frequently sought in the tables. To find the description of any compound of minor importance, consult the complete ‘‘Formula Index” on page 244, A Abbreviations, table of, xi Abietic acid, 63 Absinthin, 206 Acenaphthene, 200 Acetal, 19 behavior in Test U 16 Acenaphthene, 209 Acetal, 19 Acetaldehyde, 22 Acetic acid, 80 Acetic anhydride, 73 Acetone, 148, 144 Acetonylacetone, 142 Acetophenone, 149 Acetylacetone, 104 Acetylation test for alcohols, 152 Acetylene, 184 . Acid anhydrides, 128, 80 Acids, general characteristics, 37 generic test for, 35 losing carbon dioxide at 200°, 78 neutralization equivalents of, 77 tests for unsaturation in, 79 titrations of, 35 Aconitie acid, 49 Acrolein, 23 Adipic acid, 63 Fsculin, 98 Affinity constants, 36 Alcohols, generic tests for, 151-154 Aldehydes, general characteristics, 16 as impurities in alcohols and ketones, 135 generic test for, 15 Alizarin, 211 Bordeaux, 214 yellow ‘‘ A”, 207 yellow “C’’, 213 cyanin “R’, 214 Alkali, action on aldehydes, 16 action on anhydrides and lactones, 128 action on esters, 111, 117 action on phenols, 87-88 titrations with, 77 Allyl alcohol, 167, 114 Aluminium chloride, colorations with, 198 Ammoniacal cuprous-chloride reagent, 199 Ammoniacal silver-nitrate solution, 22 Amy! acetate, 121 Amyl alcohols, 114, 162 Analytical procedure, the general, 1 Anethol, 174 Angelic acid, 53 Aniline acetate paper, 33 Anisic acid, 67 aldehyde, 20 Anisoin, 179 Anisol, 189 Anol, 94 Anthracene, 200 Anthraflavic acid, 213 Anthraquinone, 216 Apioh i174 Apparatus, list of special, 237 Arabinose, 30 Arachidic acid, 55 Arbutin, 97 Asbestos-board screens, 10, 11, 81, 221 Ash constituents, test for, 9 Atropic acid, 58 Aurine, 213 Azelaic acid, 58 B Barbaloin, 207 Baths, covered, for heating tubes, 152 ae for melting-point determinations, 18 Behenic acid, 56 Beilstein’s Handbuch, references to, 7 Benzaldehyde, 23 Benzene, 200 Benzhydrol, 157 Benzil, 206 Benzilic acid, 63 Benzoic acid, 82 anhydride, 53 Benzoin, 139 Benzophenone, 150 Benzoquinone, 216 Benzoylacetone, 92 Benzyl alcohol, 165, 114, 167 Boiling-point determination, 4, 221 of small quantities by Siwoloboff’s Method, 115, 222 “‘Boiling-intervals,”’ 222 table of, 227 Borneol, 159 Brassidie acid, 54 Brazilin, 102 Brazilein, 212 Bradley’s color standard, 229 “Broken” colors, 231 239 240 Bromine, test for, 13 test for unsaturation, 195 water, in unsaturation tests, 195 water, in testing phenols, 89 Bumping, prevention of, 221 Butyl alcohol, 168, 115 Butyric acid, 81 C Caffeic acid, 209 Camphene, 175 Camphor, 150 Camphoric acid, 66 Cantharidin, 129 Capillaries, preparation of, 219 Capric acid, 52 Caproic acid, 75 Caprylic acid, 76 Carbohydrates, 26 generic test for, 26 generic characteristics, 27 Carbon, tests for, 9 dioxide, test for acids losing at 200°, 78 tetrachloride, bromine solution in, 195 Carnot’s procedure for identification of halo- gens, 13 Carvacrol, 105 Cellulose, 31 Cerotic acid, 56 Ceryl alcohol, 157 Cetyl alcohol, 157 Chelidoniec acid, 71 Chemical purity, thermometric indications of, 223 Chlorine, test for, 14 Cholesterine, 172 Chromic-acid mixture for oxidations, 147 Chrysarobin, 208 Chrysene, 181 Chrysophanic acid, 208 Cinnamic acid, 82 aldehyde, 21 Cinnamyl] alcohol, 157 Citraconic acid, 41 Citral, 20 Citric acid, 83 Citronellal, 20 Classification of compounds in this work, 1 Ceerulein, 214 Color, 230 comparisons, 232 standards, use of, 231 symbols, table of, 232 terminology, 230 transitions, sharpness of, in titrations with indicators, 36 Colored compounds of Order I, 204 Confirmatory specific tests, 7 Coniferine, 100 Coniferyl alcohol, 93 Constant boiling mixtures, 227 Convolvulin, 98 Cotoin, 207 Coriandrol, 163 Corrected boiling-points, 217, 222 melting-points, 217 Coumarin, 129 Cresols, 91, 104 ALPHABETICAL INDEX. Crotonic acid, 40, 74 Cymene, 190 D Daphnetin, 102 Daphnin, 100 Decinormal acid and alkali, 77 Dehydracetic acid, 58 Densities of water, table of, 229 Dextrin, 29 Dextrose, 30 Diacetyl, 215 Dibenzylidene acetone, 206 Diethyl malonate, 123 oxalate, 74 succinate, 124 succinylosuccinate, 96 y-Diketones, pyrrol-red test for, 148 Dimethyl oxalate, 40 phthalates, 119, 126 Diphenyl, 176 methane, 174 Diphenylene ketone, 207 “Divisions,” defined, 1 Drying precipitates, 235 Dulcite, 156 Durene, 176 E Ebullator tubes, 223 Elaidic acid, 54 Empirical formula, use in identifications, 7 Enols, 90 Erucic acid, 53 Erythrite, 155 Esters, 111 generic test for, 111 “‘non-saponifiable,”’ 117 saponification procedures for, 111, 113 with characteristic odors, 79 Ethers, saturated, test for, with sulphuric acid, 199 Ethyl acetate, 120 acetoacetate, 104 alcohol, 168 benzene, 189 benzoate, 123 benzoylacetate, 106 butyrate, 121 cinnamate, 126 ether, 160 isobutyrate, 120 isovalerianate, 121 propionate, 120 salicvlate, 105 Ethylene, 184 glycol, 169, 170 oxide, 160 Eucalyptol, 190 Kugenol, 106 Euxanthone, 210 Examples illustrating the analytical proced- ure, 8 Explosions in ignition tests, 10, 11 F Fehling’s solution, 33 Fenchone, 142 ALPHABETICAL INDEX, Ferric chloride, colorations with, 107 reagent, 87-88 test for a-hydroxy-acids, 78 Fisetin, 213 Filtration in tests on a small scale, 235 Flavopurpurin, 212 Fluoresceine, 213 paper, 14 Fluorescence, observation of, 233 Fluorene, 178 Formic acid, 83 Formic aldehyde, 114 Fractionation tests for purity, 224 Fructose, 30 Fuchsine aldehyde reagent, 15 “Full” colors, 228 Fumaric acid, 72 Furfurol, 24 Furoin, 96 Fusion interval, 224, 225 Fusions with sodium, 10 G Galactose, 30 Galleine, 214 Gallic acid, 70 Galloflavin, 213 Gallotannic acid, 50 Gaseous compounds, classification of, 1 Generic subdivisions, 6 tests defined, 1 tests, conclusiveness of, 7 tests, tabular summary of, 5 Genus, definition of, 1 ieee eeiec 111,35; TV, 87; V, 111; VI, Poe tielse; VIL, 151: 1X, 173 Genus, procedure for determining, 5 Geraniol, 163 Glucose, 30 Glutaconic acid, 45 Glutaric acid, 84 Glycerine, 169 Glycogen, 31 Glycollic acid, 41 Guiacol, 91 Gum arabic, 29 H . Hemateine, 214 Hematoxylin, 207 Halogens, tests for, when S and N are absent, 12 tests for, when S and N are present, 13 detection in presence of one another, 13 Heptane, 182 Hexane, 182 Homogeneity, chemical, 3 tests for, 3,223 Hue of colors, 231 Hydrocarbons, generic test for, 173 sectional tests for, 173 Hydrobenzoin, 158 Hydrocinnamic acid, 54 Hydrogen, test for, 9 Hydroquinone, 108, 8 a-Hydroxy-acids, tests for, 78 Hydroxylamine reagent for ketones, 133 Hypogeic acid, 52 241 I Ignition test for carbon, hydrogen, and ash, 9 test with sodium for non-metallic elements, 10 tubes, 10 Indene, 191 Inosite, 156 Inuline, 31 Iodine solution, 166 test for, 13 Todoform test for alcohols, ete., 166 Tron ignition tubes, 10 Isoamyl acetate, 121 alcohol, 162 benzoate, 126 butyratc, 122 isovalerianate, 123 Isobutyl acetate, 121 alcohol, 114, 170 benzoate, 125 Isobutyric acid, 81 aldehyde, 19 Tsoprene, 184 Isopropyl alcohol, 170, 114 Isophthalic acid, 85 Isopurpurin, 214 Isovalerianic acid, 74 aldehyde, 19 Itaconic acid, 48 K Ketones, generic tests for, 133, 134 L Lactic acid, 39 Lactide, 60 Lactones, 128 Lactose, 29 Lauric acid, 53 Levulinie acid, 39, 74 Lovulose, 30 Limonene, 190 Linalool, 163 Luminosity of colors, 230 Luteolin 213 M Maleic acid, 45 Malic acid, 83 Malonic acid, 45 Maltose, 29 Mandelic acid, 44 Mannite, 155 Margaric acid, 54 Meconin, 58 Melissic acid, 56 Mellitie acid, 51 Melting-point apparatus, 218, 225 corrections, 217, 218, 220 determination, 218-220 determination in sealed capillaries, 219 the true, of a compound, 220 Menthol, 157 Menthone, 143 Mesaconic acid, 50 Mesitylene, 200, 8 Mesityl oxide, 141 242 Mesotartaric acid, 46 Metallic salts, precipitations, 80 “Method of the empirical formula,” Methyl acetate, 120 alcohol, 171, 114 benzoate, 120 butyrate, 120 formate, 120 ethyl ketone, 141 propyl ketone, 141 propionate, 120 salicylate, 105 Methylal, 19 Milk sugar, 29 Mixtures, examination of, 4 Molisch, test for carbohydrates, 26 Mucic acid, 69, 34 Myristic acid, 54 ill, 7 N Naphthalene, 201 Naphthazarin, 214 Naphthols, a and £, 108 Naphthoic acid, 64, 66 a-Naphthol, as reagent for Test II, 26 a-Naphthoquinone, 216 Neutralization equivalents, determination of, “eel equivalents, formula for calculating, 77 Nitric acid, oxidations with, 198 fuming, in sectional tests with the hydro- carbons, 196 Nitrogen, tests for, 12 Nitroprusside of sodium, solution, colorations with, 146 Nitrosylsulphuric acid reagent, 13 Nonane, 183 Numbered specific, semi-specific, and sectional tests 2, 7 O Octane, 183 Octyl alcohol, 163 Odors of esters in tests for acids, 79 Oleic acid, 52 Oenanthol, 20 Oenanthylic acid, 76 Opacity, 134 Opianic acid, 63 Orcin, 95 Order, definition of, 1 determination of, 4, 9 Ordinal tests, definition, 1 directions for, 9 Orsellinic acid, 66 Osazone precipitations, 32 Oxalic acid, 84 Oxidation, of carbohydrates, 34 of side-chains, 197 of alcohols, and ketones, 147 with copper spiral, 171 with chromic acid mixture, 147, 198 with dilute nitric acid, 198 with potassium permanganate, 197 Oxybenzoic acids, 64, 68, 69 Ee Palmitic acid, 54 Paraconic acid, 40 ALPHABETICAL INDEX. Paraffin, protection of corks by, 153 Paraformaldehyde, 18 Paraldehyde, 19 Pelargonic acid, 76 Pentane, 182 Perseite, 156 Peucedanin, 119 Phenacetolin, 213 Phenanthrene, 201 Phenanthrenequinone, 216 Phenetol, 190 Phenol, 108, 114 Phenols, generic tests for, 87 properties and reactions of, 89 Phenolphthalein, solution, 35 behavior as indicator, 36 Phenylacetic acid, 55 Phenylhydrazine, as reagent, 16, 32, 134 hydrochloride, preparation, 32 Phloridzin, 99 Phenylpropiolic acid, 62 Phloroglucine, as reagent, 33 test for, 109 Phoron, 136 Phosphorus, tests for, 12, 11 Phthalein fusion, 107 Phthalic acid, 84 Phthalic anhydride, description of, 61 use as reagent, 107 Phthalid, 129 Physical ‘properties, examination of, 4 Phytosterin, 158 Picene, 181 Pycnometer, capillary, 228 Picric acid, as reagent, 89 Picrotoxine, 100 Pimelic acid, 43 Pinacone, 155 Pinacoline, 141 Pinene, 189 Piperic acid, 210 Piperonal, 17 Piperonylie acid, 72 Pipette, for specific gravities, 229 safety, 236 Polyatomic alcohols, acetylation of, 154 Polymerized aldehydes, 15 Potassium permanganate, 197 permanganate, 79 oxidations with, in tests for unsaturation, sulphate baths, 219 Precipitates, filtration and drying of, 234 Precipitation of metallic salts, 80 Propionic acid, 81 anhydride, 75 Propyl alcohol, 115, 172 acetate, 120 Protocatechuic acid, 50 Pseudocumene, 201 Pulegone, 143 Purity, chemical, evidences of, 3 of a color, 230 Purpurin, 210 Pyrene, 179 Pyrocatechin, 109 Pyrogallol, 110 Pyromucic acid, 45 Pyrrol-red, 148 ALPHABETICAL INDEX. 243 Q Quercite, 156 Quercetin, 213 Quinic acid, 48 Quinhydrone, 208 R Racemic acid, 50 Raffinose, 29 Reagents, list of special, 236 Resorcin, 110 as reagent, 85, 171 Retene, 177 Rhamnose, 30 Ricinoleic acid, 52 Rosolie acid, 213 Rufigallic acid, 214 Ss Saccharic acid, from oxidations, 34 Saccharose, 29 Safety pipette, 53 Safrol, 192 Salicin, 100 Salicylic acid, 85 aldehyde, 20 Saligenin, 93 “Salting-out” effect-of alkali, 117 Santalin, 206 Santonin, 129 Saponifications, methods, 111, 113 equivalents, 112, 113 products, neutral, 113 products, acidic, 116 Saturated colors, 230 Schotten- Baumann reaction, 37 Scoparin, 209 Sebacic acid, 61 Section, defined, 1 Sectional tests, 2 Semi-specific tests, 2 Sesquiterpenes, 193 Shades, of a hue, 231 Sharpness, in end reactions, 36 in boiling- or melting-points, 223, 226 Side-chains, oxidation of, 197 Silver nitrate, ammoniacal, 22 salts of volatile fatty acids, 148, 149 Siwoloboff’s boiling-point determination, 222 Small preparations, manipulations in, 234 Sodium, as reagent, 16, 151, 154 bisulphite, as reagent, 16 nitroprusside, as reagent, 146 Solubility, approximate determination of, 38 degrees of, 38 Sorbic acid, 61 Sorbinose, 30 Sorbite, 155 Species, chemical, 2 chemical, identification of, 6 Specific gravity, determination of, 227 gravity, determination, for small quanti- ties of liquids, 228 gravity, pipette, 229 tests, definition of, 2 Starch, 31 Stearic acid, 55 Stearolic acid, 53 Stem-exposure corrections, 218, 222 Stilbene, 178 Styrene, 189 Suberic acid, 62 Sub-order II, 204 Substitutions by bromine, 195 Succinic acid, 86 anhydride, 60 Sulphur, tests for, 11, 12 Sulphuric acid, as reagent in testing ethers and hydrocarbons, 200 fuming, use in sectional test with hydro- carbons, 196 Superheating, prevention in boiling-point deter minations, 221 Supersaturation of solutions, 235 4 Tannic acid, 50 Tartaric acid, 83 Terephthalic acid, 85 Terpineol, 165 Thermometers, 219 Thujone, 143 Thymol, 110 Thymoquinone, 205 Tiglic acid, 40 Tiles, porous for absorption, 235 Tints, of a hue, 231 Titration, of acids, 35 of acid anhydrides, 37 Tolane, 176 Tollen’s ammoniacal silver reagent, 22 Toluene, 202 Toluic acid, 66 Toluides, identification of fatty acids as, 81 Toluidine, para, as reagent, 80 Tricarballylic acid, 48 Trimethyleneglycol, 165 Triphenylmethane, 177 Triple bonding, test for, 199 Tropic acid, 61 True melting-point, 219 Truxillic acids, 70 U Undecylenic acid, 52 Unsaturated acids, tests for, 79 Unsaturation, bromine test for, 195 permanganate test for, 79 V Valerianic acid, 74 Vanilline, 17 Vanillic acid, 69 Veratric acid, 66 Volatile fatty acids, identification of, 147 W Water, table of densities for, 229 of crystallization, removal of, 38 Wave-length of standard colors, 232 x Xanthone, 180 Xanthopurpurin, 210 Xylenes, 202 Xylenols, 91, 92 Xylidene acetate paper, 33 Xylose, 30 FORMULA INDEX. Tuer Formula Index gives the page, and usually the part of the page, on which any compound of known empirical formula described in this volume will be found. The numerals following a dash—which is commonly preceded by a melting-point or boiling-point—are the page numbers. The compounds are arranged accord- ing to the kind and number of atoms represented in their symbols. This form of index—already used in Richter’s Lexicon and many of the leading chemical journals—is so simple that detailed explanations are not necessary. Polymers and compounds cf unknown molecular weight are mentioned under the simp!est formula expressing their percentage composition. Water of crystallization is always omitted from the formule. To facilitate access to the original literature, the names applied to compounds are generally literal English translations of names used in the indexes of the third edition of Beilstein’s Handbuch der organischen Chemie. Incidentally it is possible to use this index in identifying compounds by the ‘‘Method of the Empirical Formula.” C, GROUP. Glycid, bp. 161°—164 CH, Methane, bp. — 153°—182 Methyl acetate, bp. 57°—120 CH,O Formalin, bp. 98°—19 Propionie ac., bp. 141°—73 : Paratocne enn mp. abt. 120°— CHO, Dimethyl carbonate, bp. 91°—120 18 aan ac., mp. mC: ? CH,O Formic ac., bp. 101°—73 Methoxyacetic ac., bp, 203°—74 CHO Methyl alc., Gr 66°—160 Methyl glycollate, bp. 151°—121 C;H,O Isopropyl alc., bp. 88°—161 C, GROUP. tee aur bp. 11°—160 ro . 97°— C,H, Acctylons bere ea melee C.H,O, Methyl Banas 2 C.H, Ethylene, bp. — 103°—184 nae: Propylene glycol b 188°—164 C,H, Ethane, bp. —86°—182 Trimethylene gl ete 214°—165 ( O,)x Polyglycollid, mp. 220°—130 C.H.O Glycerine, bp 390°. 165 C,H.0, Oxalic av se es pet depas OHO Acetic ald., bp. 21°— ee Ethylene oxide, bp. 14°—160 C ta Ae Paraldehyde, bp. 124°—19 CHG Butadiénes, bp. 1° and 18°—184 Metaldehyde, mp. 110°—18 Caoutchene, bp. 14°—184 C,H,O, Acetic ac., bp. 118°—73 Ethylacetylene, bp. 18°—184 Methyl formate, bp. 32°—73 Butine(2), bp. 28°—184 C.H,O, Glycollic ac., mp. 78°—161 CA; Butenes, bp. 1° and 2°—184 C,H,O Ethyl alc., bp. 78°—161 : Methyleyclopropane, bp. 4°—184 Methyl eth., bp.—24°—160 CHyo Butane, bp. +1°—182 as ane hy eae mp. 0°—182 pi Fe Maleic anhyd., mp. 56°—54 C; GRODE. C,H,0, AcotylonesieNt bene ac., mp. 178° Cash, Propylene, bp. — 50°—184 —49 Cyclopropane, bp. —35°—184 C,H,O Furfurane, bp. 31°—189 Cau, Propane, mp. —38°—182 ClO, Tetrolic ac., mp. 76°—40 C,H:0 Propargyl ald., bp. 60°—19 C,H,0, Succinic anhyd., mp. 119.6°—60 CaO: Propiolic ac., bp. 144°—73 C Ho Fumaric ac., sb. w. m. 200°—68 C,H,O Acrolein, bp. 52°—19 Glycolid, mp. 86°—129 Allylene oxide, bp. 62°—160 Glutinic ac., mp. 145° d—46 Propargyl! alc., bp. 114°—164 Maleic ac., mp. 130°—45 C,H,0, Acrylic ac., bp. 140°—73 Cro: Oxalacetic ac., mp. 172° d—48 C.H,O, Pyruvic ac., bp..165°-—/4 C,H,0, Dioxymaleic ac., d. abt. 155°—64 C,H,0O, Malonic ac., mp. 132°—45 C,0,0 a-Crotonic ald, bp. 104-5°—19 OA sit 6» Tartronic ac., mp. 186° (?)—49 Hydrofurfurane, bp. 67°—189 , CH OF Mesoxalic ac., mp. 119°—44 Methyl propargyl eth., bp. 61°— C,H,O Acetone, bp. 56.5°—141 160 Ally] afc., bp. 97°—161 Vinyl eth., bp. 39°—160 Metapropionic ald., mp. 180°—18 UT. Allyl formate, bp. 82.5°—i20 Propionic ald., bp. 48.8° ¢.—19 Butenoic ac., bp. 168°—74 Propylene oxides, bp. 35°, 50°—160 y-Butyrolactone, bp. 206°—~-131 C.H,O, Acetylearbinol, bp. 147°—142 Crotonic ac., mp, 72°—40 Ethyl formate, bp. 54°—120 Diacetyl, bp 88°—2Z15 244 C,H,0; C,H,0, C,H,0, C,H,0, C,H,,0, CHO; C,H yO, C,H, FORMULA INDEX. Erythrite anhyd., bp. 1388°—164 Isocrotonic ac., bp. 169°—74 Methacryliec ac., bp. 162°—73 Methyl acrylate, bp. 80.3°—120 Trimethylenezaroonic ac., bp. 182° —74 Acetic anhyd., bp. 137°—73 Methyl pyruvate, bp. 135°—121 Acetylperoxide, mp. 30°—52 Dimethyl oxalate, mp. 54°—40 Isosuccinic ac., mp. 1385°—45 Succinic ac., mp. 1&85°—49 Diglycollic ac., mp. 14S8°—47 Glycollic anhyd., mp. 129°—61 Isomalic ac., abt. 140°—46 Malic acids, mp. 100°, 133°—43, 45 Methyltartronic ac. mp., 178° d.—49 Mesotartaric ac., mp. 142°—46 Racemic ac., mp. 205°—50 Tartaric ac., mp. 169°—48 Dioxytartaric ac., mp. 115° d.—44 Butyric ald., bp. 73-4°—19 Crotyl alc., bp. 117°—161 s-Dimethylethylene oxide, bp. 56° —160 Isobutylene oxide, bp. 51°—160 Isobutyric ald., bp. 63—4°—19 Methy! allyl eth., bp. 46°—160 Metyl ethyl ketone, bp. 81°—141 Vinyl ethyl eth., bp. 35°—160 n-Butyric ac., bp. 162°—73 Dioxyethylene, bp. 102°—164 Ethyl acetate, bp. 77°—120 Isobutyric ac., bp. 155°—73 Isopropyl formate, bp. 69°—120 Methyl propionate, bp. 79.9°—120 Propyl formate, bp. 81°—120 Ethyl glycollate, bp. 160°—122 Ethoxyacetic ac., bp. 206°—74 Methyl ethyl carbonate, bp. 109°— 120 Methyl lactate, bp. 145°—73 Methyl methoxyacetate, bp. 127.3° —121 a-Oxybutyric ac., mp. 43°—39 a-Oxyisobutyric ac., mp. 79°—41 af-Dioxybutyric ac., mp. 74°—40 Methylisoglyceric ac., mp. 74°—40 Methylpropanedioic ac., mp. 100°— 43 Trioxyisobutyric ac., mp. 116°—44 Butyl alc., bp. 117°—161 sec.-Butyl alc., bp. 100°—161 Isobutyl alc., bp. 106°—161 Ethyl eth., bp. 35°-—160 Methyl propyl eth., bp. 40°—160 Trimethylearbinol, bp. 83°—161 Butanediols, bp. 204°—164, 165 Dihydroxybutane, bp. 183°—164 Dihydroxymethylpropane, bp. 177° —164 Dimethylacetal, bp. 64°—19 Ethyleneglycol monoethy] eth., bp. 135°—164 Glycol dimethyl eth., bp. 83°—161 Diethylene glycol, bp. 250°—165 Erythrite, mp. 126°—155 C, GROUP. Cyclopentadiéne, bp. 42°—185 C,H, CsHi. C,H,0, CHO. C;H,O; C,H 2 C5H.0s C.H,O, C.H,0, C.H,0, C,H,O C;H,05 245 Valylene, bp. 50°—185 Pirylene, bp. 60°-—185 Isopropylacetylene, bp. 28°—184 Isoprene, bp. 36°—la4 Methylbutadiéne, bp. 41°—184 Piperylene, bp. 42°—1&5 Cyclopentene, bp. 45°—185 Propylacetylene, bp. 48°—185 Valerylene, bp. 56°—185 Dimethyleyclopropane, bp. 21°— 184 Isopropylethylene, bp. 21°—184 Methylethylethylenes, bp. 31° and 36°—184 Trimethylethylene, bp. 37°—184 Propylethylene, bp. 39°—184 Methyleyclobutane, bp. 40°—182 Cyclopentane, bp. 50°—182 2-Methylbutane, bp. 31°—182 Pentane, bp. 37°—182 Croconic ac.—213 Coumalin, bp. 207°—131 Furfurol, bp. 161°—20 Citraconic anhyd., 0. 213°—76 Glutaconic anhyd., mp. 87°—56 Pyromeconic ac., mp. 117°—59 Pyromucic ac., mp. 183°—45 Ethyl propiolate, bp. 119°—121 Furfuralcohol, bp. 169°—164 Leevulinice anhydrides, bp. 167°, 208°—131 Pentinoic ac., mp. 102°—43 Propargyl acetate, bp. 124°—121 Glutaric anhyd., mp. 56°—54 Tetrinic ac., mp. 189°—67 Citraconic ac., mp. 80°—41 Ethylenemalonic ac., mp. 140°—46 Glutaconic ac., mp. 132°—45 Itaconic ac., mp. 161° d.—48 Mesaconic ac., mp. 202°—50 Paraconic ac., mp. 57°—40 Trimethylenedicarbonic ac., mp. 175°—48 Acetonedicarbonic ac., mp. 135° d.—45 159° Ethenyltricarbonic ac., mp. 7 Acetyltrimethylene, bp. 114°—141 Cyclopentanone, bp. 180°—141 Ethylideneacetone, bp. 122°—141 Ethyl propargyl] eth., bp. 80°—161 Leevulinie ald., 187° d.—20 Methylbutenon, bp. 100°—141 Tetramethylene ald., bp. 116°—19 Tiglic ald., bp. 116.6°—19 Acetylpropionyl, bp. 108°—215 Allyl acetate, bp. 103.5°—120 Allylacetic ac., bp. 188°—75 Angelic ac , mp. 45.5°—53 Dimethylacrylic ac., mp. 70°—40 Ethyl acrylate, bp. 98.5° c.—120 a-Ethylacrylic ac., mp. 45°—39 Methylbutyrolactone, bp. 204°— 131 Methyl crotonate, bp. 120.7°—121 Methyltrimethylene carbonic ac., bp. 191°—74 Pentenoic ac ds, bp. 194°, 200°—74 Tetramethylenecarbonic ac., bp. 195°—75 246 C;Hs03 CHO; C.H,O, C;H,O, C,H,,0 C,H,,0, C,H, 003 FORMULA INDEX. Tiglic ac., mp. 64.5°—40 y-Valerolactone, bp. 207°—131 Itaconic anhyd., mp. 68°—55 Levulinic ac., bp. 239°—74 &-Methoxyisocrotonic ac., mp. 128° —61 Acetoxylpropionic ac., mp. 166°— 48 Dimethylmalonic ac., mp. 192° d.— 50 Ethylmalonic ac., mp. 111°—43 . Glutaric ac., mp. 97.5°—42 a-Hydroxylevulinic ac., mp. 103° —43 Methyl ethyl oxalate, bp. 174°— 122 Methyl malonate, bp. 181°-—122 Pyrotartaric ac., mp. 112°—43 Citramalic acids, mp. 95°, 119°— 42, 44 Ethyltartronic ac., mp. 115°—44 Methylmalic ac., mp. 123°—44 6-Oxyglutaric ac., mp. 95°—42 Trioxyglutaric acids, mp. 128°, 152°, 154°—45, 47 Diethyl ket., bp. 105°—141 Kthylallyl eth., bp. 66°—160 a-Ethylallyl ac., bp. 134°—162 Ethyl isopropenyl eth., bp. 62°— 160 Tsovalerianic ald., bp. 92.5°—19 Methylallylearbinol, bp. 115°—161 Methyl isocrotyl eth., bp. 72°—185 Methyl isopropyl ket., bp. 95°— 141 Methyl propyl ket., bp. 102°—141 1, 4-Oxypentane, bp. 78°—161 Pentamethylene oxide, bp. 81°— 161 Trimethylacetic ald., bp. 74.5°—19 Valerianic ald., bp. 103°—19 Vinylethylcearbinol, bp. 114°—161 Acetylearbinolethylether, bp. 128° 141 Acetylpropyl alc., bp. 208°—143 tert.-Butylcarbinol, mp. 52°—155 Butyl formate, bp. 107°—120 Ethyl propionate, bp. 98°—120 Hydracetylacetone, bp. 176°—142 Isobutyl formate, bp. 98°—120 Isopropyl acetate, bp. 91°—120 Isovalerianic ac., bp. 176° ¢.—74 Methyl butyrate, bp. 102.3°—120 Methylethylacetic ac., bp. 177°—74 Methyl isobutyrate, bp. 92.38°—120 Propyl acetate, bp. 102°—120 Trimethylacetic ac., mp. 35°—39 n-Valerianic ac., bp. 187°—74 Diethyl carbonate, bp. 126°—121 Methyl ethoxyacetate, bp. 145°— 121 a-Ethoxypropionic ac., bp. 196°— 74 Ethyl lactate, bp. 154°—73 Ethyl methoxyacetate, bp. 131°— 121 Methyloxybutyric ac., mp. 67°—40 Oxyvalerianic acids, mp. 31°, 85°— 39, 41 Propyl glycollate, bp. 170°—122 C,H, 0% C.H,,.0; CH, 0, C5Hi205 C,H,,0 CoH, CoH, C,.H,0, CHO, Angliceric ac., mp. 110°—43 Tigliceric ac., mp. 88°—41 Arabinose, mp. 160°—30 Xylose, mp. abt. 150°—30 Arabonic ac., mp. 89°—41 act. Amyl alc., bp. 129°—162 n-Amyl alc., bp. 138°—162 Diethylearbinol, bp. 116°—161 Dimethylethylcarbinol, bp. 102°— 161 Ethyl propyl eth.. bp. 64°—160 Isoamyl alc., bp. 180°—162 Methylbutylearbinol, bp. 136°—162 Methyl] butyl eth., bp. 70°—185 Methylisopropylearbinol, bp. 112° —161 Ethyl isopropyl eth., bp. 54°—160 Methylpropylearbinol, bp. 118°— 161 Trimethyleneglycol ethyl eth., bp. 160°—164 Dihydroxypentanes, bp. 187°, 221° —164, 165 Methylene diethyl ether, bp. §9°— 19 Ethyl glyceryl eth., bp. 227°-—165 Pentaerythrite, mp. 253°—156 Arabite, mp. 102°—155 C, GROUP. Benzene, bp. 80°—189 Hexadiéne, bp. 86°—186 Diallylene, bp. 70°—185 Hexadiéne, bp. 80°—185 1, 2-Dihydrobenzene, bp. 83°—185 1, 4-Dihydrobenzene, bp. 85°—185 Dimethylbutine, bp. 38°—184 Diallyl, bp. 59°—185 Butylacetylene, bp. 70°—185 Methylpentadienes, bp. 70° and 77°—185 Methylcyclopentenes, bp. 70° and 72°—185 Methylpentine, bp. 72°—185 Ethyldivinyl, bp. 73°—185 Hexadiéne (1, 3), bp. 73°—185 Methylpropylacetylene, bp. 83°— 1 85 Dimethylethylethylene, bp. 66°— 185 s-Methylpropylethylene, bp. 68°— 185 Butylethylene, bp. 69°—185 Methylethylpropylene, bp. 70°— 185 Methylcyclopentane, bp. 71°—182 Tetramethylethylene, bp. 73°—185 Cyclohexane, bp. 81°—182 Trimethylethylmethane, bp. 50°— 182 Diisopropyl, bp. 58—182 2-Methylpentane, bp. 62°—182 Methyldiethylmethane, bp. 64°— 182 Hexane, bp. 69°—182 Diacetylenedicarbonic ac, 177°—49 Benzoquinone, mp. 116°—206 mp. Gs ROP C,H,0; CsHe6O C,H,O, C,H,O, CoH,O3 C.H,O, C.H,O, C.H,Os C,H,O C,H;0, C,H;0; C.H3:0, C.H,.02 FORMULA INDEX. Coumalic ac., mp. 207° d.—69 Comanic ac., mp. 250°—71 Comenic ac., d. 260°—71 Furfuranedicarbonic ac., (2 Phenol, mp. 42°—91 Hydroquinone, mp. 169°—99 Methylfurfurol, bp. 187°—20 Pyrocatechin, mp. 104°—94 Resorecin, mp. 116°—95 Betulin, mp. 258°—159 Maltol, mp. 159°—98 sbl. w. Methylpyromucic ac., mp. 108°—59 Oxyhydroquinone, mp. 140.5°—97 Phenoglucin, mp. 200.5°—100 Phloroglucine, mp. 217—9°—101 Pyrogallol, mp. 133°—96 Dimethyl acetylenedicarbonate, bp. 196°—123 Muconic ac., d. abt. 320°—72 Aconitic ac., mp. 191° d.—49 Trimethylenetricarbonic acids, mp. 151°, 184° c., 220°—47, 49, 51 s-Ethanetetracarbonic ac., mp. 170°—48 Dimethylfurfurane, bp. 93°—189 Hexinone, bp. 149°—142 Dihydroresorcin, mp. 105°—94 Propylacetylenecarbonic ac., mp. at 39 Sorbic ac., mp. 134°—61 s-Dimethylsuccinic anhyd., mp. 87°—56 Ethylsuccinylosuccinic ac., mp. 128°—96 Allylmalonic ac., mp. 103°—43 Dimethyl fumarate, mp. 102°—119 Dimethyl maleate, bp. 205°—123 Ethylfumaric ac., mp. 194°—67 Monoethyl fumarate, mp. 70°—55 Ethylmaleic ac’, mp. 100°—43 Hexenedioic ac., mp. 195°—67 Lactide, mp. 128°—60 Methyleyclopropanedicarbonic ac., mp. 113°—43 Methylglutaconic ac., mp. 137°—46 Methylitaconic ac., mp. 166°—48 Tetramethylenedicarbonic acids, Beals too, 138°, 157°, 170°— 45, 46, 47, 48 Ethyl oxalylacetate, mp. 96°—94 Glucuronic anhyd., mp. 176°—49 Tricarballylic ac., mp. 166°—48 Citric ac., mp. 153°—47 Allylacetone, bp. 128°—141 Allyl eth., bp. 94°—161 Cyclohexanone, bp. 155°—142 Mesityl oxide, bp. 129.5°—141 Methylethylacrolein, bp. 137—19 Methylcyclopentanone, bp. 142°— 142 Methyl tetramethylene ket., bp. 135°—142 Acetonylacetone, bp. 194°—142 Acetylisobutyryls, bp. 115°, 128°— 215 y-Caprolactone, bp. 220°—131 Dimethylbutenoic ac., mp. 70°—40 Ethyl a-crotonate, bp. 142°—121 CoH,.O; CoH,0, (C,H,,O0;)% C.H,.0¢ CoH O08 C,H,,0 247 a-Ethylerotonic ac., mp. 41°—53 Ethyl isocrotonate, bp. 136°—121 Ethyl methacrylate, bp. 117°-—121 Hexenoic acids, mp. 33°, bp. 206° 203°—53, 75 , Isocaprolactone, bp. 207°—131 Methylpentenoic acids, mp. 24°; bp. 211°, 213°—52, 76 Methylvalerolactone, bp. 206°— 131 Pentamethylenecarbonic ac., bp. 214°—76 Propionylpropionic ald., mp. 40°— 17 y-Acetylbutyric ac., bp. 275°—74 $-Ethoxycrotonic ac., mp. 137°—62 Ethyl isoacetoacetate, bp. 128.5°— 121 Ethyl methylformylacetate, bp. 161°—20 Glycerine eth., bp. 171°—164 Propionic anhyd., bp. 169°—75 £-Propionylpropionic ac., mp, 32°— 39 Adipic ac., mp. 153° c.—63 Diethyl oxalate, bp. 186°—74 Dimethylsuccinic acids, mp. 129°, 139°, 195°, 209°—45, 46, 67, 50 Ethoxylsuccinic ac., mp. 86°—41 Ethylsuccinie ac., mp. 98°—42 Jsomannide, mp. 87°—155 Isopropylmalonic ac., mp. 87°—41 Methylethylmalonic ac., mp. 118°— 44 a-Methylglutaric ac., mp. 77°—41 Methyl isosuccinate, bp. 179°—122 3-Methylpentanedioic ac., mp. 85° —41 Methyl succinate, bp. 195°—123 Propylmalonic ac., mp. 96°—42 Cellulose—31 Dimethylmalic ac., mp. 130°—45 Ethoxysuccinic ac., mp. 78°—41 Glycogen, mp. abt. 240°—31 Lactic anhyd., mp. 255°—71 a-Oxyadipic ac., mp. 151°—47 Saccharin, mp. 160°—129 Starch—31 Dimethyl racemate, mp. 85°—119 Dimethyl tartrate, mp. 48°—118 Monoethyl tartrate, mp. 90°—42 Isosaccharic ac., mp. 185°—49 Mucic ac., mp. 206° d.—69 Saccharic ac.—34_ Talomucic ac., mp. 158° d.—47 Caproic ald., bp. 129°—19 Cyclohexanol, bp. 160°—163 Dimethylallylearbinol, bp. 119°— 162 Ethyl isocrotyl eth., bp. 93°—186 Ethyl isopropyl ket., bp. 114°— 141 Ethyl propyl ket., bp. 123°—141 Hexenyl alc, bp. 187°—162 Methyl] butyl ket., bp. 127°—141 Minho bp. 138°— Methylethylacetone, bp. 118°— 141 248 C.H,,0, C.H,.0; C,.H,,0, C.H,,0; C.H,,0. C,H,,0 C,H,,0, FORMULA INDEX. Methyl] isobutyl ket., bp. 116°— 141 1, 5-Oxyhexane, bp. 106°—161 Pinacoline, bp. 106°—141 Amyl formate, bp. 130°—121 Butyl acetate, bp. 125°—121 Caproic acids, bp. 197°, 206°—75 Diacetone alc., bp. 164°—142 Diethylacetic ac., bp. 190°—74 Dimethylethylacetic ac., bp. 187°— 75 Ethyl butyrate, bp. 120°—121 Ethyl isobutyrate, bp. 110°—120 Isobutyl acetate, bp. 116°—121 Isobutylacetic ac., bp. 208°—75 Isoamyl formate, bp. 123°—121 Methylpropylacetic acids, bp. 190°, 193°—75, 74 Methyl] isovalerianate, bp. 127°— 121 Methyl trimethylacetate, bp. 101°—120 Methyl valerianate, bp. 127°— 121 Allyl glyceryl eth., bp. 240°—165 Cyclohexantriol, mp. 184°—156 Ethoxyisobutyric acids, bp. 181°, 217°—75, 74 Ethyl ethoxyacetate, bp. 152°— 121 Ethyl oxyisobutyrate, bp. 150° —121 Ethyl a-oxybutyrate, bp. 165°— 122 Methylpentanoloic ac., mp. 73°—40 a-Oxycaproic ac., mp., 61°—40 Oxydiethylacetic ac., mp. 80°—41 Paraldehyde, bp. 124°—19 Ethyl dioxybutyrate, bp. 227°— 124 Quercite, mp. abt. 230°—156 Rhamnose, (isodulcite)—30 Fructose (Levulose), mp. 94°—30 Galactose, mp. 168°—30 Glucose, mp. 146°—30 Inosite, mp. 225° c.—156 Mannose,—29 Sorbinose mp. 164°—30 Dimethylisopropylcarbinol, bp. 118° —16l Ethylisopropylearbinol, bp. 128°— 162 Ethyl butyl eth.. bp. 92°—186 Ethyl! isobutyl eth., bp. 79°—185 Ethylpropylearbinol, bp. 1385°— 162 act.-Hexyl alc.. bp 154°—162 Hexyl ale. bp 157°—163 Isopropyl eth.. bp 69°—160 Isohexylearbinol, bp. 150°—162 Methyldiethylearbinol, bp. 123°— 162 Methylisobutylearbinol, bp. 130°— 162 Methylpropylearbincarbinol, bp. 147°—162 Pinacoline ale . bp. 120°—162 Propyl ether, bp. 91°—161 Acetal, bp 104°—19 Dihydroxyhexane, bp. 206°—165 BA Sly 4 C,H,,0. C,H,,0 Glycol diethyleth., bp. 123°—162 Pinacone, mp. 36°—155 Triethylene glycol, bp. 290°—165 Rhamnite, mp. 121°—155 Mannite, mp. 163°, 166°, 168°— 155, 156 Dulcite, mp. 188°—156 Sorbite, mp. 110°—155 Pinacone hydrate, mp. 56°—155 C, GROUP. Toluene, bp. 111°—189 Tropilidene, bp. 114°—189 Dihydrotoluene, bp. 107°—186 Heptone, bp. 115°—1&6 Cycloheptadiéne, bp. 120°—189 Ethylpentadiéne, bp. 97°—186 (inanthylidene, bp 102°—186 Heptine, bp. 103°—1&6 Ethylpropylacetylene, bp. 105°~ 186 Toluenetetrahydride, bp. 105°— 186 Methylbutylacetylene, bp. 112°~ 186 Cycloheptene, bp. 114°—1&6 Dimethylpentene, bp. 77°—185 Trimethylbutene bp. 79°—185 Dimethylpentene, bp. £3°—185 Dimethylcyclopentane, bp. 94°-— - 182 Ethylpentene, bp. 97°—1&6 Heptene(1), bp. 98°—1&6 Hexahydrotoluene, bp. 101°—182 Cycloheptane, bp 118°—182 Dimethyldiethylmethane, bp. 86°— 182 Methylhexanes, bp. 90° and 91°— 182 Triethylmethane, bp. 96°—182 Heptane, bp. 98°—182 Chelidonic ac., mp. 262°—71 Benzaldehyde, bp. 179.5°—20 Benzoic ac., mp. 121.2° e.—60 Furfuracrolein, mp. 51°—17 Oxybenzaldehydes, mp. 115°—17, 18 Salicylic ald., bp. 196.5°—20 Toluquinone, mp. 68°—205 Furfuracrylic ac., mp. 141°—62 m-Oxybenzoic ac., mp. 200°—68 p-Oxybenzoic ac., mp. 210°—69 Salicylic ac., mp. 158° e.—64 Dioxybenzoic acids, mp. 199°, 204°, 205°, 232°—50, 50, 69, 51 Protocatechuic ac., mp. 199° d.— Gallic ac., mp. abt. 230°—70 Pyrogallocarbonic ac., mp. 197° d. =n 104°, Trimethylenetetracarbonic ac., mp. abt. 97°—42 Anisol, bp. 155°—189 Benzyl ale., bp. 205°—165 p-Cresol, mp. 36°—91 o-Cresol, mp. 30°—9i m-Cresol, bp. 203°—104 Dibydrpben at aa bp. 170° d ae o_ C;H,0, C,H,O; C,H,0, C,H.0, C,H,,0 C,H,,0; C,H, 0, C,H,.Os qe 10.6 C,H,,0 C,H,,0, C,H,,0, C,H,,0, FORMULA INDEX. Guiacol, mp. 31°—91 m-Oxybenzyl ale., mp. 67°-—93 Dioxytoluenes, mp. 64°, 103°, 124° —92, 94, 96 Homopyrocatechin, mp. 51°—92 Hydroquinone methyl eth., mp. 53°-—-92 Isohomopyrocatechin, mp. 47°—92 Orcin, mp. 107°—95 p-Oxybenzyl alc., mp. 110°—95 Saligenin, mp. 86°—93 Ethyl pyromucate, mp. 34°—118 Methylpyrogallol, mp. 129°—96 Uvic ac., mp. 135°—62 Dicarboxyglutaric ac., mp. 167° d.—48 Tretol, mp. 186°—100 Cinchoic ac., mp. 168°—65 Tetrahydrobenzaldehyde, bp. 187° Ethyl tetrinate, mp. 30°—118 Diacetylacetone, mp. 49°—92 Dimethyl citraconate, bp. 210°— 123 Dimethy] mesaconate, bp. 206°— 123 Dimeth yltrimethylenedicarbonic acids, mp. 176°, 213°—49, 50 Ethylitaconic ac., mp. 164°—65 Ethylmesaconic ac., mp. 172°—65 Dimethyl itaconate bp. 211°—123 Pentamethylenedicarbonic acids, mp. 88°, 140°, 159°—41, 46, 64 Teraconic ac., mp. 162° d.—48 Terebic ac., mp. 174°—66 Hydrochelidonic ac., mp. 142°—62 Dicarboxylpentanoic ac., mp. 141° d.—46 Diallylearbinol, bp. 151°—162 Methylcyclohexanone, bp. 169°— 142 ; Propionyleyclobutane, bp. 155°— 142 Suberone, bp. 180°—142 Acetylisovaleryl—215 Allyl butyrate, bp. 142°—121 Allyl isobutyrate, bp. 133°—121 Ethyl allylacetate, bp. 143°—121 Ethyl angelate, bp. 141°—121 Ethyl tetramethylene carbonate, bp. 161°—122 Ethy] tiglate, bp. 156°—122 Ethylvalerolactone, bp. 219°—131 Heptenoic ac., bp. 227°—76 Hexahydrobenzoic ac., mp. 30°—52 y-Ginantholactone, bp. 235°—131 Teracrylic ac., bp. 218°—76 Acetylvalerianic ac., mp. 41°—39 Ethyl levulinate, bp. 205°—123 Ethyl @-methoxyisocrotonate, bp. 178°—122 Mesitonic ac., mp. 74°—40 Butylmalonic acids, mp. 76°, 101° —40, 43 Diethyl malonate, bp. 198°—123 Diethylmalonic ac., mp. 121°—44 Dimethyl dimethylmalonate, bp. 178°—122 s-Dimethylglutaric 128°, 140°—44, 46 acids, mp. C,H,,0; C,H,,0.¢ C,H,,0 C,H,,0, C,H1,0, 249 Dimethylpentanedioic acids, mp, 84°, 100°—41, 42 Ethyl acetoxylpropionate, bp. 178° —122 Tsobutylmalonic ac., mp. 107°—43 Isopropylsuccinic ac., mp. 117°— Sh Methylcarboxylpentanoic ac., nip. 103°—43 Methyladipic ac., mp. 94°—42 Methylethylsuccinic acids, mp. 101°, 169°, 180°—43, 65, 49 Methyl ethyl succinate, bp. 208°— 123 Methylpropylmalonic 106°, 121°—43, 44 Pimelic ac., mp. 105°—43 Propylsuccinic ac., mp. 91°—42 Trimethylsuccinic ac., mp. 152°— 47 Diethyl tartronate, bp. 223°—124 s-Methylethylmalic ac., mp. 132°— 45 acids, mp. Diethyl mesoxalate, mp. 57°— 118 Quinic ac., mp. 162° c.—48 Diisopropyl ket., bp. 124°—141 Dimethylpentanones, bp. 182°, 137°, 126°—144, 142, 141 Dipropyl ket., bp. 144°—142 Ethyl isobutyl ket., bp. 136°—142 Ethylpentanone, bp. 138°—142 Ethyl valeryl eth., bp. 112°—186 Methyl amyl ketones, bp. 144°, 151°—142 (nanthic ald., bp. 155°-—20 Polycenanthylic ald., mp. 52°—17 Suberyl alc., bp. 184°—164 Amy] acetates, bp. 139°, 148°—121 Amylacetic ac., bp. 221°—76 Ethyl isovalerianate, bp. 134°—121 Ethyl methylethylacetate, bp. 134° —121 Ethylpropylacetic ac., bp. 209°—75 Ethyl trimethylacetate, bp. 118°— 121 Ethyl valerianate, bp. 144°—121 Isoamylacetic ac., bp. 209°—75 Methyldiethylacetic ac., bp. 207°— 75 Methyl caproate, bp. 150°—121 2-Methylhexanoic(1) ac., bp. 210°— 5 7 Methyl isobutylacetate, bp. 150°— 121 Hexyl formate, bp. 154°—121 (&nanthylic ac., bp. 223°—76 Dipropyl carbonate, bp. 168°—122 Ethyl a-ethoxypropionate, bp. 155° —121 Ethyl a-oxyisovalerianate, bp. 175° —122 Ethyl a-oxyvalerianate, bp. 190° —122 2-Methylhexanoloic ac., mp. 64.5° —40 Methyl oxydiethylacetate, bp. 165° 122 Oxycenanthylic ac., mp. abt. 60°— 54 250 C,H,,0, CsHyi¢ CsHis C;H,0, C,H,0, C;H,O, CHO, FORMULA INDEX, Galactosecarbonic ac., mp. 145°— 47 Mannoheptonic ac., mp. 175° d.— 49 C,H,O; Diisopropylearbinol, bp. 140°—162 Dimethylisobutylearbinol, bp. 130° —162 Dipropylearbinol, bp. 154°—162 Ethyl isoamyl eth., bp. 112°— 186 C.H,O, Ethyl isobutylearbinol, bp. 147°— | C,;H,;O 162 Heptyl alc., bp. 176°—163 Propyl butyl eth., bp. 117°—186 Methylamylearbinol, bp. 164°—163 Methylethylpropylearbinol, bp. 140° —162 Methylisoamylearbinol, bp. 149°—. 162 Trimethylbutanol, bp. 131°—162 Triethylearbinol, bp. 141°—162 Trimethylene glycoldiethyl eth., bp. 140°—187 Rhamnohexite, mp. 173°—156 Perseite, mp. 188° c., 203° c.—156 C, GROUP. Phenylacetylene, bp. 142°—189 Styrene, bp. 146°—189 Ethylbenzene, bp. 186°—189 n-Xylene, bp. 138°—189 m-Xylene, bp. 139°—189 o-Xylene, bp. 142°—189 m-Dihydroxylene, bp. 133°—187 o-Dihydroxylene, bp. 134°—187 Octone, bp. 134°—187 p-Dihydroxylene, bp. 135°—187 Trimethyleyclopentene, bp. 108°— 186 Dimethylhexadiéne, bp. 113°, 133° —186, 187 2-Methylheptadiéne, bp. 117°—186 Octadiéne, bp. 118°—186 Ethylhexadiéne, bp. 122°—186 Octine(1), bp. 131°—186 Octine(2), bp. 183°—187 Diisobutylene, bp. 102°—186 s-Dimethyldiethylethylene, bp. 115° —186 s-Diisopropylethylene, bp. 117°— 186 C,H,O, CsH,O3 Hexahydroxylenes, bp. 118° and 120°—182 Methylethylcyclopentane, bp. 124° —183 Octene(1), bp. 125°—186 Dimethylhexane, bp. 108°—182 Octane, bp. 125°—183 Phthalic anhyd., mp. 128°—61 Phthalid, mp. 73°—129 Aldehydobenzoic acids, mp. 97°, 165°, 285°—17, 18 Benzoylformic ac., mp. 65°—40 Piperonal, mp. 37°—17 Aldehydosalicylic acids, mp. 179°, 234°, 243°, 248° 18 Isophthalic ac., mp. a.300°—72 o-Oxyphenylglycollic ac., mp. 48°— 39 Cs;H,O, C,H,0; C;H,Os ’ Phthalic ac., mp. 184° d.—67 Piperonylic ac., mp. 228°—70° Terephthalic ac., sbl. w. m.—72 Furalmalonic ac., mp. 205° d.—69 Oxyisophthalic acids, mp. 248°, 388° c., 305°—70, 72 Oxyphthalic ac., mp. 181° d.—49 a-Resodicarbonic ac., mp, 276°—71 Tetrahydroxyterepthalic ac., mp. 139°—46 Acetophenone, bp. 202°—142 Phenylacetic ald., bp. 193°—20 m-Toluic aldehydes, bp. 199°, 200° Anisic ald., bp. 248°—21 Dimethylquinones, mp. 55°, 72°— 205 Furfuralacetone, mp. 39°—136 Methyl benzoate, bp. 199°—123 Methylenedihydrobenzoic ac., mp, 33°—53 Methoxybenzoic ald., mp. 35°—17 Oxyacetophenone, mp. 86°—138 Oxybenzoicaldehydemethyilether, bp. 230°—20 Oxytoluic aldehydes, mp. 54°, 56°, 110°, 115°, 172°, 209°—17, 18, 65, 20 | Phenyl] acetate, bp. 196°—123 Phenylacetic ac., mp. 76°—55 Phloron, mp. 125°—206 Toluic acids, mp. 102°, 110°, 176° —58, 59, 66 Anisic ac., mp. 184.2° C.—67 Diphenyl p-oxybenzoate, mp. 131° —119 Mandelic ac., mp. 118°—44 m-Methoxybenzoic ac., mp. 106°— 58 Methylethersalicylic ac., mp. 98.5° —d57 Methylphenolcarbonic ac., mp. 183° —66 Methylphenolmethanoic ac., mp. 168°—65 Oxyphenylacetic acids, mp. 129°, 137°, 148°—45, 46, 47 o-Oxymethylbenzoic ac., mp. 120° —60 Oxyxyloquinone, mp, 103°—206 Oxytoluic acids, mp. 151°, 163°, 172°, 177°, 183°, 20670702 63, 65, 66, 49, 69, 50 Phenoxyacetic ac., mp. 96°—42 Piperonyl ale., mp. 51°—157 Quinacetophenone, mp. 202°—209 Resacetophenone, mp. 142°—97 Vanilline, mp. 80°—17 Dehydracetic ac., mp. 108.5°—58 Dihydrophthalic ac., mp. 215°—70 Gallacetophenone (alizarin yellow C), mp. 168°-—99; 253 Homogentisic ac., mp. 147°-—47 Isodehydracetic ac., mp. 155°—64 Methoxysalicylic ac., mp. 154°—63 Orsellinic ac., mp. 176° d.—66 Vanillic ac., mp. 207°—69 Carbopyrotritaric ac., mp. 230°—70 Methyl gallate, mp. 192°—119 C,;H;O; C,H,,O CsH 0, CgH yO; Cs Hy O, CsHio O 6 CsH Os CsH,,05 CsH,,0, CsH,,05 CsH,,0, CsH,,0; C;H,,0 FORMULA INDEX. Methylfurfurancarbonacetic mp. 204°—68 Tetramethylenetetracarbonic mp. 200° d.—50 Benzvlearbinol, bp. 212°—165 Cresyl methyl ethers, bp. 171°, 175°—190 p-Ethylphenol, mp. 46°—92 Methyl benzyl] eth., bp. 167°—190 Methylphenylearbinol, bp. 203°— 164 Phenetol, bp. 172°—190 Tolylearbinols, mp. 34°, 59°, 217°— 157, 165 Xylenols, mp. 26°, 49°, 65°, 66°, 74°, 75°—91, 92, 93 Anisic ale., mp. 45°—157 B-Orcin, mp. 163°—98 Diethyl hydroquinolyl eth., mp. §5°—175 Dimethyl resorcinyl eth., bp. 214° —192 Dioxyxylol, mp. 120°, 149°—95, 97 Homosaligenin, mp. 105°—94. Hydroquinone, ethyl eth., mp. 66° 3 ac., AC., Phthalic alc., mp. 64°—155 Pyrocatechin, mp. 104°—94 Saligenin methyl eth., bp. 247°— 165 Styrolene alc., bp. 205°—192 Tolylene alc., mp. 112°, 46°—155 Veratrol, bp. 205°—192 m-Xylorcin, mp. 125°—96 Methyluvinic ac., mp. 98°—57 Pyrogalloldimethylether, mp. 51°— 92 Pyrogallol ethyl eth., mp. 95°—94 Vanillyl alc., mp. 115°—95 Biphenyldiolcarbonic ac., mp. 270° 71 Diallyl oxalate, bp. 216°—124 Dimethylapionol, mp. 105°—95 Oxalyldiacetone, mp. 120°—95 Tetrahydrophthalic acids, mp. 120°, 215°—44, 69 Diacetylsuccinic ac., mp. d. 160°— Dicarboxyl-hexanedioic 189°, 236°—49, 51 Diethylacetic anhyd., bp. 230°—76 Diallylacetic ac., bp. 227°—76 Ethyl sorbate, bp. 195°—123 Diallyloxalic ac., mp. 48°—53 s-Diethylsuccinic anhyd., bp. 245° Ac. emp, ethyleneacetoacetate, bp. Ethyl diacetoacetate, bp. 202°—75 Diethyl fumarate, bp. 218°—124 Diethyl maleate, bp. 225°—124 Hexahydrophthalic acids, mp. 192°, 215°—67, 69 Terpenylic ac., mp. 90°—42 Trimethylpentanedioldioic ac., mp. 120°—44 Crotonyl eth., bp. 144°—189 Diisobutylene ald., bp. 230°—20 Methyldiallylearbinol, bp. 158°—163 CsH,,0, C3H,,03 C,H,,0, C;H,,0; CsH,,0 6 C;H,,O03 CsH,,0 C3H,,0, Onli gs 251 Methylheptenone, bp. 173°—142 Acetylisocaproyl, bp. 163°—215 Allyl isovalerianate, bp. 154°—121 Cycloheptanecarbonic ac., bp. 246° -—76 Ethyleaprolactone, bp. 254°—131 Ethyl a-ethylcrotonate, bp. 165°— 122 Methylhexamethylenecarbonic ac., bp. 235°—76 n-Butyric anhyd., bp. 182°—75 Ethyl dimethylacetoacetate, bp. 184°—122 Ethyl a-propionylpropionate, bp. 199°—123 Isobutyric anhyd., bp. 182°—75 Octanonoiec ac., mp. 29°—39 Dialdane, mp. 130°—18 s-Diethylsuccinic acids, mp. 129°, 192°45, 67 Diethyl isosuccinate, bp. 198°—123 Diethyl succinate, bp. 216°—124 s-Dimethyladipic ac., mp. 140°, 75° —62, 40 Dimethylethylsuccinic 139°—46 Dipropyl oxalate, bp. 213°—124 Isoamylmalonic ac., mp. 93°—42 Isobutylsuccinic ac., mp. 107°—43 Pentylmalonic ac., mp. 82°—41 Suberic ac., mp. 140°—62 Tetramethylsuccinic ac., mp. 195° d.—68 Diethyl diglycollate, bp. 240°—125 Diethyl i-malate, bp. 255°—126 Diethyl tartrate, bp. 280°—126 Methyl, gallate, + 3H,O, mp. 192°d. —119 Allyl isoamy! eth., bp. 120°—186 Diethylallylearbinol, bp. 157°—163 Dimethylhexanone, bp. 151°—142 Ethyl amyl ket., bp. 170°—142 Methylbutyrone, bp. 180°—142 Methylheptenol, bp. 175°—163 Methylheptanone, bp. 170°—142 Methyl hexyl ket., bp. 172.5°—142 Propy] isobutyl ket., bp. 155°—142 Butyl butyrate, bp. 165°—122 Caprylic ac., bp. 237°—76 Dipropylacetic ac., bp. 219°—76 Ethyl caproate, bp. 167°—122 Ethyl isobutylacetate, bp. 161°— 122 Ethyl diethylacetate, bp. 151°—121 Ethyl methylpropylacetate, bp. 153°—121 Heptyl formate, bp. 176°—122 Hexyl acetate, bp. 169°—122 Isoamyl propionate, bp. 160°—122 Isobutyl butyrate, bp. 157°—122 Methylcenanthylate, bp. 173°— 122 Ethyl ethoxybutyrate, bp. 168°— 122 vulpes bith ay Ethyl oxydiethylacetate, bp. 175° —122 a-Oxycaprylic ac., mp. 69°—55 Trimethylpentanoloic ac., mp. 92° —42 252 C,H,,0 C,H,3,0, C,H, C.Hio C.His FORMULA INDEX. Butyl ethers, bp. 141°, 120°—187, 186 Diethylisopropylearbinol, bp. 160° —163 Diethylpropylearbinol, bp. 160°— 163 Ethyl hexyl eth., bp. 185°—187 Isobutyl eth., bp. 122°—186 Methylhexylcarbinol, bp.179°—163 Methyl heptyl eth., bp. 150°—187 Methyldipropylearbinol, bp. 161°— 163 Octyl ale., bp. 195°—163 Diisopropylglycol, mp. 51°—155 Dimethylpinacone, mp. 49°—155 Ethylidene dipropyl eth., bp. 147° —20 C, GROUP. Indene, bp. 1£0°—191 Phenylallylene, bp. 185°—191 Benzylethylene, bp. 155°—189 p-Methylstyrene, bp. 172°—190 Allylbenzene, bp. 174°—190 Hydrindene, bp. 176°—190 Cumene, bp. 153°—1&9 Propylbenzene, bp. 158°—189 Methylethylbenzenes, bp. 158°, 162° —189, 190 Mesitylene, bp. 164°—190 Pseudocumene, bp. 170°—190 v-Trimethylbenzene, bp. 175°—190 Nonone, bp. 156°—187 Campholene, bp. 135°—187 Trimethyleyclohexene, bp. 138°— 187 Dimethylheptadiéne, bp. 142°—187 Nonylene, bp. 139°—187 Methvloctene, bp. 141°—187 Propylhexamethylene, bp. 148°— 187 Methylethyleyclohexane, bp 151° Dimethyleycloheptane, bp. 153°— 187 Hexahydropseudocumene, bp. 135° | —1§ Mesitylenehexahydride, bp. 136°— Hexahydrocumene, bp. 148°—183 8-Nonane, bp. 130°—183 a-Nonane, bp. 136°—183 Nonane, bp. 148°—183 Trimellitic anhyd. mp. 157°—64 Truxone, mp. 289°—140 Coumarin, mp. 67°—129 Diketohydrinden, mp. 130°—96 Phenylpropiolic ac., mp. 136°—62 Cumarilic ac., mp. 192°—67 Daphnetin, mp. 254°—210 Aldehydoxyisophthalic acids, mp. 237°, 260°—18 Hemimellitic ac., mp. 185° d.—67 Trimellitic ac., mp. 216° d.—50 Trimesic ac., mp. 345°, 347°—72, 51 Cinnamic ald., bp. 130° (20 mm.)— 21 Hydrindones, mp. 40°, 61°—136, 137 Vinyl phenyl ket., mp. 42°—136 C,H,0, C,H,O, C,H,0, C,H 305 C,H,,0 CoH Oe C,H,.9, Acetylbenzoyl, bp. 217°—215 Allocinnamic ac., mp. 68°—55 Atropic ac., mp. 106°—58 Cinnamic ac., mp. 1383°—61 Homococeaic ac., mp. 150°—63 Isocinnamic ac., mp. 57°—54 Melilotic anhyd., mp. 25°, bp. 272° —129; 132 Acetophenonecarbonic ac.; mp. 115° —bY p-Acetylbenzoic ac., mp. 200°—68 Acetylsalicylic ald., mp. 37°-—17 Benzoylacetic ac., mp. 103°—58 Cumaric acids, mp. 191°, 206°, 208° —67, 69 Hydrocumarilic ac., mp. 116°—43 Phenylpyruvic ac., mp. 154°—63 p-Toluylearbonic ac., mp. 96°—57 Acetoxybenzoic acids, mp. 127°, 185°—60, 67 Caffeic ac., mp. 195°—209 Homophthalic ac., mp. 175°—66 Homoterephthalic ac., mp. 237°—70 Methylisophthalic ac., mp. 325°— 72 Methylphthalic ac., mp. 144°—62 Methylterephthalic ac., mp. 281°— 72 Methoxylphenylglyoxylic ac., mp. 89°—41 Monomethylphthalate, mp. 82.5°— 56 Phenylmalonic ac., mp. 152°—47 Salicylic ac. acetate, mp. 118°—59 Umbellic ac., d. 260°—71 s-Uvitic ac., mp. 287°—72 Aldehydovanillic acid, mp. 221°— 18 m-Oxyuvitic ac., mp. 290°—72 p-Anol, mp. 93°—94 Cinnamyl alc., bp. 254°—165 Hydrocinnamice ald., bp. 208°—20 a-Hydroxindene, mp. 54°—157 Methyl] benzyl ket., mp. 27°-—136 p-Methyl tolyl ketones, bp. 222°, 224°—143 Propiophenone, bp. 218°—143 Benzyl acetate, bp. 206°—123 p-Cresyl acetate, bp. 214°—124 Dimethylbenzoic acids, mp. 98°, 126°, 132° 144°, 163°, 166°—57, 60, 61, 62, 65 Ethylbenzoic acids, mp. 47°, 68°, 112°—53, 55, 59 Ethy] benzoate, bp. 212°—123 Hydrocimean ac., mp. 48.7°— 54 Methyl phenylacetate, bp. 220°— 124 Pheny! propionate, bp. 211°—123 Pheriylpropionic ac., bp. 264°—76 m-Oxybenzoic aldehyde ethylether, bp. 245°—21 Tolylacetic acids, mp. 61°, 88°, 91° — 654, 56, 57 Acetovanillon, mp. 115°—9 Alorcinic ac., mp. 97°—57 Atrolactic acid, mp. 90°—42 Dimethylphenolearbonie ac., mp. 199°, 223°—68, 70 C,H, C,H,,0, C,H,,0, C.H,.0, C,H,,0, C,H,.0, FORMULA INDEX. Ethoxybenzoic ac., mp. 137°, 195° —62, 67 Ethylether salicylic ac., mp. 19°— 52 Ethyl oxybenzoates, mp. 116°, 72° —95, 119 Hydrocumaric acids, mp. 82°, 111°, 128°—41, 48, 61 Fluorenecarbonic ac., mp. 175°—66 Methyl anisate, mp. 45°—118 Methyl mandelate, mp. 52°—118 Methylmandelic acids, mp. 84°, 145°—41, 62 Methyl methylethersalicylate, bp. 2235°—125 Methoxyphenylacetic ac., mp. 72°— 55 Methyl oxyphenylacetate, bp. 310° —127 Orcacetophenone, mp. 146°—97 Oxymesitylenic ac., mp. 179°—66 Paoénol, mp. 50°—92 Phenyllactic acids, mp. 93°, 97°-—42 Phenoxypropionic ac., mp. 112°— 59 Phloretic ac., mp. 129°—45 Tropic acids, mp. 117°, 123° and 127°—44, 60 Ethyl-dioxybenzoate, mp. 75°—119 Hemipinic ac , mp. 161°—64 Hydrocaffeic ac., mp. 139°—46 Methy! vanillate, mp. 62°—119 Phenylglyceric ac., mp. 143°—46 Veratric ac., mp. 181°—66 Cyclopentane-tetracarbonic ac., mp. 187° d.—49 o-Cresyl ethyl ethers, bp. 180°, 189° —191 Dimethyl] orcinyl eth., bp. 244°— 193 Ethyl benzyl eth., bp. 185°—191 p-Isopropylphenol, mp. 61°—92 Methylbenzylearbinol, bp. 215°— 163 Mesitol, mp. 68°—93 Phenylpropy] alc., bp. 235°—165 m-Propylphenol, mp. 26°—91 Pseudocumenol, mp. 71°—93 Trimethylphenols, mp. 81°, 95°— 93, 94 Methylphenylethyleneglycol, mp. §2°—155 Trimethylbenzoic ald.,mp. 105°—17 Trimethylphendiole, mp. 149°, 169°, 156°—97, 99, 98 Iridol, mp. 57°—92 Phloroglucin trimethyl eth., mp. 52° —175 Propylpyrogallol, mp. 79°—93 Mercato trimethyl eth., mp. 47° —175 Ethyl pyrotritarate, bp. 214°—124 Metacrolein, mp. 45°—17 Trimethylphloroglucin, mp. 184°— 99 Diallylmalonic ac., mp. 1383°—45 Anhydrocamphoric ae., mp. 1389°— 46 Hexamethylenetricarbonic ac., mp. 152°—47 253 Trimethyl aconitate, bp. 270°—126 Camphenylon, mp. 36°—136 Diallylacetone, bp. 174°—142 Phoron, mp. 25°—136 Campholitic ac., mp. 133°, bp. 241° —61, 76 Ethoxytetrahydrobenzoic ac., mp. 73°— 55 Ethyl trimethyleneacetoacetate, bp. 226°—124 Pinonic ac., mp. 128°—61 Diethyl citraconate, bp. 231°—125 Diethyl ethylenemalonate, bp. 213° ”) el Diethyl glutaconate, bp. 237°—125 Diethyl itaconate, bp. 228°—124 Diethyl mesaconate, bp. 229°—125 Diethyl acetylmalonate, bp. 239°— 76 Diethyl ketipate, mp. 76°—93 Camphoronic acids, mp. abt. 150°, 166°—47, 48 Trimethyl citrate, mp. 79°—119 Ethyldiallylearbinol, bp. 175°—163 Isobutyl angelate, bp. 177°—122 Diethylacetylacetone, bp. 203°— 123 Ethyl a-butyrylpropionate, bp. 208°—123 Ethyl mesitonate, bp. 210°—123 Ethyl methylethylacetoacetate, bp. 200°—123 Azelaic ac., mp. 106°—58 Diethyl dimethylmalonate, bp. 196°—123 Diethyl ethylmalonate, bp. 207°— 123 Diethyl glutarate, bp. 237°—125 Dipropyl malonate, bp. 228°—125 Dimethylheptanone, bp. 181°—142 Dipropylacetone, bp. 173°—142 Ethyl hexyl ket., bp. 190°—142 Ethyl isoamylacetate, bp. 177°— 122 Heptyl acetate, bp. 190°—123 Isoamyl butyrate, bp. 179°—122 Isoamy] isobutyrate, bp. 169°—122 Methyl caprylate, bp. 193°—128 Octylformate, bp. 193°—123 Pelargonic ac., bp. 253°—76 Dibutyl carbonate, bp. 208°—123 Diisobutyl carbonate, bp. 190°— 122 Parapropionic ald., bp. 169°—20 Ethyldipropylearbinol, bp. 179°— 163 Ethyl heptyl eth., bp. 166°—187 Methyl octyl eth., bp. 173°—187 Nony]l alc., bp. 213°—163 Propylidenedipropy] ether, bp. 166° —20 Ethyl orthocarbonate, bp. 158°— 122 C,, GROUP. Naphthalene, mp. 80°—176 Phenylcrotonylene, bp. 187°—191 Ethylphenylacetylene, bp. 202°— 192 v-Methylindene, bp. 205°—192 254 C,H, C,H, C, oH, 6 C,H; C,H, Cy Ho» C,.H,O, Up ee 63 Cy HO, Cio H(Os CyoH,0 CioHs02 Cy) HO; FORMULA INDEX. Naphthalenedihydride, bp. 212°— 192 Butenylbenzene, bp. 186°—191 Dicyclopentadiéne, mp. 33°—175 Isobutenylbenzene, bp. 181°—191 p-Tolylpropylene. bp. 199°—192 Naphthalenetetrahydride, bp. 205° —192 Phenylbutylene, bp. 177°—191 Butylbenzenes, bp. 168°, 171°, and 180°—168, 190, 191 Cymene, bp. 175°—190 m-Methylisopropylbenzene, bp.175° —190 Diethylbenzenes, bp. 181°, 182°, and 185°—191 Dimethylethylbenzenes, bp. 1°3°, 185°—191 Durene, mp. 79°—176 Naphthalenehexahydride, bp. 205° —192 Tetramethylbenzenes, bp. 196°, 204° —192 Camphenes, mp. 47°, 51°—175 Decone, bp. 147°—187 Pinene, bp. 156°—189 Phellandrene, bp. 171°—190 Limonenes, bp. 176°, 181°—190, 191 Sylvestrene, bp. 176°—191 Terpinene, bp. 180°—191 Terpinolene, bp. 184°—191 Naphthaleneoccahydride, bp. 187° —191 Decenylene, bp. 150°—187 Dimethylactadiéne, bp. 168°—187 Propylheptadiéne, bp. 158°—187 Menthene, bp. 167°—187 Naphthalenedecahydride, bp. 176°, 177°—187, 183 Diamylene, bp. 155°—187 Dekanaphthene, bp. 161°—183 a-Terpenetetrahydride, bp. 161°— 183 6-Terpenetetrahydride, bp. 164°— 83 Terpane, bp. 170°—183 Decane, bp. 173° c.—183 Dimethyloctane, bp. 160°—183 a-Naphthoquinone, mp. 125°—207 f-Naphthoquinone, d. 117°—206 Juglon, mp. 152°—208 a-Dioxynaphthoquinone, mp. 276° —211 Furil, mp. 162°—208 Naphthazarin—214 Benzenetetracarbonic acids, 237°, 238°, 264°—51 a-Naphthol, mp. 94°—94 6-Naphthol, mp. 122°—96 Dioxynaphthalenes, mp. 134°, 140°, 159°, 178°, 190°—96, 97, 98, 99, 100 Hydronaphthoquinones, mp. 60°, 175°—92, 99 Indenecarbonic ac., mp. 230°—70 Methylphenylpropiolic ac., mp. 109° 59 Aldehydocinnamie ac., mp. 247°— 18 Cio HO, Cy HO CHO, Ci oHsO; Cy HO, CypH 05 CoH Oe Cy H,,0 Benzoylacrylic ac., mp. 99°—57 6-Hydrojuglon, mp. 96°-—96 Methylcumarilic ac., mp. 188°—67 Trioxynaphthalene, mp. 120°—95 Anemonin, mp. 156°—98 Benzalmalonic ac., mp. 195°—68 Furoin, mp. 135°—96 Benzalacetone, mp. 41°—136 Benzoyltrimethylene, bp. 240°— 144 Methylhydrindones, mp. 59°, 63°, 95°, bp. 246°—137, 138, 144 Allyl benzoate, bp. 230°—125 Benzoylacetone, mp. 60°—92 Benzalpropionic acids, mp. 74°, 82°, 86°—55, 56 Butenylonphenol, mp. 139°—97 Hydrindoncarbonic ac., mp, 130°— 61 il attra ac., mp. 257°— i Tsosafrol, bp. 247°—193 Methylatropic ac., mp. 135°—61 Methylcinnamic acids, mp. 115°, 169°, 197°—59, 65, 68 Methyl cinnamate, mp. 36°—-118 Phenylerotonic ac., mp. 65°—55 Phenyldiacetyl, bp. 175°—215 Propenylbenzoic ac., mp. 160°—64 Safrol, bp. 233°—193 6-Benzoylpropionic ac., mp. 116°— 59 Cubebin, mp. 125°—96 Ethylbenzoylformate, bp. 256°— 126 Methy] m-coumarate, mp. 85°—119 Methoxycinnamic acids, mp. 88°, 115°, 171°—56, 59, 65 Benzoyllactic ac., mp. 112°—59 Benzylmalonic ac., mp. 117°—44 Dimethy] isophthalate, mp, 64,5°— 119 Dimethyl terephthalate, mp. 140°— 119 Dimethylterephthalic ac., mp. 206° —69 Dimethyl phthalate, bp. 282°—-126 Dimethylphthalic ac., mp. 96°—57 Ferulic ac., mp. 168°—65 Hydrocinnamocarbonic acids, mp. 165°, 277°— 65, 71 Isoferulic ac., mp. 280°—70 Meconin, mp. 102°—58 Phenylsuccinic ac., mp. 167°—65 Dimethyl oxyphthalaets, mp. 96°, 102°—119 Opianic ac., mp. 150°—63 Veratrinketonic ac., mp. 138°—46 Hemipinic acids, mp. 180°, 161°— 66, 64 Anethol, mp, 22°—174 Benzylacetone, bp. 235°—144 Anisoin, mp. 142°—179 Cuminie ald , bp. 235°—20 Ethyl benzyl] ket., bp. 224°—143 Ethyl p-tolyl! ket., bp. 238°—144 Isopropyl phenyl ket., bp. 217°— 143 Metanethol, mp. 132°—179 C,H,,.0, CioH205 C,.H,,0, CyoH,,05 CoH 1206 Co H205 C,)H,,0 FORMULA INDEX. Methy! xylyl ketones, bp. 224°, 246° —143, 144 Photoanethol, mp. 207°—180 Propyl phenyl ket., bp. 221°—143 p-Lolylacetone, bp. 232°—144 Trimethylbenzoic aldehydes, mp. 52°, bp. 237°—17, 20 Benzylpropionic ac., mp. 47°—53 Cuminic ac., mp. 116°—59 Dimethylphenethanoic ac., 102°-—58 Etyhlphenylacetate, bp. 229°—125 Ethylphenylacetic ac., mp. 42°—53 Ethyl toluates, bp. 221°, 227°—124 Methylhydrocinnamie ac., mp. 37° —53 Methyl hydrocinnamate, bp. 238° 125 Mp. Methyl phenylpropionate, bp. 221° —124 Prehnitylic ac., mp. 167.5°—48 p-Propionylanisol, mp. 27°-—136 Propylbenzoic acids, mp. 51°, 58°, 140°—54, 62 Propyl benzoate, bp. 229°—125 Tetramethylquinone, mp. 111°— 206 Thymoquinone, mp. 45°—205 Tolylpropionic ac., mp. 102°, 125° —58, 60 Trimethylbenzoic acids, mp. 127°, 149°, 152°, 215°—60, 63, 69 Coniferyl ale., mp. 73°—93 Dimethyldiacetylfurane, mp. 63° —176 Ethyl mandelate, mp. 34°—118 Ethyl anisate, bp. 269°—126 Ethyl methylether salicylate, bp. 235°—125 Methyl ethylether salicylate, bp. 245°—125 Methylethermelilotic ac., mp. 92°— 57 Methoethylphenolearbonic acids, mp. 71°, 94°, 142°—55, 57, 62 Methylphenyllactic acid, mp. 95°— 42 Oxyisopropylbenzoic ac., mp. 155° —64 : Phenyloxybutyric ac., mp. 75°—55 Trimethylphenolmethanoic acids, sbl. 148°, 181°—63, 66 Cantharic ac., mp. 278° c.—71 Cantharidin, mp. 218°—129 Ethyl vanillate, mp. 44°—118 Methyl veratrate, mp. 59°—118 Ethyl isocarbopyrotritarate, mp. 110°—59 Monoethy1 carbopyrotritarate, mp. 83°—56 Dimethyl succinylosuccinate, mp. 152°—97 Hexamethylenetetracarbonic mp. 219° d.—58 tert.-Butylphenol, mp. 99°—94 p-Cuminie ale., bp. 247°—165 Eucarvol, bp. 212°—143 Tetramethylphenol, mp. 86°, 117°, 108°—93, 95 Thymol, mp. 49.6°—92 ac. dg C,oH,,0, 10°"14~3 C, oH, Or C,»H,.03 C,H, 0. C,oH.05 C,H, sO, 255 Oxythymol, mp. 139°—97 Camphoric anhyd., mp. 220°—70 ‘Pyrogalloldiethylether, mp. 79°~- 93 Camphanic ac., mp. 201°—50, 68 Diallyl succinate, bp. 249°—126 Pinoylformic ac., mp. 79°—56 Camphenic ac., mp. 199°—50 Tetramethyl — s-ethanetetracarbo- nate, mp. 138°—119 Anthemol, bp. 214°—163 Camphor, mp. 176°—139 Citral, bp. 228°—20 Dihydrocarvone, bp. 221°—143 Fenchone, bp. 192°—142 Pinol, bp. 183°—191 Pulegone, bp. 221°—143 Thujone, bp. 203°—143 Campholenic acids, mp. 53°, bp. 265°—54, 76 Ethyl diallylacetate, bp. 195°—123 Trimethyleyclohexenecarbonic ac., mp. 106°—58 Camphylenic ac., mp. 172°—65 Methoethylolheptanonolid, mp. 63° —129 Pinonic acids, mp. 98°, 103°—57, 58 Diethyl allylmalonate, bp. 222°— 124 Diisopropyl fumarate, bp. 225°~ 124 Camphorie acids, mp. 181° c., 208° —66, 69 Isocamphoric ac., mp. 171°, 191°— 65, 67 Cineolic ac., mp. 196° d —68 Triethylmethanetricarbonate, mp. 29°—52 Borneols, mp. 203°, 210°—159 Coriandrol, bp. 196°—163 Citronellal, bp. 207°—20 Diisovalerianic ald., bp. 190°—20 Eucalyptol, bp. 176°—190 Geraniol, bp. 229°—163 Isoborneol, mp. 216°—159 Linalol, bp. 192°—163 __ Menthones, bp. 206°, 207°-—143 Terpineol, bp. 218°—165 Camphene glycol, mp. 192°—159 Campholic ac., mp. 105°—58 Citronellic ac., bp. 257°—76 Isoamyl tiglate, bp. 204°—123 Pinolhydrate, mp. 150°—155 Dimethyloctanonoic ac., bp. 292° 6 Ethyl! diethylacetoacetate, bp. 218° —124 Ethyl isobutylacetoacetate, 217°—124 Ethyl methylpropylacetoacetate, bp. 214°—124 Valerianic anhyd., bp. 215°—76, 131 Dibutyl oxalate, bp. 243°—125 Diethyl adipate, bp. 245°—125 Diethyl s-dimethylsuccinates, bp. 221°, 232°—124, 125 yee ethylsuccinate, bp. 225°— bp. 256 C,,H,.0, C,,H,.05 C, oH,,0 C,,H.0. FORMULA INDEX. Diethyl methylethylmalonate, bp. 207°—-123 Diethyl propylmalonates, bp. 221°, 213°—124 Diisobutyl oxalate, bp. 229°—125 Dipropy! succinates, bp. 249°, 247° —126, 125 Sebacic ac., mp. 133°—61 Diisopropyl tartrate, bp. 275°-—126 Diethyl mucate, mp. 158° d.—119 Diamylene oxide, bp. 175°—190 Isocapric ald., 169.6°—20 Isopropyl hexyl ket., bp. 205°—143 Menthol, mp. 42°—157 Methyloctonone, bp. 197°—142 Propyl hexyl ket., bp. 206°—143 n-Amyl valerianate, bp. 204°—123 Capric ac., mp. 31°—52 Ethyl caprylate, bp. 207°—123 ee dipropylacetate, bp. 183°— Howl butyrate, bp. 205°—123 Isoamyl isovalerianate, bp. 194°— 123 Methyl pelargonate, bp. 213°—124 n-Octyl acetate, bp. 210°—123 Ethyl oxycaprylate, bp. 231°—125 Methyl octyl ket., bp. 211°—143 Decyl alc., bp. 231°—163 Diamyl alc., bp. 211°—163 Ethyl octyl eth., bp. 189°—188 Isoamyl eth., bp. 173°—187 Propylhexylearbinol, bp. 210°—163 s-Dimethy]l dipropyl glycol, bp. 222° —165 s-Tetramethylpinacone, mp. 27°— C,, GROUP. Methylnaphthalenes, bp. 241°, 242°, mp. 32°—193 Amenylbenzene, bp. 173°—190 Tolylbutylene, bp. 195°—192 Amylbenzene, bp. 201°—192 Butyltoluenes, bp. 177°, 187°-—191 Diethylphenylmethane, ‘bp. 178°— 191 Diethyltoluene, bp. 199°—192 Dimethylethylphenylmethane, bp. 190°—191 s-Dimethylpropylbenzene, bp. 208° —192 Ethylisopropylbenzene, bp. 191°— 192 Isoamylbenzene, bp. 193°—192 Isopropylxylene, bp. 194°—192 Propylxylenes, bp. 206°, 208°, 209° —192 Pentamethylbenzene, bp. 53°—175 Undecine, bp. 212°—188 Undekanaphthene, bp. 190°—183 Undecylene, bp. 195°—188 Undecane, bp. 194°—18&3 Naphthoic ald., mp. 61°—17 Iso-naphthoic ac., mp. 184° e.—66 a-Naphthoic ac., mp. 160°—64 Naphtholcarbonic acids, mp. 169°, 185°—48, 67 2- Oxynaphthoic acids, mp. 156°, 216°, 210°, 235°—64, 69, 70 C,,H,,0 C,,H,,05 C,,H,,0, Methylnaphthol, mp. 89°—94 Methyl a-naphthy! eth., bp. 269°— 193 Metay pieny a mp. 41°— 175 Naphthylmethyl alcohols, mp. 60°, &0°—157, 158 Nerolin, mp. 72°—176 Dihydronaphthoic acids, mp. 91°, 105°, 125°, 161°—57, 58, 60, 64 Methylindenecarbonic ac., mp. 200° —68 Acetcumaric ac., mp. 146°—63 Allylacetophenone, bp. 238°—144 Benzoylcyclobutane, bp. 259°—144 Cinnamenylpropionic ac., mp. 31— 52 Ethyl] cinnamate, bp. 271°—126 Methylhydrinencarbonic 8C., 5 JG 80°—56 Phenylangelic ac., mp. 104°—58 Phenylpentenoic ac., mp. 104°— 58 Tetrahydronaphthoic acids, mp. £5 94°—56. 57 o-Ethoxycinnamic acids, mp. 103°, 135°—5S8, 61 Ethylbenzoylacetic ACs 114°—59, 43 Ethyl p-toluylearbonate, mp. 263° —119 Mpls Methyl {-benzoylpropionate, bp. 290°—127 Phenyllevulinic ac., mp. 55°—40 Toluylpropionic ac., abt. 120°—60 Acetylphenyllactic ac., mp. 100°— 58 a-Hydropiperic ac., mp. 75°—55 Sinapic ac., mp. 189°—209 p-Acetylcumene, bp. 254°—144 Acetylmesitylene, bp. 235°—144 p-Acety Props bp. 259°— Butyl phenyl ket.—144 Ethyl xylyl ketones, bp. 237°, 238° —144 Isobutyl phenylket., bp. 225°— 144 Isopropyl] telyl ket., bp. 235°-—144 | Methylbenzylacetone, bp. 238°— 144 Butyl benzoate, bp. 247°-—125 Ethylbenzylacetic ac., bp. 272°—76 Ethyl 1,3- -dimethylbenzoate, bp. 241° —125 Ethyl hydrocinnamate, bp. 248°— 125 Bees a-phenylpropionate, bp. 230° 125 Bihyl m-tolylacetate, bp. 237°— 12! Tahun acids, mp. 127°, 164°—60, 65 Isobutyl benzoate, bp. 237°—125 Methocthylphenethanoic 8C.;. (Tap: 52°—54 Methy] ethylphenylacetate, bp.228° —125 Methy! methylhydrocinnamate, bp. 232°—125 C,,H oP C,,H,,0 C, iH 2202 FORMULA INDEX, Methylpropylbenzoic ac., mp. 75° —55 Methyl pseudocumy] ket., bp. 246° —144 Phenylvalerianic ac., mp. 58°—54 Tetramethylbenzoic acids, mp. 165° 179°—65, 66 Tolylisobutyric ac., mp. 91°—57 p-Propionylphenetol, mp. 30°—136 o-Ethylethermelilotic ac., mp. $0° —56 Ethyl m-ethoxybenzoate, bp. 263° —126 Ethyl ethylethersalicylate, bp. 251° —126 Ethyl o-hydrocoumarate, mp. 34° —118 Phenyloxyvalerianic ac., mp. 131° o-Thymotic ac., mp. 123°—60 Ethyl veratrate, mp. 43°—118 p-lsoamylphenol, mp. 92°—94 Isoamyl phenyl eth., bp. 217°—192 Methyl thymyl eth., bp. 216°—192 Camphocarbonic ac., mp. 128°—61 Pentamethylphloroglucin, mp. 114° —95 Undecolie ac., mp. 59.5°—54 Diethyl pentamethylene dicarbon- ate, bp. 251°—126 Monomethyl camphorate, mp. 86° —56 Phoronic ac., mp. 184°—67 Triethyl ethenyltricarbonate, bp. 278°—126 Undecylenic ac., mp. 24°—52 Dibutyl malonate, bp. 251°—126 Diethyl isobutylmalonate, bp. 225° —124 Diethyl isopropyl succinate, bp 238°—125 Diethyl diethylmalonate, bp. 223° —124 Diethyl methylpropylmalonate, bp. 222°—124 Heptylsuccinic ac., mp. 90°—41 Diethyl butylmalonate, bp. 233°— 125 Diethyl methylisopropylmalonate, bp. 221°—124 Caprone, bp. 226°—144 Diisoamyl ket. bp. 226°—144 Methyl nonyl ket., bp. 224°—143 Ethyl pelargonate, bp. 227°—124 Isoamyl isobutylacetate, bp. 217° —124 Methyl caprate, bp. 223°—124 Umbellulic ac. mp. 22°, bp. 277°— 52 Undecylic ac., mp. 28°—52 Diisoamyl carbonate, bp. 229°—125 Dioxyundecylic ac., mp. 85°—56 C,, GROUP. B-Naphthylacetylene, mp. 36°—175 Acenaphthylene, mp. 92°—177 Diphenyl, mp. 70°—176 Acenaphthene, mp. 95°—177 $-Ethylnaphthalene, bp. 251°—193 a-Ethylnaphthalene, bp, 258°—193 Cy C,.Hys _ iS) 2.2 bof = tb i) > © sofas [o;) to ay iY) ee Se) fe) isles fey Co — fod Eh Le.) oo w CROs OCHS C,,H,,05 C,.H,,0; 257 Dimethylnaphthalene, bp. 263°— » 3193 allylisopropylbenzene, bp. 229°— 192 p-Dipropylbenzene, bp. 220°—192 Kthylbutylbenzene, bp. 202°—192 Hexamethylbenzene, mp. 164°— 179 Isohexylbenzene, bp. 214°—192 p-Propylisopropylbenzene, bp. 212° —192 p-Isoamyltoluene, bp. 213°—192 s-Triethylbenzene, bp. 216°—192 Dodecon, bp. 197°—188 Triisobutylene, bp. 178°—187 Dodekanaphthene, bp. 197°—183 Duodecylene, bp. 214°—188 Dodecane, bp. 214°—183 Acenaphenequinone, mp. 261°-~ 210 Mellitic ac., mp. 287°—51 Acenaphthenone, mp. 121° C.—139 Biphenylene oxide, mp. 86°—177 Benzfuril, mp. 41°—205 Naphthoylformic ac., mp. 113°—43 Naphthalic ac., mp. 270°—71 Naphthalenedicarbonic acids, mp. d7s007,1/5- 72, 66 Paracotoin, mp. 152°—208 Methyl] $-naphthyl ketones, mp. 51° 295°—137, 145 Phenyl eth., mp. 28°—174 Acetylnapthol, mp. 173°—99 6-Biphenol, mp. 161°—98 Methyl oxynaphthyl ket., mp. 103° —206 a-Naphthylacetic ac., mp. 131°— 61 Methyl $-naphthoate, mp. 77°—119 Methylphenylfuranecarbonic ac., mp. 180°—66 Dipyrocatechin, mp. 84°—93 Piperic ac., mp. 216°—210 Quinhydrone, mp. 171°—208 Dimethylnaphthol, mp. 185°—96 Ethyl naphthyl ethers, mp. 37°, 281°—175, 194 Methyl cinnamenylvinyl ket., mp. 68°—137 Benzalleevulinic ac., mp. 125°—60 Benzoyltetramethyleneearbonic ac., mp. 142°—62 Diacetylbenzoyl methane, mp. 35° 91 Ethyl {-methylcoumarilate mp. 51°—118 Triacetylbenzene, mp. 162°—139 Acetophenonacetacetic ac., mp. 135°—61 Ethyl benzoylpyruvate, mp. 43°— 91 Benzyllevulinic ac., mp. 98°—57 Apiol, mp. 30°—174 Diethyl isophthalate, bp. 285°— 126 Diethyl phthalate, bp. 295°—127 Diethyl terephthalate, mp. 44°— 118 Diethyl oxyisophthalate, mp. 52° —118 208 C,,H,,O, C,,H,.O C,,H, Oz C,,H,.O3 C,.H,.0; Unt; Cryo Gwe ba ee C,,H,,0, C,2H290, C,,H,,O. Cine) gee 2us— 7 Cy 5H O10 ( C,,H,.0 C,,H,.0, C,,H,.03 C,,H 2204 FORMULA INDEX. Diethyl hydroquinonedicarbonate, mp. 133°—96 Dimethyl hemipinate, mp. 61.5°— | 119 Diethylacetophenone, bp. 231°— | 144 Tsoamyl phenyl ket , bp. 242°—144 Isopropy! xylyl ket., bp. 289°, 256° —144 Methyl o-cymy] ket., bp. 258°—144 Methyl duryl ket., mp. 73°, 254°, 259°—137, 144 Propyl xylyl ket., bp. 249°, 251°, 244°—144 Ethyl cuminate, bp. 240°—125 Isoamyl benzoate, bp. 261°—126 p-Isoamylbenzoic ac., mp. 153°— Pentamethylbenzoic ac., mp. 210° Asarone, mp. 67°—176 Isoamyl salicylate, bp. 270°—126 Diethyl carbopyrotritarate, bp. 284°—126 Diethyl succinylosuccinate, mp. 126°—96 Ethyl thymyl] eth., bp. 227°—192 Xylitone, bp. 251°—144 Ethyl diallylacetoacetate, bp. 240° —125 Phloroglucin triethyl eth., mp. 43° —175 Diethyl diacetylsuccinate, mp. 88° —94 Triethyl aconitate, bp. 275°—126 Dimethyl camphorate, bp. 265°— 126 Triethyl tricarballylate, bp. 300°— 127 Triethyl citrate, bp. 294°—127 ?) Dextrin, —29 Inulin—31 Diallyl eth., bp. 180°—187 Hexenyl eth., bp. 117°—186 Methyl undecylenate, pb. 248°— 126 Diethylacetic anhyd., bp. 230°—76 Ethyl dipropylacetoacetate, bp. 235°—125 Lanolic ac., mp. 76°—55 Diethyl isoamylmalonate, bp. 241° —125 Diethyl suberate, bp. 284°—126 Diisoamyl oxalate, bp. 263°—126 Diisobutyl succinate, bp. 265°—126 Dimethyl sebacate, mp. 38°—118 Diisobutyl tartrate, mp. 68—119 Lactose—29 Maltose—29 Saccharose, abt. 160° d.—29 Lauric ald., mp. 44°—17 Diisoamylacetic ac., mp. 46°—53 Ethyl caprate, bp. 244°-125 Lauric ac mp. 43.6°—53 Diisoamyloxalic ac., mp. 122°—60 Paraisobutyric aldehyde, mp. 59°- 60°—17 Dodecy] ale., mp. 24°—157 Ethylidenediisoamyl eth., bp. 211° C,3H,,03 C,3H,.O, C,,H Os C,3H,,0 C,,H,,0, C,, GROUP. Sequoiene, mp. 105°—178 Fluorene, mp. 112°—178 y-Methylenebiphenyl, mp. 116°— 178 Phenyltolyl, bp. 259°—193 Diphenylmethane, bp. 261°—193 p-Phenyltolyl, bp. 265°—193 m-Phenyltolyl, bp. 275°—193 Diphenylmethane, mp. 26°—174 -Propylnaphthalene, bp. 265°— 193 Heptylbenzene, bp. 233°—193 Tridekanaphthene, bp. 209°—C, ,H,, Tridecylene, bp. 233°—188 Tridecane, bp 234°—183 60)o (?) Galloflavin—213 O Diphenylene ket., mp. 84°—205 Isodiphenylene ket., mp. 83°—138 Pseudodiphenylene, ket. mp. 85°— 205 Pyrene ket., mp. 142°—207 Fluorenequinone, mp. 181°—209 . Xanthone, mp. 173°—180 Oxyxanthones, mp. 146°, 231°-- 207, 210 Euxanthone, mp. 240°—210 Benzophenone, mp. 48°—137 Benzophenone allotropic, mp. 20.6° —136 Fluorene alc., mp. 153°—159 Xanthene, mp. 100°—177 p-Benzoylphenol, mp. 134°—96 ~ Naphthylacrylic ac., mp. abt. 210° —69 Oxybenzophenones, mp. 40°, 116°— 91, 95 Phenyl benzoate, mp. 68°—119 Phenylbenzoic ac., mp. 110°, 160°, 218°—59, 64, 70 Benzohydroquinone, mp. 125°—206 Benzopyrocatechin, mp. 145°—97 Benzoresorcin, mp. 144°—97 Dioxybenzophenones, mp. 59°,143°, 162°—98, 205, 207 Diphenyl carbonate, mp. 78°—119 Euxanthoic ac.. mp. 201°—209 Phenylethersalicylic ac., mp. 113° —59 Phenoxybenzoic ac., mp. 159°—64 Phenyl p-oxybenzoate, mp. 116°— 99 Salol, mp. 42°—91 Alizarine yellow A, mp. 140°—207 Salicyloresorcin, mp. 133°—207 Tetraoxybenzophenone, mp. 149° —208 Benzhydrol, mp. 68°—157 -Benzylphenoj, mp. 84°—93 henyl benzyl eth., mp. 38°—175 Propanoylnaphthene, bp. 306°— 145 Benzhydroxylphenol, mp. 161°— 98 Dioxydiphenylmethane, mp. 158° 8 Ethyl 8-naphthoate, bp. 309°—127 Ethyl a-naphthoate, bp. 309°—127 Ethylnaphthoic ac., mp. 132°—61 NOTE ON REAGENTS FOR REDUCTION TESTS. (To face page 17 of ‘‘ The Identification of Commercial Dyestuffs.”’) While the original descriptions of all color discharges obtained in Tests 8 and 11 that are tabulated in Volume III are basea on the use of a solution of Rongalite C, practically identical results under the same experimental conditions are secured by the employment of a reducing mixture prepared by the following empirical procedure: Place in a 300-cc. flask 15 grams of dry sodium bisulphite and 8 grams of zine dust. Add 75 cc. of distilled water. Shake to dissolve the bisulphite and wet the zine. Then add from a burette 7.5 cc. of commercial “ formalin ”’ (40 per cent formic aldehyde solution). After mixing thoroughly, heat quickly to boiling on a wire gauze over a Bunsen flame, and boil moderately for just 5 minutes. Dilute at once with 45 cc. of cold distilled water, and then cool and filter. Or, double all the quantities mentioned may be taken, and the mixture boiled for the same period of 5 minutes. The commercial dry sodium bisulphite of the quality placed on the American market by reputable manufacturers as the ‘‘ U.S.P. viii’’ grade, if taken from full recently purchased bottles, is generally suitable for the preparation of this reagent, even when not absolutely fresh. The finished reagent should not be preserved for more than a few days, and should not smell of formic aldehyde when warmed. It should be understood that the times required for discharges in reduction tests and the color-returns in oxidation tests as stated in the tables are only approximations, and will be found to vary slightly in independent experiments with the same dyestuff whichever reagent is employed. In Tests 6, 11, and 21 it is permissible to substitute any good commercial sodium hydrosulphite for Blankit T. y ‘i o C,H,,0 C,,H wOs C, 3H,,0, C,H, .O, 132-16 7 13°18 C,H, C,H 16 Ci, HL, FORMULA INDEX. Camphorphoron, bp. 202°—143 Ditetramethylene ket., bp. 204°— 143 Ethyl benzalacetoacetate, mp. 59° —118 Ethyl benzoylacetoacetate, mp. 27° —118 Diacetylmesitylene, mp. 46°—137 Helicine, mp. 175°—18 Cumylacetone, bp. 262°—145 Methyl pentamethylphenyl ket., mp. 85°—138 Phenyl hexyl] ket., bp. 271°—145 Ethyl cymy] ket., bp. 267°—145 Hexyl benzoate, bp. 272°—126 Salicin, mp. 201°—100 Ethyl camphocarbonate, bp. 276° —126 Diethyl diallylmalonate—125 Ethyl undecylenate, bp. 259°—126 Brassylic ac.. mp. 112°—59 Diethyl azelate, bp. 291°—127 Diisoamylmalonic ac. mp. 147°— 63 Dihexyl ket., mp. 30°—136 Methyl undecyl ket., mp. 28°—136 Tridecylic ac., mp. 40°—53 Dihexylearbinol, mp. 41°—157 C,, GROUP. Anthracene, mp. 216° c.—180 TIsoanthracene, mp. 134°—179 Phenanthrene mp. 100°—177 Tolane, mp. 60°—176 Anthracenedihydride, mp. 108°— 178 a-Diphenylethylene, bp. 277°—194 Stilbene, mp. 124°—178 m-Benzsyltoluene, bp. 275°—193 Dibenzyl, mp. 52°—175 Di- or Bitolyl, bp. 275°, 280°, 288°, mp. 121°—193 194, 173 m-Ethylbiphenyl, bp. 283°—194 Phenanthrenetetrahydride, bp. 310° —194 Anthracenehexahydride, mp. 63°— 176 Diphenylpropane, bp. 280°—194 Isobutylnaphthalene, bp. 280°— 194 tert. Dibutylbenzene mp. 70°—176 Diisobutylbenzene, bp. 235°—193 Octylbenzene, bp. 262°—193 Tetraethylbenzene, bp. 250°, mp. 13°—192, 174 Perhydroanthracene, mp. 88°—177 Phenanthreneperhydride, bp. 272° —193 Tetradecine(4), mp. 6°—174 Tetradekanaphthene, bp. 243°— 183 Tetradecane bp. 252°—183 Anthraquinone, mp. 273°—211 Isoanthraquinone, mp. 211°—209 Phenanthrenequinone, mp. 202°— 209 Diphenyleneketonecarbonic acids, mp. 191°, 227°-—209, 210 m-Oxyanthraquinone, mp. 302°— 211 C,,H30, 2 i=. 1 _ a ice QEOAAe ssfasfasfas|se[ss © roy ° — am a oe (ve) (=) OG: ry » t C,,H,,03 C00. 14 100s 14 130 C,,H,,0, C,,H,,0, Alazarin, mp. 289°—211 Anthraflavic ac.—213 Anthrarufin, mp. 2¢0°—211 Benzdioxyanthraquinone, mp. 292° —211 Dioxyanthraquinone—214 Isoanthraflavic ac.—212 Xanthopurpurin, mp. 262°—210 Anthragallol, mp. 310°—211 Flavopurpurin—212 TIsopurpurin—2Z14 Purpurin, mp. 256°—210 Alizarin Bordeaux—214 Alizarincyanin ‘‘R’”’—214 Rufigallic ac.—214 Anthranol, mp. 165°—99 Phenanthrol, mp. 112°—95 Benzil, mp. 95°—206 Dioxyanthracene, d. 220°—210 Dioxyhydrobenzoin - diesoanhydr., mp. L1G 1 7s Dioxyphenanthrene, mp. 143°—97 Diphenylene acetic ac., mp. 221°— 70 Fluorenecarbonic ac., mp. 175°—66 Fluorenic ac., mp. 245°—71 Benzoic anhyd., mp. 42°—53 Benzoylbenzoic acids, mp. 93°, 161°, 194°—57, 64, 67 Diphenyleneglycollic ac., mp. 162° —65 Disalicylic ald., mp. 128°—18 Benzoylperoxide, mp. 103°—129 Diphenic ac., mp. 229°—70 Diphenyl oxalate, mp. 130°—119 Gentianine, mp. 267°—210 C,,H C,,H,,0,(?) Gallotannic ac., mp. abt. 210°—50 C,H Acetylbiphenyl, mp. 121°—139 Desoxybenzoin, mp. 60°—137 Dihydroanthranol, mp. 129°—96 Oxystilbene mp. 135°—97 Phenyltolyl ket., mp. 49°—bp. 315° —137. 145 Benzoin, mp. 133°—139 Benzyl benzoate, bp. 323°—127 Benzylbenzoic acids, mp. 107°, 114°, 154°—58, 59, 63 Diphenylacetic ac., mp. 148°—63 Methyl phenylbenzoate, bp. 308°— 127 Oxyhydroanthranol, mp. 99°—94 Phenyltolyl carbonic ac., mp. 243° —70 Tolylbenzoic ac., mp. 204°—68 Benzilic ac., mp. 150°—63 Methyl phenylethersalicylate, bp. a. 360°—127 Phenylethermandelic ac., mp. 108° 5 —58 Phenyl methylethersalicylate, mp. 59°—118 Cotoin, mp. 180°—207 Benzyl eth., bp. 296°—194 Isopropyl! naphthy] ket., bp. 309°— 145 Propyl naphthyl ket., mp. 50°—137 Phenylbenzylearbinol, mp. 42°— 157 Phenyltolylearbinol, mp. 52°—157 Cresyl eth., mp. 50°—175 260 “A C,,H,,0, C, 4H, Or C,H, On 14 20 [= ~ HO HO H,,O Ay, H,,0 H,,O avaloe velele: C,,H.,0 Gin C,,H,,O C,,H,,03 C,,H,,0 30 FORMULA INDEX. Bicresol, mp. 161°—98 Ethylene diphenyl eth., mp. 98°— 177 Hydrobenzoin, mp. 188°—158 Isohydrobenzoin, mp. 119°—158 p-Diphenolethane, mp. 122°—96 Curcumin, mp. 178°—208 Ethyl piperate, mp. 77°—119 Diethyl benzalmalonate, mp. 32°— 118 Filixic ac., mp. 184°—99 Tolvl hexyl ket., mp. 42°—136 Tetraethyl ethylenetetracarbonate, mp. b/ 11s Diethyl camphorate, bp. 285°—126 Dicenanthylie ald., bp. 279°—20 Ethyl diisobutylacetoacetate, bp. 251°—126 (Enanthylic anhyd., bp. 269°—132 Diethyl sebecate, bp. 307°—127 Diisoamy] succinate, bp. 295°—127 Dodecanedicarbonic ac., mp. 123°— 60 Myristic ald., mp. 52°—17 Tetradecanone (2), mp. 33°—136 Amylheptylacetic ac., bp. 305°— 76 Ethyl laurate, bp. 269°—126 Myristic ac., mp. 54°—54 Oxymyristic ac., mp. 51°—54 Heptyl eth., bp. 261°—188 Tetradecyl alc., mp. 38°—157 C,, GROUP. Fluoranthene, mp. 109°—178 Methylanthracenes, mp. 199°—180 Isomethylanthracene, mp. 203°— 180 Phenyltolylethylene, mp. 118°— 178 Benzyl-p-xylene, bp. 294°—194 Benzyltolylmethane, mp. 27°—174 Dimethyldiphenylmethane, bp. 281° —194 Ditolvlmethanes, bp. 286°, mp. 22° —194, 174 Ethylbenzylbenzene, bp. 294°—194 p-Phenyltolylethane, bp. 286°—194 Sesquiterpenes, bp. 250°-280°—193 Cadinene, bp. 275°—193 Benylene, bp. 225°—192 Pentadekanaphthene, bp. 247°— 183 Triamylene, bp. 233°—188 Pentadecane, bp. 270°—183 Fluoranthenequinone, mp, 188°— 209 Anthraquinonecarbonic ac., 283°—211 Alizarincarbonic ac., mp. 305°—211 Purpurinxanthincarbonic ac., mp. 231°—210 Purpurincarbonic ac., mp. 219°— 210 Anthracenecarbonic ac., mp. 206° —209 Methylanthraquinone, mp. 177°— 203 Phenanthrenecarbonic acids, mp. 251°, 266° —71 mp. C, 5H 003 C, sH, 0, C,5HO6¢ C,;H,,O;7 C,,H,,0 C ld ,O3 C,;H,,0; C, H,,0, Diphenylpropanetrione, mp. 69°— 205 Chrysophanic ac., mp. 178° (?)— 208 Dioxyflavone, mp. 275°—211 Fisetin—213 Luteolin—213 Quercetin—213 Benzylideneacetophenone, mp. 57° 137 Phenylindanone, mp. 78°—138 Dibenzoylmethane, mp. 81°—93 Phenylcinnamic ac., mp. 172°—65 Phenyl cinnamate, mp. 72°—119 Stilbenecarbonic ac., mp. 159°—64 Toluylbenzoic ac., mp. 146°—63 Diphenylmethanedicarbonic _ac., mp. 290°—72 Benzylacetophenone, mp. 72°—137 Dibenzyl ket., mp. 34°—136 s-Dimethylbenzophenone, mp. 92° —138 p-Ethylbenzophenone, bp. a. 300° 145 Phenyl xylyl ket., mp. 36° 94°, bp. 322°—136, 188, 145 Methyldiphenylacetic ac., mp. 178: 65 Ethyl phenylbenzoate, bp. 314°— 127 Phenyltolylacetic ac., mp. 115°—59 Benzoylveratrol, mp. 99°—138 Diphenyllactic ac., mp. 159°-—64 Lapachol, mp. 140°—207 Methyl benzilate, mp. 74°—119 Benzocotoin, mp. 98°—94 Oxylapachol, mp. 127°—207 Peucedanin, mp. 109°—119 C,;H,,0, (?) Santalin, mp. 104°—206 15°16 C,5H,,0, C,5H,,0, C 5H,,03 C,sH03 C,5H..0, C,H, C,5H..0, Dibenzylearbinol, bp. 327°—165 Ditolylearbinol, mp. 69°—157 Diphenyloldimethylmethane, 151°—97 /Esculin, mp. 160°—98 Daphnin, mp. 200°—100 Perezinon, mp. 143°—207 Santonin, mp. 169°—129 Pipitzahoic ac., mp. 103°—206 Santanous ac., mp. 178°—66 Oxypipitzahoic ac., mp. 130°—207 Santonic ac., d. 120°—60 . Isobutyl isocymyl] ket., bp. 271°— 145 mp. Octyl benzoate, bp. 305°—127 Octylbenzoic ac., mp. 139°—62 Alantolic ac., mp. 94°—57 Photosantonic ac., mp. 154°—63 Ledum camphor, mp. 104°—138 Cimicic ac., mp. 44°—53 Dihepty: ket., mp. 40°—136 . Methyl tridecy] ket., mp. 39°—136 Pentadecylic ac., mp. 51°—54 Oxypentadecylic ac. mp. 51°—54 C,, GROUP. Diphenyldiacetylene, mp. 88°—177 Pyrene, mp. 148°—179 Phenylnaphthalenes, bp. 324°, mp. 102°—194 178 C,,H,; C,.H,,0, C, eH,.0. C,.H, Os FORMULA INDEX. Dimethylanthracenes, mp. 71°, 231°, 246°—176, 180, 181 Diphenylbutadiéne, mp. 148°—178 Ethylanthracene, mp. 60°—176 Dimethylanthracenehydride, 181°—180 Dimethylstilbene, mp. 179°—180 Diphenylbutene, mp. 39°—175 Distyrene, mp. 124°—178 Ethyl] stilbene, mp. 89°—177 Ditolylethylene, bp. 304°—194 Benzylmesitylene, mp. 36°—175 s-Benzyltolylethane, bp. 293°—194 Dimethyldiphenyl ethane, mp. 123° —178 s-Diphenylbutane, mp. 52°—175 Ditolylethane, bp. 296°—194 Di-p-xylyl, mp. 125°—178 p-Ethyldibenzyl, bp. 294°—194 Methylethyldiphenylmethane, mp. 128°—178 Diisoamylbenzene, bp. 265°—193 Pentaethylbenzene, bp. 277°—193. Cetylene, bp. 282°—188 Hexadecine(1), mp. 15°—174 Cetene, bp. 274°—188 Hexadecane, bp. 287°—183 Dimethyltetradecane, bp. 268° c.— 183 Pyrenequinone, mp. 282°—211 Biphthaly]l, mp. 334°—130 Anthraquinonedicarbonic ac., mp. 340°—211 Phenylnaphthoquinone, mp. 109°— 206 mp. Stilbenedicarbonic anhyd., 155°— 64 Diphenylfurfurane, mp. 91°—177 Methyl anthracenecarbonate, mp. 111°—119 Phenacetolin—213 Dibenzoylacetic ac., mp. 109°—59 Diphenylbutanoltrione, mp. 170°— 208 Brazilein—212 mp. Diphenylmethanetricarbonic ac., mp. 219°—70 Hemateine—214 Piperonyloine, mp. 120°—139 Dimethyldihydroanthrenone, mp. 93°—138 Diphenylbutanedione, mp. 144°— 139 Toluic anhyd., mp. 36°—53 Bibenzyldicarbonic ac., mp. 252°— 71 Diphenyl succinate, mp. 118°—119 Diphenylsuccinic ac., mp. 183°— 66 Ethyl benzosalicylate, mp. 79°— 119 Hematoxylin, mp. 140°—207 Protocotoin, mp. 141°—97 Benzoinethylether, mp. 95°—138 Benzyltolylacetic ac., mp. 95°—57 Dibenzylacetic ac., mp. 87°—56 Ethyldiphenylacetic ac., mp. 173° —65 Dihbenzyleglycollic ac., mp. 157°—64 Ethyl benzilate, mp. 34°—118 a cone fesf=ets= oo aefaslen oR o 1 eee Bie: e- Rm [oo i=) ts = ao iS) i=) a _ fox) OO NOO. 2a000 & be be 6 lore ROS i) je 2° _ a os to ‘coo lal Teles OO & Ce) C, 7H,.0, C,,H,,05 x asfaefsr _ oa SOCCCO 1] ee _ ae”) i) ~ Naa aA A — oO asfarfar ra to o is) nD COO ~ wo oO SOOO) OO000o = as]esfae[se ~ YN vy vw wo rg 261 Anisoin, mp. 109°—138 Methylhydrocotoin, mp. 115°—138 Acetophenonepinacone, mp. 120°— 158 Hydranisoin, mp. 170°—159 Hydroceerulignon, mp. 190°—100@ Barbaloin, mp. 147°—207 Coniferine, mp. 185°—100 Palmitolic ac., mp. 47°—53 Palmitoxylic ac., mp. 67°—55 Hypogeic ac., mp. 33°—52. Caprylic anhyd., bp. 285°—132 Oxyhypogeic ac., mp. 34°—53 Agaricic ac., mp. 142°—62 Hexadecanone(2), mp. 48°—137 Palmitie ald., mp. 58°—17 Diheptvlacetic ac., mp. 26°—52 Ethyl myristate, bp. 295°—127 Palmitic ac., mp. 63°—54 Lanopalmitic ac., mp. 87°—56 a-Oxypalmitic ac., mp. 82°—56 Dioxypalmitic ac., mp. 115°—59 Cetyl alc., mp. 50°—157 Octyl eth., bp. 294°—188 Cetene glycol, mp. 75°—157 Isoamyl orthoformate, bp. 266°— 126 C,, GROUP. a-Benzylnaphthalene, mp. 59°— 176 Trimethylanthracenes, mp. 222°, 227°, 243°—180 Isopropylstilbene, mp. 84°—177 Retenefluorene, mp. 97°—177 Benzyleymene, bp. 308°—-194 Benzylduryl, mp. 60°, 145°—176, 179 Phenylxylylpropane, bp. 324°—194 Heptadecane, mp. 22°—174 Chrysoketone, mp. 133°—207 Pyrenecarbonic ac., mp. 267°—71 Chrysofluorene, ale., mp. 166°—159 Phenyl naphthyl ketones, mp. 75°, 82°—137, 138 Chrysenic ac., mp. 186°—67 Cinnamylene acetophenone, 102°—206 Dibenzylideneacetone, mp. 112°— 206 Atronic ac., mp. 164°—65 Isatronic ac., mp. 156°—64 Acetonephenanthrene ket., mp. 90° —205 Dibenzoylacetones, mp. 82°, 108°— 93, 138 Retene ket., mp 90°—205 Diphenylglutaric ac., mp. 164°—65 Retenefluorene ale.. mp. 183°—158 Ditolylpropionic ac., mp. 151°—63 Carminic ac.—212 Diethyldiphenolmethane, mp. 199° —100 Podocarpic ac., mp. 187°—67 Roccellic ac., mp. 132°—61 Oxyroccellic ac., mp. 128°—60 Diheptylacetone, bp. 302°—145 Methyl quindecyl ket. mp. 48°— 137 mp. 262 C, 7H,,0, _ oo soBssie= bo to ro) oo ~ _ oo »~ oe is = ive) is) Oe ae, ol ole tole) ja ry « m hh & Sao Q a a © Qa0 Ford koko ~ oo [J eo _ oo Q0 ie i} _ ao © sofsefa+ ashes ANololo OOOO _ o ow i) wo _ lo} w i el ° & ~) ~ Come _ oo ob Nn FORMULA INDEX. Margaric ac., mp. 60°—54 Daturic ac., mp. 54°—54 Methy! palmitate, mp. 28°—118 C,, GROUP. Chrysene, mp. 250°—181 Isochrysene, mp. 196°—180 Naphthanthracene, mp. 141°—179 Truxene, mp. a. 360°—-181 Diphenylbenzene, mp. 205°—180 Retene, mp. 98°—177 Tetramethylanthracene, mp. 231° —180 Jsobutylanthracene, mp. 57°—175 Diethylstilbene, mp. 134°—179 Tetramethylanthracenehydride, mp 171°—179 Tetramethylstilbene, mp 105°, 157° —179, 178 Diethylanthracenedihydride, 49°—175 Dixylylethane, bp. 324°—194 Hexaethylbenzene, mp. 129°—178 Tributylbenzene, mp. 128°—178 Octadecines, mp. 26°, 30°—174 Anthemene, mp. $3°—176 Octadecylene, mp. 18°—174 Octadecanes, mp. 28°, bp. 317° e.— 174, 183 Chrysoquinone, mp. 235°—210 Naphthoylbenzoic ac., mp 173°— mp. 66 Oxynaphthoylbenzoic ac., mp. 256° =i Phenylbenzoylpyronone mp. 171° —208 Diphenylfurandicarbonic ac., mp. 238°—70 Pulvic ac., mp. 214°—209 Benzyl! naphthyl ket., mp. 57°-—137 Cinnamic anhyd., mp 132°—61 Pyrogalloquinone—214 Octylene oxide, bp. 145°—187 Retenequinone, mp. 198°—209 Isoatropic acids, mp. 206°, 237°— 69, 70 Phenoquinone, mp. 71°—205 Truxillic acids, mp. 228°, 274°—70, 71 Carbousnic ac., mp. 200°—209 Usnic ac., mp. 195°—209 Trigenin, mp. 186°—100 Ditoluylethane, mp. 159°—139 Dibenzylacetoacetic ac., mp. 89°— 56 Diethyl diphenate, mp. 42°—118 Hexamethyl mellitate, mp. 187°— 119 Methyltolylpinacone, mp. 90°—158 Camphoronic anhyd., mp. 175°—66 Stearolic ac., mp. 48°—53 Ricinostearolic ac., mp. 51°—54 Ricinelaidic ac., mp. 50°—54 Ricinstearoxylic ac. mp. 78°—56 Stearoxylic ac., mp. 86°—56 Raffinose, mp. 118°—29 Elaidic ac., mp. 51°—54 Isoéleic ac., mp. 44°—53 Oleic ac., mp. 14°—52 3 HAs Hs, O O :sH,,0 O 84 36 H is: _ Cc ls i] oO _ Ke} ielelowwen se iets on ~ i) _ Vo} By Mele tm ih io) OO fos e Vo} ao = bo at © - vo} ae iy © _ fos} ~ lelete ~ pe} _ © w oz} of COs GO Co CCC Cy avpeetarter|cefael ogerfari css -_ © ©) CooHig CoH. CooHis Ricinoleic ac., mp. 16°—52 Ketostearic ac., mp. 84°—56 Dioxyricinoleic ac., mp. 64°—55 Octadecanone mp. 51°—137 Stearic ald., mp. 63°—17 Ethyl diheptylacetate, bp. 310°— 127 Ethyl palmitate, mp. 24° - 118 Stearic ac., mp. 69°—55 Oxystearic acids, mp. 84°—56 Dioxystearic acids, mp. 995 136° 142°—57, 62 Trioxystearic ac., mp. 141°—62 Tetraoxystearic ac., mp. 173°—65 Octadecyl ale., mp. 59°—157 C,, GROUP. Biphenylenediphenylmethane, mp 145°—179 Phenylenediphenylmethane, mp. 148°—179 Benzyldiphenyl, mp. 85°—177 Triphenylmethane mp. 92°—177 IJsoamylanthracene, mp. 59°—176 Diphenylheptane, bp. 14°—174 Nonadecane, mp. 32°—175 Aurine, 213 Phenyl phenylethersalicylate, mp. 109°—119 Phenyl phenoxybenzoate, mp. 75° —119 Vulpic ac., mp. 148°—208 Trioxyaurine—212 Resaurine—213 Triphenylearbino], mp. 162°—159 Cinnamylenebenzylideneacetone mp. 106°—206 Dioxytriphenylmethane, mp. 161° —98 Benzaurine—214 Tetraoxytriphenylmethane, mp. 171°—99 Euxanthic ac., mp. 157°—208 Abietic ac., mp. 153°—63 Lichen-stearic ac., mp. 124°—60 Dioctylmalonic ac., mp. 75°—55 Cetylmalonic ac., mp. 122°—60 Dinonyl ket., mp. 58°—145 Dioctylacetone, bp. 327°—145 Methyl heptadecyl ket., mp. 56°— 137 Methyl stearate, mp. 38°—118 Nondecylic ac., mp. 66°—55 C,, GROUP. : Dinaphthyls, mp. 79°, 187°, 154°— 176, 180, 179 Phenylanthracene, mp. 152°—179 Benzylfluorene, mp. 102°—178 Diphenyltolylmethane, mp. 128°— 178 Phenylanthracenedihydride, 120°—178 Dibenzylbenzenes, mp. 78°, 86°— 176; re Diphenyltolylmethanes, mp. 59° 71°—176 Methyltriphenylmethane, mp. 62° 6 Triphenylethane, bp. 397°—194 mp. fo" 8 x to o wo o $ $8 a sofas}se}ss)as}erfas]sefer at ea 3 (ae, i) oS ~ lolelolelolore) a i=) fe) sn wb o to i= — to CoH, 0, CoH, ,O C,9H,,0, so? a a 6 & wo tin jole) = ° cr es s [1 lele) to o [S) =) to rs a to (=) ry (Ganon G aca |aef=— == |==]=nfor SOx Oo to o is} tN Cc nN oo fo i) . i) wo i) to SO 0G to °o eiois A ein ~ Cc to o wo fo) is) Co oO O006 ts o is) Cr Hy4o FORMULA INDEX. Hexamethylstilbene, 161°— 179 Diterebenthyl, bp. 344°—194 Diterpenes, bp. a. 300°—194 Dicamphenehydride, mp. 94°—177 Hicocylene, bp. 314°—188 Tetraamylene, bp. 395°—194 Eicosane, mp. 37°—175 Coeruleine—214 Galleine—214 Dinaphthalene oxides, mp. 184°— ——180; 161°—179 Hydroquinonephthalein, mp. 202° —100 Fluoresceine—213 Naphthylnaphthoquinone, 177°—208 Naphthyl ethers, mp. 105°, 110°, 161°—178, 179 Phenyloxanthranol, mp. 208°—139 Phenylene diphenyl! ket., mp. 100° —138 Terephthalophenone, mp. 159°— 139 mp. m p. Diphenyl phthalate, mp. 70°—119 Fluorescine, mp. 125°—60 Resorcinoxalein—212 Triphenylacetic ac., mp. 264°—71 Triphenylmethanecarboniec acids, mp. 161°, 162°—64 Rosoliec ac.—213 Triphenylearbinolcarbonic ac., mp. 200°—68 Resorcinphenylacetein, mp. 267°— 210 Diphenyltolylearbinol, mp. 150°— 159 Phenolphthalol, mp. 190°—100 Diacetyldibenzylethane, mp. 174° —139 Scoparin, mp. abt. 210°—209 Ethyl dibenzylacetoacetate, 57°—118 Benzoylsalicin, mp. 180°—99 Bithymoquinone, mp. 200°—209 Cuminyl eth., bp. 350°—194 Bicarvacrol, mp. 154°—98 Bithymol, mp. 165°—99 Absinthin, mp. — 122°—206 mp. 6 (2?) Cholanic ac., mp. 285°—72 Cupreol, mp. 140°—158 Quebrachol, mp. 125°—158 Eikosinic ac., mp. 69°—55 Lithofellic ac., mp. 204°—68 Eikosenic ac., mp. 50°—54 Arachidic ac., mp. 77°—55 Ethyl stearate, mp. 34°—118 Eikosanoloic ac., mp. 91°—57 C,, GROUP. Benzylphenanthrene, mp. 155°— 179 Dinaphthylmethane, mp. 92°—177 Methylphenylanthracene, mp. 119° —176 Phthalacene, mp. 173°—180 Dibenzyltoluene, bp. 394°—194 Phenylditolylmethane, mp. 55°— 175 | C,,H,,.0, C,H,,0,5 is) bs a ole) sofas 2 i @ 8 ~ 2 fsstes|esl=n ‘° & iS) i] SD O000 iS) tN oO i) lacfae to bo OO wo rd Oo ~ i) i) Rac eo ey OS AGRS ND OO wo j= ts ~ to © i) is] tS aie) Ae seise Oo 263 Heneicosane, mp. 40°—175 Picylene, ket. mp. 185°—209 Dinaphthyl ket., mp. 1385°—139 Picenic ac., mp. 201°—68 Methylenedinaphthol, mp. 194°— 100 Phenyldibenzoylmethane, mp. 119° 9 Resorcincinnamyleine—214 Triphenylmethanedicarbonic ac., mp. 278°—72 Dicinnamenyl vinyl ket., mp. 142° —207 Methyltriphenylmethanecarbo nie ac., mp. 203°—68 Methyltriphenylmethanecarbonic ac., mp. 217°—70 Tolyldiphenylmethanecarbonic ac., mp. 154°—63 Triphenylpropionic ac., mp. 177°-— 66 Dioxydimethyltriphenylme thane, mp. 170°—208 Phloridzin, mp. abt. 170°—99 C,. GROUP. Picene, mp. 364° c.—181 Dinaphthylethylene, mp. 149°—179 Dinaphthostilbene, mp. 161°—179 Dinaphthylethanes, mp. 136°, 160°, 253°—179, 181 Dixylvlbenzenes, bp. 394°—194 Cetylbenzene, mp. 27°—174 Docosane, mp. 44°—175 Naphthoic anhydrides, mp. 133°, 145°—61, 62 Dibenzoylstyrene, mp. 129°—207 Triphenylbutanedione, mp. 126°— 139 Orcinaurine—212 Cresolaurine—212 Diethyl truxillate, mp. 146°—119 Dithymolethane, mp. 185°—100 Anacardic ac., mp. 26°—52 Phenyl pentadecyl ket., mp. 59°— 137 Cholestol, mp. 139°—158 Illicyl ale.. mp. 175°—159 Behenolic ac., mp. 57°—54 Brassidic ac., mp. 60°— 54 Erucic ac., mp. 33°—53 Isoerucic ac., mp. 55°—54 Behenic ac., mp. 84°—56 Oxybehenic ac., mp. 96°—57 Isodioxybehenie ac., mp. 98°-—57 C,, GROUP. Benzylnaphthalene, mp. 35°—175 Dibenzylmesitylene, mp. 131°—179 Phenyldixylylmethane, mp. 92°— Lig Benzylpentaethylbenzene, mp. 88° —177 Methylhexadecylbenzenes, mp. 11°, 27°—174 Tricosane, mp. 48°—175 Dibenzoylmesitylene, mp. 117°— 138 2 99 bo bt o N > i © to ~ to to 1) to rs wo ° io iS) to cs ~ ° rs to ~ ~ fos) No to ~ od oo asfasfasfasf=s[aefas|sn DOO00009 ~ Go QAM AA AAA tb ~ tw t ao [ o is] a to iv) to on ~ ~ to o to (a7) © No Oo wo Go xa ~ to jole by & on QA AAA AA so) a+damma |=] = famt=a=~ O00 FORMULA INDEX. Tolylpentadecyl ket., mp. 60°—137 Fellic ac., mp. 120°—60 Methyl behenolate, mp. 22°—118 Laurone, mp. 69°—137 Dilauryl] ale., mp. 75°—157 C,, GROUP. Carbopetrocene, mp. 268°—181 Benzerythrene, mp. 307°—181 Triphenylbenzene, mp. 169°—179 Octadecylbenzene, mp. 36°—175 Dimethylhexadecylbenzene, mp. 33°—175 Tetracosane, mp. 51°—175 Diacenaphthylidendione, mp. 295° —211 Naphthalfluoresceine, mp. 308°— 211 Duryldibenzoyl, mp. 269°—140 Hexaethyl mellitate, mp. 73°—119 Paraphytosterine, mp. 149°—159 Choleic ac., mp. 187°—67 Cholic ac., mp. 195°—68 Ethyl brassidate, mp. 29°—118 Cerosine, mp. 82°—158 Carnaubic ac., mp. 72°—55 Lignoceric ac , mp. 80°—56 Paraffinic ac., mp. 46°—53 Carnauby] alc., mp. 68°—157 C,, GROUP. Biphenylphenylenemethane, mp. 162°—179 Trixylylmethane, mp. 188°—180 Trimethylhexadecylbenzene, mp. 40°—175 EKupittonic ac., mp. 200°—209 (?) Arbutin, mp. 145°—97 Cholanic ac., mp. 285°—72 Isocholanic ac., mp. 245°—71 Tolyl heptadecyl ket., mp. 67°—137 Hyaenic ac., mp. 77°-—56 C,, GROUP. Dibiphenyleneethylene, mp. 187°— 180 . Tetraphenylethylene, mp. 221°— 180 Dibenzylbiphenyl, mp. 113°—178 Tetraphenylethane, m. p. 209°— 180 Tetraphenylethylene dioxide, mp. 315°—181 Benzhydrol eth., mp. 111°—178 Benzpinacoline, mp. 204°—180 Benzopinacone, mp. 168°—159 Ergosterine, mp. 154°—159 Cholesterine, mp. 148°—158 Paracholesterine, mp. 134°—158 Phytosterine, mp. 182°—158 Cerotic ac., mp. 78°—56 C,, GROUP. Tritolylbenzene, mp. 171°—179 Cerotene, mp. 57°—176 Heptacosane, mp. 59°—176 Benzaldinaphthyl oxide, mp. 189° —180 C,,H,.0, Rutin, mp. a. 190°—209 Isocholesterine, mp. 137°—158 Myristone, mp. 76°—138 Ceryl alc., mp. 79°—157 C,, GROUP. Bianthranyl, mp. 300°—181 Lepidene, mp. 175°—180 Oxylepidenes, mp. 220°, 232°—210, 139 Anthrapinacone, mp. 182°—159 Hydroxylepidene, mp. 254°—181 C,,H,,O, Tetraphenylsuccinic ac., mp. 261° Cox H,,0, C,sH..0. C,sH,s0 iS) o iS] @ w o OOOO OOOOOR as}asfas}es}as|as]sn]as]se]se fox) °o 1X] ioz) © x wo o = © = 09 7) ro) ~~ OO wo So wo o a l=) tb oo So ojee) ict) So loz] o ~ Oo [*) o stl ee H mie gotten H,.O Fi dohensee! anhyd., mp. 126°— Phesyltolyiene mp. 164°— Homccholedaees mp. 183°—159 C,, GROUP. Lactarone, mp. 82°—138 C,, GROUP. Tetratolylethylene, mp. phe et Melene, mp. 62°—176 Chrysarobin, mp. 175°—208 Picrotoxin, mp. 200°—100 Santononic ac., mp. 215°—70 Lithobilic ac., mp. 199°—68 Melissic ac., mp. 90°—56 Oxymelissic ac., mp. 95°—57 Lanoceric ac., mp. 104°—58 Myricyl ale., mp. 85°—158 Coccerylic ale., mp. 102°—158 C,, GROUP. Hentriacontane, mp. 68°—176 Palmitone, mp. 83°—138 Coceric ac., mp. 92°—57 Palmitic anhyd., mp. 64°—129 Dipalmitylcarbino 1, mp. 84°—158 C,, GROUP. Dotriacontane, mp. 72°—176 (?) Convolvulin, mp. 158°—98 Ethylmelissate, mp. 72°—119 Cetyl eth., mp. 55°—17 5 C,, GROUP. Tetraxylylethylene, mp. 244°—18€ C,, GROUP. Pentriacontane, mp. 75°—176 Stearone, mp. 88°—138 C,, GROUP. Inulin, mp. 178°—31 Stearic anhyd., mp. 73°—129 C,, GROUP. Resorcinbenzeine,—213 ; Dibenzaltriacetophenones, mp. 1° ~ 256°—139, 140 NS a ~ aie a 4 ie io rd "% a: Ad Be) ie ee | 1 VT ; = (¢p) Z 2 O am