A STUDY OF THE FORMATION OF HYDROXAMIG ACIDS FROM KETENE II Y P. v B.°GOCHRAN THESIS FOR THE D E G R E E O F RACHEL O R OF SCIEN C E IN CHEMISTRY COELEGE OF LIBERAL ARTS AND SCIENCES UNIVERSITY OF ILLINOIS 1922 UNIVERSITY OF ILLINOIS -M§ 5 L_?JL 192JL THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION BY P. B. Cochran entitled A STUDY OP THE FORMATION OP HYDROXAllIC ACIDS PROM XETENE IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE DEGREE OF Bachelor ox Science in Cherniciry -A-'-d Instructor in Charge Approved :__z sd HEAD OF DEPARTMENT OF 500269 Digitized by the Internet Archive in 2015 https://archive.org/details/studyofformulatiOOcoch ACKNOWLEDGMENT The author wishes to take this opportunity to express his appreciation to Dr. Charles D. Hurd, at whose suggestion this work ms carried out, and to whose aid and advice its successful completion is largely due. TABLE OF CONTENTS Page ACKNOWLEDGMENT I. INTRODUCTION 1 II. THEORETICAL 4 III. EXPERIMENTAL A. Description and Operation of Apparatus 7 E. Action of kstene and hydroxyl amine 11 C. Action of ketene amic acid and pyromucyl hydrox- 11 D. Action of ketene hydroxaniic acid and diphenyl acet- 13 E. Action of ketene acid and benzhydroxamic 13 CONCLUSION 14 V, BIBLIOGRAPHY 15 - 1 - I INTRODUCTION ( 1 ) Standinger in 1905 prepared the first ketene, di-phenyl ketene, using diphenyl chlor-acetyl chloride and zinc shavings. (3) Two years later, Wilsmore prepared ketene from both acetone and acetic anhydride by the use of an electric coil im- mersed beneath the surface of the liquid. He suggested at this time, that the ketene might be used as an acetylating agent, since it has the advantage, that no by-products are formed in the re- action. (3) Schmidlin and Bergman also obtained ketene from acetone by heating it in a combustion tube filled with pumice stone at 500- 600°, with a resulting yeild of 10-14$. The reaction at this temperature may be indicated as follows; CH3COCH3 iSL Q . - ch 2 = C = 0 -f CH^ and above 600° 3 CH3COCH3 * 3 CH -t 3 CO 4 C 3 E 4 If acetic anhydride is used instead of acetone, it breaks down first to acetone and then to ketene. They also found that the gas would react with water to form acetic acid. (4) Ketene was prepared by Standinger and Kubinsky from brora- aoetyl bromide and zinc shavings, with a yield of 7-13$, but found that no ketene was formed from chlor-acetyl chloride under - 2 - the same conditions. The yield of ketene with brom-a cetyl chloride was 3-4$. (5) Staudinger and ICLiver, working on the properties of ketene stated that it was poisonous, melted at -151° and boiled at -51°. They also proved that the structure was CH 2 :C:o instead of CH=C-OH as some reactions might indicate. “ (6) Wilsmore and Chick found that ketene, if allowed to stand, condensed to a brown, pungent smelling liquid, which was acetyl ketene, CH 3 C0CH=C=0. This bears the same relation to acetoacetic acid as ketene does to acetic acid. The condensate will react with water to give aceto-acetic acid, and with aniline to give aceto-acetanilide. In the experimental work of this paper, ketene was prepared by the pyrogenic decomposition of acetone. It is interesting, therefore, to record the results of other investigators who have treated acetone similarly, but with other objects in view. ( 7 ) Maihle and Godon claimed to have obtained mesityl oxide by heating acetone at 410-420° with thoria as a catalyst. They make no mention of the presence of ketene. Alumina and zirconia were also used as catalysts with similar results. The reaction may be represented as follows: CH3COCH3 : '-3^ c = CH-COCH3 ch 3 ^ The above catalysts are known as "dehydrating" catalysts, so that a Condensation to mesityl oxide could be expected. It - 3 - would also be expected that phorone, or even mesltylene would be formed by further dehydration. This would serve to explain, in part, the higher boiling portions obtained in the fractionation of the mesityl oxide. It is quite possible that in this work some ketene was obtained, but if so, it was disregarded by the authors. (8) Idle. E. Peytral studied the decomposition of acetone vapor at 1150° in a platinum tubs, 11 cm. long. She noticed a pro- nounced odor of ketene when the acetone was forced through the tube rapidly. An ahalysis of the gases given off at a slower rate was made and the following gases identified; ethylene, carbon monoxide, methane., and traces of acetylene and hydrogen. Her conclusions were, that there was but one primary reaction when acetone is decomposed, namely, to form ketene and methane. Ketene, in turn, then is broken further into ethylene and carbon monoxide. : ' . . , 4 II THEORETICAL. The object of the present investigation was to study the effect of ketene upon hydroxylamine, and upon certain hydroxy amio acids. The only work done upon this subject was that of (9) Jones and Hurd. They prepared diphenyl acethydroxamic acid by the action of diphenyl ketene and free hydroxylamine, accord- ing to the equation (C 6 Hs) 2 C=C=0 f HH s OH— *(C 6 H s ) 2 -0-0-0 # I I H 1'IHOH The similarity of ketene and phenyl isocyanate might also ( 10 ) be noted. Kjellin prepared phenyl hydroxy urea by the action of phenyl isocyanate and hydroxylamine. C 6 H 5 - N= C= 0f HH 2 0H — * C gHs IT - C = 0 I I H NHOH Ketene with a structure very similar to the above, might be expected to react with hydroxylamine in the same manner. C eH 2 = C = 0 +■ NH 2 0H >H 2 C - C = 0 I I H HHOH would expect in view of these results, that this reaction would take place. The results of the experiment verified this prediction. - 5 - The reaction of ketene on certain hydroxamic acids was also studied. Here there is a possibility of three reactions as follows : 1. R -CO - N— OH * CH S - C = 0 — *R-CO - N - OCOCH 3 ^ CO 0h 3 3. R - CO - N-OH * CH S = C = 0 — »R - CO — N - OH H CH 2 — C = 0 3. R - CO-± - OH +■ CH 2 - C = 0 — *R - "CO HHOH Experimental evidence shows that only reaction (1) takes place. For example, pyromucyl hydroxamic acid, reacts with one mole of ketene to form the known acetyl ester, Further treatment of it replaces the second hydrogen to give the diacetyl ester, which is a new compound. When diphenyl acethydroxamic acid was treated with ketene, the diacetyl ester resulted. . 0C0CH 3 (C^ 5 ) s CH.C 0.UH0H + CH 2 = C=0— .(CeHsJsCH.CO-K - 000H S (9) Jones and Hurd describe this compound and also the preparation of the monoacetyl derivative of this acid by means of acetic anhydride. The mono-acetyl ester was obtained only by destroying the excess of acetic anhydride as soon as the presence of the diphenyl acet -hydroxamic acid was no longer in- dicated by the ferric chloride. It appears that the di-acetyl derivative is much more readily formed. Thus, it is natural to suppose that it would be formed when ketene is used, even in a 6 slight excess. Eenzhydroxamic acid was also treated with an excess of ketene. In this case an oil was formed, which was probably the diacetyl ester. .OCOCH3 (C 6 Hs).0O^HHOH + CH 2 = C = 0— ♦(C 6 H 5 ).C0.N - COCH 3 7 III EXPERIMENTAL A. Description and Operation of Apparatus. (3) The method of Schmidlin and Bergman, modified to some extent, was used throughout the experimental work. The ketsne was obtained by the decomposition of acetone in a combustion furnace at 600°. CH3COCH3 • = C = 0 * CH 4 Ketene is quite soluble in acetone. It was found that about 50^ of the acetone went through the combustion tube unchanged. In previous methods, this acetone was condensed in a series of U-tubes, which were immersed in an ice-salt mixture. Thus, when ketene passed through the U-tubes, much of it was dissolved and lost. To avoid this, the vertical condenser, shown in the diagram was employed. It was provided with an outlet at the bottom to remove the acetone as it condensed. The acetone, after absorbing some ketene, became brown in color. It possessed a pungent odor, suggesting the possibility of the formation of the acetyl ketene ( 6 ) studied by Wilsmore and Chick, After considerable experimenting, to obtain an efficient apparatus, that indicated by the following diagram was designed: 9 (A) is a pressure equalizer, provided to neutralize the back pressure from the combustion tube. This will permit a steady dropping of acetone from the separatory funnel and insure an even flow of ketene through the apparatus. The flask (B) is heated in a water bath, causing the immediate vaporization of each drop of acetone as it strikes the bottom of the flask. The combustion tube is filled with cracked porcelain as a contact agent. (C) is an outlet tube provided with a pinch clamp, from which the condensed acetone may be drawn at short intervals, thus preventing a the absorption of ketene. The two U-tubes are immersed in^freez- ing mixture, as safety traps to catch any acetone, which might escape condensation in the vertical condenser. This precaution is necessary since the acetone would react with the hydroxyl afrnine to- form acetone oxime. Operation of Apparatus. The combustion tube is heated to 600° and kept at this temperature for a short time, in order to drive out any moisture which would react with the ketene to form acetic acid. The acetone is placed in the separatory funnel and allowed to drop slowly into the flask (B) , which is immersed in a heated water bath. Here it is immediately vaporized and passes over into the combustion tube, where it is decomposed at 600°. CH3COCH3 600 ° CH 2 = C = 0 + CH* - 10 Some acetone (about 50$>) goes through unchanged. The acetone vapor and the gases resulting from the decomposition pass on to the vertical condenser. The former is condensed and is drawn off into the flask E. It may be returned to the dropping funnel and subjected to decomposition, again. The more volatile material passes on to the U-tubes. Traces of acetone, which it is essential to remove when ketene reacts with hydroxylamine , are liquified at this point. The gases then pass to the reaction flask (F). Here the ketene will be absorbed and the methane and other such gases will pass off. In order to determine the yield of ketene from such an apparatus, aniline, dissolved in ether, was used as the reacting substance, since the ketene will react quantitatively with this compound to form acetanilide, c 6 h 5 nh 2 * ch 2 = c = o — .c 6 h 5 hhcoch 3 . 55 grams of acetone were Ideated as described and the gases were passed through 15 grams of aniline, dissolved in ether. 38 grams of acetone were condensed by the vertical condenser. Thus, only 37 grams of the acetone reacted to form ketene. The ether and excess aniline were distilled, leaving a residue of acetanilide. The acetanilide, after purification with ether and drying, melted at 113°. '"eight 11 grams. This is a yield of 17.5 fo ketene, based upon the acetanilide formed, and upon the acetone which was not recovered. The yield reported by Schmidlin and Bergman was 11 % - 11 B. Ketene and Hydroxyl amine . CH 2 = C = 0 + ITHgOH >CH 3 C0.m.0H The hydroxylamine was prepared by treating 1 a solution of hydroxyl amine hydrochloride in methanol, with sodium methylate. This was filtered from sodium chloride and partially evaporated in a vacuum. It was then filtered again and the filtrate was distilled in vacuo. Three cubic centimeters of free hydroxylamine were obtained, which distilled at 55-60°, at 30 mm. pressure. It was mixed with dry ether and treated with an excess of ketene. The ether was distilled and the oily residue remaining was placed in a vacuum desiccator over sulfuric acid. After a week, trans- parent crystals formed. These, when pressed on a clay plate, melted at 86-88°, the melting point of acethydroxamic acid. The ic crystals showed a discoloration with fern/chloride solution, indicating that the product was not the acetyl ester, which melts at 89°. C. Ketene and Pyromucyl Hydroxamic acid. 1. Nr CO.NHoH 4* CH L -C = 0 Sr H co.ti-cocrii 3. -h 2 c H=C= o .OCO CH 3 cow-~ coc h 3 V CO.NHOH ^ 1, One gram of pyromucyl hydroxamic acid was dissolved in ethyl acetate and treated with ketene until no discoloration . - 13 resulted when a drop of the solution was treated with ferric chloride solution. 7 cc. of acetone was used. The apparatus, however, was filled with ketene, before the acid solution was introduced in the reaction flask. This, of course, left the same amount of ketene in the apparatus at the conclusion of the experiment, as was there at the start. The solvent was then distilled and the residue was dried over sulfuric acid in a vacuum. The compound was purified with ether and pressed on a clay plate. It melted at 34-96°, indicating that the compound was the monoacetyl ester of the pyromucyl hydroxamic acid. 2. A new sample of the acid was dissolved in ethyl acetate to -form the d i acetj / esfer. and treated with an excess of ketene A An oil resulted after distillation of the solvents. This was dried over sulfuric acid in vacuo for four days. Crystallization took place readily when the oil was cooled to 0°. The crystals were dissolved in alcohol and twice the volume of water added. This caused a white crystal- line precipitate when the walls of the container were scratched with a glass rod. It was filtered and dried in a vacuum. M.P. 54-55°. The compound is soluble in hot alcohol and benzene. It is insoluble in water and in petroleum ether. Analysis. Subs., 0.3573: N, 15.60 c.c. (35.5° and 737.0 mm. (at 35.0°) ). Calc, for C9H9O5IT: II, 6.65. Found 6.63 D. Ketene and Diphenylacethydroxamic acid. COCH3 3 CHg = C = 0 f {C 6 H 5 ) S CH. CO.HHOH *(C6H 5 ) 3 CH.C0-< - 13 A solution oi tn s acid in ethyl acetate ms treated with ketene in the same manner. The solvent ms distilled and the residue was dried over sulfuric acid in a vacuum. The resulting di-acetyl ester was pressed on a clay plate. The melting point was S5.5-97®, showing the compound to be the di-acetyl ester indicated by the ( 9 ) above equation. This is to be expected, 3ince Jones and Hurd obtained this e3ter with acetic anhydride and found that the mono- acetyl derivative could only be obtained by stopping the reaction as soon as the diphenyl acethydroxamic acid was used up. E. Ketene and Benzhydroxamio acid. The acid was dissolved in ethyl acetate and treated with an excess of ketene. After the reaction, the ethyl acetate was distilled leaving an oil. This showed no reaction with ferric ben z-hydroxcrnic chloride, indicating that there was no free^acid present. The composition of this derivative was not determined. - 14 - IV CONCLUSION 1. Ketene and hydroxyl amine react normally to form acethydroxamic acid. 3. The reactions between ketene and certain hydrox- amic acids have been studied. Either the mono - or the di-acetyl ester can be formed, depending upon the quantity of ketene present. 3. The addition of ketene to hydroxarnic acids follows the reaction: R - CO.NHOH 4- CH 2 = C and with an excess R. CO. NH.O. COCKs t CH 3 = 0 — *R- CO - NH - 0C0CH 3 = C - 0 — *R. CO. N ,COCH a , OCOCH; - 15 - V BIBLIOGRAPHY 1 . Ber. 36, 1735 (1905) 3. Jour. Chem. Soc. 31, 1938 (1907) 3. Ber . 43, 3831 (1910) 4. Ber. 43, 4313 (1909) 5. Ber. 41. 594 (1908) 6. Jour. Chem. Soc. 93, 346 (1906) 7. Bull. Soc. Chim. 31, 61 (1917) 6 . Bull. Soc. Chim. 31, 133 (1913) 9. J. Am. Chem. Soc. 43, 3 433 (1931)