INVESTIGATION OF BROMONITROCAMPHANE BV PAUL MEADE GINNINGS B. S. University of Illinois, 1919 M. S. University of Illinois, 1920 THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN CHEMISTRY IN THE GRADUATE SCHOOL OF THE UNIVERSITY OF ILLINOIS, 1922. URBANA, ILLINOIS I UNIVERSITY OF ILLINOIS THE GRADUATE SCHOOL .May:_'L8^ . 192 ^ I HEREBY RECOMMEND THAT THE THESIS PREPARED UNDER MY SUPERVISION BY P^l ^ U&eul &^ i tin lug-a- ENTITLED _ e ati BE ACCEPTED AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE DEGREE OF Do cto3i-Qf - PhJLLoa-gph.y- stxy / In Charge of 1 hesis l\T. ^ ^ /\T cad of Department Recommendation concurred in* Committee on Final Examination* s aioHMj! YTtBJiravmu _ JOOHJ^ STAUQASJD SHT !-■: <*( ^ht TAirr i _ *|tir.T li iSAoi' J ub S. J4 i.vis: Yfl KOI2lV>.. i. ft ? ^ !* ’ - k‘J ._..._ ...l:-- ..M ■" I - Kc/i '■n< MvjjirH) ^iMr An^hf^ ^riH' y;^t.uiw,rr^ 2 a ajfsi^rM a« fp . .%yj4:»aCt '^O ,T,-t>f;,K^a HlHT ‘ ^ AGKIT0\7LEDGMENT. The author wishes to take this opportunity to express his indebtedness to Prof. U. A. Noyes, upon whose sugges- tion this inve stigati on was undertaken, and under whose kind direction it was carried out. i Digitized by the Internet Archive in 2016 https://archive.org/details/investigationofbOOginn TABLE OF CONTENTS. Pag © I- INTRODUCTION^-; 1 II- HISTORICAL 1 III- THEORETICAL 7 1- Oxidation of broaoni trocamphane with nitric acid 7 2- Mechanism of action of potassium hypobromite on c ampho roxime . 8 Oxidation of inf ra-campholeneni trile . 15 4- Action of dehydrating agents on bromoni trocamphane l4 5“ Structure of the two isomeric anhydrides. 14 aw Action of the Grignard reagent on the first form of the bromonitro camphane anhydride. 17 b- Action of hydroxylamine on the second isomer of bromonitro camphane anhydride. 17 6- Action of alcoholic sodium hydroxide on the compound prepared in 18 IV- EXPERIMENTAL. 20 1- Preparation of campho roxime . 20 2- Preparation of bromonitrocamphane . 20 5~ Oxidation of bromoni trocamphane with dilute nitric acid. 22 4- Oxidation of bromonitrocamphane to camphor. 24 5- Investigation of the so-called "hydrate" compound. 25 6- Attempt to prepare the bromonitroso compound by the action of bromine on the camphoroxime in glacial acetic acid and sodium acetate. 26 TABLE OP CONTENTS -2. 7- Atteapt to synthesize bromoni tro caaphane by the action of bromine on campho roxirte in pyridine solution. 27 8- Attempt to prepare the bromonitrosocamphane. 27 9- Quantitative observations on the course of the action of potassium hypobromite on camphoroxime . 29 10- Preparation of the hydroxy-nitrosocamphane by the action of potassium permanganate on camphoroxime. ^0 11- Action of potassium ferricyanide on camphoroxime in alkaline solution. 51 12- Control of reaction with potassium hypobromite to produce the hydroxy-ni trosocamphane as the main product. 5^ Oxidation of inf ra-campholenenitrile by the action of potassium permanganate , 5^ 14- Preparation of bromoni tro camphane anhydride. 5^ 15“ Attempt to prepare the organo-magnesium compounds of the bromonitrocamphane and also the bromonitro- camphane anhydride. 5^ 16- Action of the Grignard reagent on the bromonitro- camphane anhydride. Methyl magnesium iodide being used ^6 17- Action of alcoholic sodium hydroxide on the compound produced by the Grignard reaction (see 16). 5S V- SUMMARY. 40 VI- BIBLIOGRAPHY 4l VII- VITA. 42 pJTk ^ ' ■'’ ' ‘ ■ ' "• ' '. ’ ' 'i. ^" ■ ' ’ ' ’^li .'* - ’ 4 r ■ ' ... v/fr V'’ ‘1 ^ ’ T *t2vt W- 3U 4 -.. ', ',»} % 410 ^^ a > '»r^ ‘ < ' V- ' - ■ . XI%I ®.j iaC^C*o'^ 4 k'WpiVf^ . Rfr* ilP -. ■ : -'jaf.' . '■■: ;W't •jrM ''Trf ;b'* ’ gc| f 7 ^* ' ■ '■ v' ‘...> Tlif,' 3 HI . ^/iil'Xfj'^ f> :•. rfi.»r nti mUtM, f.wtkHmA ’ll!. Krtf.rx.«L^. 7T9^Bflaiuir ¥/* ^ * ' A. ' ’ ^‘' 'i ' r ''>£• ' '. o' ’«>^-'ar£’*'-»it; •' katfj . I I « o Xi -• ., Sir- ' V f. « c *t‘4 ,f ‘ " V ■>» It ; ?/i;l5'<» t <|'; In ■ “V j| • . /,/ " ' ' ii ' ‘ ^ -fttJ’ fuojattd *x»/ i_'c iTi«>;twaA r - i' ^ ■' '' “• », * • ' ^ " "^1 ■•t XJroi JrriiaU . Xvj-jj t.orrroa «>»■.’ 00 “<;^-i&'Trt xr.i»21bo« o^Xoffoeld- noXi.oA UBI^ ^ • 1 ' ' •♦■*•"'•• YJK54JiLjl^,X'*Iff3t5. -XY ■ •’ :^(.V E'M ^ — a* , -i, , - ,- I --‘‘ . /< V -‘ '■ ' ■ -r -r- A r--- *AtI ‘^ -117 . ■ ■'■ y '.y-L' '■ ■ ■•• • ^r, n ?F=’.tr CHARTS. page I- General chart of the cocipounds related to bromonitro- camphane. (Historical Section) 2a II- Chart of the mechanism of the reaction, camphor oxime to bromonitrocamphane. 8a III- Curve of the mechanism of the action of potassium hypobromite on campho roxime . Grams of bromine used up per unit time. 11a IV- Chart of the structural relationships of bromonitro- camphane anhydride. I6a V- Chart of the structural relationships of the two iso- meric bromonitrocamphane anhydrides. ^9®- If. W“* v -T i’ •X. .■'fr*' ' ' ''f iR'''3»l ,vV_ ‘ i * .‘i ,v ■1. ’’r'v' »<-P^ 1 • ' * ' ' V. * .•%: r' t ’ui QUat^f^mxiiO -9i^l ' ' * !’flw:v*D0Q *. '*• lE . % n ft «t V 0 • 4; ' '•‘* , ■!■ '*‘'^ '^’'^ c r n lo <»rfKl tc- i^•ZA<<^^oalr• . vifi . oV7iifO,;**XX.X ' , ^ ’ ’ • *' •» '•■■' t ’ 1 m ' N . “ ‘ ._ . ’. ' , ’ \’ ' . lil* l). iMj^-i . oj»l9t.<>t o-dqi^' a, "Vv^ - ‘I •; , - . '■* Ttu'i ■ n- J‘. IH' ■ ■ ’’ , : /.C''^ '>• ?*“ -Mi ti-at »/(i ... ii'*r-(lMilt.v ,t“Sii«f»T^»' ■ ' 1. vtt' v y , # #i* ;:,*ti^ .;k • u ortotqMavd^'t^^^iSO.tCf oi;t»if ■ vl' ^ ’'',iA 3K{ fift ‘ '• * .<■ ^]| ,‘;,i 'i , , ■ . ■■ ,. k'^'' ‘..V. -I ■'. • U ■ !r ■'*« i>;' ''.f^ '-.'i,'^!' V VI ,r . . ■■■';■ V . ‘W .- ' * ■.. *. . I'n’''*/ .} .f . ; f ,*>• ..■. .4 ' wf# ;.t.i '.•<* :. ' ' ..‘I'-ifw ym’ „,y,,,i ,n^|j„ ,, ■ ', 7 ,v;' ,YV>' . ''.^*' ^ '■&> ' !^ll!RiiJ ' . v". . •' . ;^ ^ T i ^ . r. ? . 1 I- INTRODUCTION. Caraphor and its many co-related compounds undergo numer- ous interesting reactions. Although most of the reactions have been explained satisfactorily, there still remain a few which are somewhat doubtful. Among these is a reaction in- volving the conversion of camphoroxime into bromonitrocamphane by the action of potassium hypobromite, which was discovered by Forster (2) about twenty years ago. In view of the fact that bromoni tro camphane undergoes so many interesting and un- usual reactions, and that its method of synthe sis is so unique, it seemed advisable to investigate further the formation of this compound and of others closely related. II- 'HISTORICAL. Forster, after an unsuccessful attempt (1) to prepare alpha-bromo camphoroxime by the direct action of bromine on camphoroxime, tried the behavior of potassium hypobromite on the oxime. He found camphoroxime with this reagent undergoe simultaneous biomination and oxidation to give a compound which he thought at first was a nitroso compound, mainly be- cause of the fact that it gave Liebermann's reaction for nit compounds. (2) In a later paper (5)> however, he demonstrated that the compound formed was not a nitroso derivative but a nitro com pound, in spite of the fact that it gave Liebermann's reacti for nitroso compounds. The most reasonable structure for this new compound seemed to be c//, c 1 ( df-C-CUj -Clf ro so on 4 * . % f‘ ' X. '?’ ‘ ■~-r-jgcs-:»Bea6r -.-ajalBUMW-cac : V "h- ' '' ' , "'“•f. - ■ ■ ji»r" /^j -'i^*3J^IT »p?, U&fllL <>Vi OP ^ V ^ . ■ t'ij . ■ > ■: ftii J%,4. tT%<^ ttsdV>ri/iA.‘ . r»i^ >^ r •?^ i^^eaaati* ivta *loi^ i- - . ■ f\ _/-.. Yv=. ’^t^Cilf O'!'* 9iTi«i ejr f • i V '“■ --^ '.J '.I?, J i %VOil?ixI’ S.rtW f If *0 coJt^Q3 9iti' *^*1 0diV ' v.,_ ■ N '1^ . '>oe jf 'tf t:. of 3CC— «* 3 ilv 3 F^.i(CTi'ii 30 j'r>ridi?Jfi^ k ■■ ' '■ . ' .- .: - - ., ' . , -. !f ' “yj; 1 taijfl 'atJj.lj “!(« t>t<><.» »1J -Ji J»'ti.f ^»u , >!floiJ(l/ia-I litVgH h ■ ' ■ ' ^ ’ to.-L: ti/1 aJ ^*r '»X44r»pXv^. Las'^w* ,$ i Pj -'** ' ^'^''' ' '3 L- ^’V»4i4’c &3j3pqyo^ . B | ‘ A I lAi^iq. oj . r r.AcJt ♦*?- « f 11*=^ »x«fX'aio^ ■A‘ ' rio aitl^TvTi 5^0 Hv^^j-os, • ‘-jAV >aj^ 5 o*io><^3fJr# ' '■ ••, ••■ “■'•■" .'■ .’ '■■ ; f‘; . »/ftc ^tlL %tJLyt^Ai^.u tfOJ^ t. ' .■>■■' , " ■ ' A '- '- *\UO JWUO , ■' 4‘ ‘ 7 ‘ ™ -f a A eit xs^i.T/ii/J • f iiii^ «0li^44i iji. 0t4» -e'X«^lif';f.esi ,l^A«o«£.fcT: Xttcn yrtt .ir/jiiaoaaoii . otfotita tol • _ . . wnr ' L *’' ' V . ><: ' f vf^ if ^ f #a f»rt « li*/ .'vi: d'-on - 2 - which was the structure assigned to it, and it was named 1:1- bromoni trocamphane by Forster. This compound then became the nucleus of many interesting and unusual reactions. (See chart) On one hand, if it is treated with concentrated sulphuric acid, it loses the elements of water to form a compound which appears to be the anhydride but whose structure has never been satisfactorily solved up to the present time. (4) Under the influence of many mild reagents this anhydride changes readily into an isomer which yields a derivative with benzoyl chloride. Forster proposed several structural formulas for these two isomers but the data he obtained were so conflicting that the question remained open and the structures uncertain. In his latest paper on the structure of these two isomeric anhydrides (4), the struc- ture in greatest favor for the first isomer was that contain- ing a ketone group but all the conventional ketone reagents failed to indicate the presence of a ketone group. Conse- quently, the question remained unsettled at this point. A very surprising change takes place when either of the isomeric anhydrides is heated with alkali. (5^ The exact mech- anism is not known, but eventually an unsaturated nitrile is produced. The structure of this unsaturated nitrile is fairly well established by several facts. On reduction with sodium and ethyl alcohol, al pha- campholeneamine is obtained, the same compound that is produced by treating alpha- campholeni c acid amide with sodium hypobromite. This would lead one to suppose that the double bond would be in the ring next to the methyl group but if this is true, it would have the same -ocr. . ^ * ' '’N* ~ ^ - . I ^ 0 ; iki^ , , ; J • ■ 1 *'. .!t;.'j .V i; » . i.i,(t. . . . t: ^q:: •, JuT ' ^ '». • . 0 (, • . liTli* .' . ^v'fr '■•vj: ‘ . :.r . .. ? : ; ,:V.^ ....■<- " /t“ - •' ■ iJ6T.lv ••;•*'•.- f - L . : * *r a ‘j Cl : f • • a, ■ ‘ *aj ' v' -•• j - . c . . T : . ’ I ^ ' aatevi^ »»v . ' . ; I'^xi ^ ■" > . '• . ' ■ ' 1 t'* ■ - • «! '. n V /<• -5 -■ J - .^-1 ;■ ■ w-v . . . i. i i si 1 'u *r> ve »'1 jniii^do S*' _ ... V. .. I. ^ 2 L * ! f't ■• ■ t- • inm netiv .o. : -i*£' . - VC. •! .t i.v. « - T. M . .1- T-I 'iCV:' .'J&v- ../ -**i: . ■'••■ f . r' - I-T-o’rr . 3«f: f';j - 2:;i . ..‘i. *1 '- ~t . - ■-c : ': i- •■-•!/ 1: -. / ■ r.^. ■ ■ 0-^' ri^(..i’0 , •- t JLV \t,e ./v'^v .*> ~ao»ia .-■I- •: -'w i .’ ■■ .. . ' : _ - „J, ^'1-1^1:. '■ .; J '^■i. , J r.;t Ic v-c i J ■ fi'!' . w' . i ■ j ^ I'i. ;■ TiCi . : c r. ■-■ . j j, ;■ . ao ’ti i ^ Jao 1 S ■’■ j/ivi , '- ; I- ' ’c ■• ;• • i»r .'. )' ^ . 5{ ' > or"' '... . s -.' /■ , J. J -,• jt I '-.vi : >o;.L..'S'. _ i J, _•...■ . _ .:.-ai; M . . j: I’;,rv . ' \ 'i,- is-.c^'ulc ' iiiivj .x&j {;n .' c i> 1 .. M:-.-. yr';j J'/fJ'cj' - i. »’ -^i.c 'V .. -^1 , 9 in '• .! -• -J - .L :i.c L -. • r i.i^c '■■ _ -* . -l. i'C : J , r..-, r ' c .'i - . <: » - vJf©J « - » - ■s*! .' . ■ .. r, 4 tvC ti ■» j ' -V i.r ir lo -• n.j*’ i" -.>•« itfl C.i/iiJt .'* - 5 - etructure as alpha- campholy tic acid, which compound is al- ready definitely known. Further facts solve the enigma. The unsaturated nitrile, called inf ra- camphol enenit ri le by Forster, on alcoholic potassium hydroxide hydrolysis gives an amide entirely different from alpha- campho lyti c acid amide or beta- campholytic acid amide ( i so- lauronolic ) but is readily con- verted into the latter by means of dilute hydrochloric acid, showing that it must be closely realated to both, all t^ree being isomers. The unsaturated acid obtained by careful hydrolysis of the unsaturated nitrile also changes over read- ily under the influence of acids into beta-campholytic acid. This unaaturated acid, called, "inf ra-campholenic acid" by Forster, has a free hydrogen alpha to the carboxyl group, indicated by the formation of a tri-bromo acid derivative. All of these facts combined, point to one formula for the unsaturated nitrile, 'see chart) Returning to our nuclear compound, bromoni tro camphane , we find that with alcoholic potassium hydroxide it yields nitro camphane (5) and this on reduction with zinc gives amino- camphane and also beta- bornyl -hydroxylamine .• Inci- dentally this proves the position of the nitrogen atom on the ring. The pseudo form of nitro- camphane with bromine or the normal form -with potassium hypobromite, yields the original bromonitro camphane . One of the most interesting and unexpected series of reactions takes place when bromoni tro camphane is treated as follows;- If it is allowed to react with alcoholic silver nitrate, it is converted into a compound which Forster first \ ( r T" X : I • ' > V i • ^jrrx. - ir f ^ ^ ii> w » 1 X.* o ic ■ V .. ' ■ J ‘t ‘:, ;> - ) f*ira" ‘ . ft vis. -u ' t • 0 . ' :' -1, V. *i(j A %’.i iuj “ f 1 II i< I ii }i - r I, s >V -, . f t > • '•. J- !*•’’ f , ^ ^ ■■;!■ ' , ' ’ ‘ ' • 1 ■ Jk’~ v! ' • i .' . V* c ; • . r 9. oi; I *ti "i -3;::o ; loUii «. / f - 4 - thought vraa a camphene derivative. He called it nitro-cam- phene, (6) althq^h it is really not a camphene derivative, according to the real structure of camphene. The main in- terest at the time the nitro- camphene was prepared, was that it seemed to open up the road to the preparation of the enolic form of camphor. V/hen the hydrobromic acid is removed from bromonitrocamphane , the ordinary type of unsaturated compound is not produced but a trimethylene ring is formed and this simulates the double bond. ( 7 ) The so-called ni tro-camphene has many characteristics of an unsaturated compound forming addition compounds v^it h halogens, halogen acids, etc. For instance, addition of hydrobromic acid produces the other bromonitrocamphane \vhich is very similar in some respects to the 1 : 1 -bromoni tro camphane . The nitro- camphene can be reduced with zinc dust and acetic acid to give the corre- sponding amino- camphene . This with nitrous acid will give the corre spending hydroxy- camphene , and in the first paper of Forster's this compound was thought to be the enolic mod- ification of camphor, although its characteristics were very different from the enolic forms of various di-ketones and ketonic esters. The hydroxy-camphene with (dilute mineral acids is changed readily into camphor, but displays no ten- dency to do so under ordinary conditions, which is rather peculiar. The presence of the trimethylene ring, which sim- ulates the double bond was finally demonstrated by Forster ( 7 ) by causing the so-called hydroxy- camphene to react v7ith bromine in glacial acetic acid and sodium acetate. This formed the • \ V , ^4 |i!V J.i ;>J5', tj ■>».: s' ■' '•“> t.tf .,MoV; ; p^'- i ;i4 % ■ ^ > -jc! ,' . , 7/ji /) ^ i(» ' f ^i^ « 3,*^ n-s'-.l i ^‘:>.'M\ /i ‘r -iSl* >^.9gJSJao •'lo .-a-xii 1 ., l^4a'^tuV l ' .. •), r'l' r- f f*' ^■‘.. *' mV''' 4 / ‘ *\.V « iM^ b9H i • ■'. ,fM’ i «»fif> ’ - u ^3^fi*c,94;Vp eJ:' Ai >3 J t *'•• ' -■* » - ' ^ . > t d\l» ' Jll^ ’ (?'**• ; n«v= \t ;jpt ; *3 ' /'i,-/.-' f ly." • 4 4r/^6t! • JCAd! i< <■ • 7/Pli.fi*; •rf‘J , i . . '4 VI. ' ^ v< \ ' ''-'i ) . . ... ' '' . ..:’kX':<.. BV» "tS*V 1 11/ l.r-Ii-l'S V * 4t r doTii^^Sfricf., . y 4V .^yr .^- ■ >il r*»'i> ••:. - i iJriW *1, ■ , * 5Ji ifirr. '• B-lVifi .6 ? j ‘tu/;/ ill «v^.. I {*i1 ♦/i.T ' off 4«‘‘ J * ou‘v* ^ ^tnofxr;n«oI.v,'X?)iV3>^4 . , : . -. • ,; : -tv.- I'V w.t J.rt;j,ji&tf4 #i* ' ■• * 5 ^ ^' ‘.^ ft.’J 'pc ^ ^ A i* ., ■ ■ ' i‘ ■ ' fl '«’’^ ’ ■ -,'ll»s o, V'4<*y 0H»'i *£jy ■ 'I j J fiiiWC ,tf4 . *" 4 ,' ‘ ■ > 4 , I'. "I ' . ' ' / A ‘ ■■'• .--Bi V* * 'i? ’ i* V ' ' ’ w 7 ■. • / xr . 5j«. J . a ^ ^st t«'. - \ ? fll' - 1 »'^ » 'y « ' ' '» ^ i’ ' : • '■ . * * -i 4. g\/^ 44?CT 0-PX "tXi>Ao5 :/:' i., ' 4v.ia # :V* »: - I ^ .'iWtsiJ ll/irVA; .l? ' /fjj, “Sif V •.«;h (?iv;£j*‘ «rf'3 'i-c tspxi •'•^l 'V, K? «/ii ;:-,r V«|’ nMv^^v\oAo*i ©,*• ^v’ i- - ..' ■ ¥ , ft®* . ^ I l|^... AkftitW t. i.vljt... ... . 'h ."-• .i-'o-:#! W 4 . ■j.Jii.-:- r'.i - 5 - compound beta-bromo caraphor and shovired vrithout a doubt a tri- methylene bridge to be present bet\Teen the two carbon atoms, which ;/ould really not be expected to be so far apart accord- ing to our valency conceptions of the carbon atom. The position of the bromine atom in the 1 : 1 -bromonit ro- camphane was localized to one of the two top carbon atoms by Forster (8) by his inve s tigation of the decomposition products from the action of concentrated sulphuric acid on bromonitro- camphane to form the anhydride. This was performed by For- ster under charring conditions and he isolated as a by-product from this reaction a bromo- cymene , in which the bromine was in the position ortho to the methyl group, thus proving the bromine in bromonitrocamphane to be on one of the two top carbons. The tertiary character of the carbon holding the nitro group in the bromoni tro camphane tended to place the bromine on that carbon atom although the proof was not com- plete at that time. The formation of bromo-cymene here from bromoni trocamphane is very similar to the formation of or- dinary cymene from camphor by the action of phosphj rj^s pent- oxide . To generalize on the question of the formation of the trimethylene ring among this type of compounds, Forster (9) tried out a similar set of experiments on bromonitrocamohor. He tried to get the trimethylene ring by removal of hydro- bromic acid from bromonitrocamphor , according to more or less of the following order: (on next page) .‘;Xflu,< ' t''-)* V'-i '•iiy' • %d BjrrJ.J rcl^“-o nv/ oVs^^i^ lo y.,.-.^../ v..g^±T'^ ^-■r ^ 'v ' “ , ^' ^ 1 ■ nu|.r ■»k 4 <|, '** 4^ tr" | V *-ra1 w .i.Dv;ao'u 1 »^jb 'dr^iw.;i >U>4 4 m' i dfi^.o[ j," ^ ' f'' V ' ', ' ','''<'^5^" '' '"3 Oift onc«o-i\/ kdJ 4‘-‘if* ci , ’;»•'- 1*'' o^'• .vmJ . **•«■' ' • - t ' t.' •' VA . rtf .'^i #ic»jr< Ci,, Ytt- <\r v«/l jiltfr, ' ■'■ vot43^V'^iy-'5rt4 ,||jj -X6 'i' Avij^- -n.A%tv4f |f'‘- I m:. ■ 4 . 'IX*. ■ Th ' ><;,' ,,.j"'^,l' ■ ■'f* * i^ i 4 J. fi -tv'f'* ;?! 'url w/ 1 ' J'ft' i!-..t A.« f< 4 ' ■ A^' f "■•. .. ‘ '-'» ■ (. •*■ t-aJlann^'' It wiiV-t'Vii? " iSi't f •'^ c ' •*• ' <■«’ ■• ’■' i'.'' ■' ' ■ ■ ■ if >.■■•_• ■;.“ > ■ ;■ !' IV ‘ETjj: . 1'<1 /3 ■ ; - ' « • i'-' 'c.'t 'V , i'o ' « i'?** *i’« ♦ ■ ^ «? 4 yjp t ■'i f -i * ti^ » iSs I / f •* O’* V v4 '4^ : tti, . ‘Jt t i Jt >•'«?■ y l;«iy ft jrifii'. 4 C >Ai, « % ,«?it;£' ,;f ^3 ■ c - C//- C-C/(‘3 C/t CM^ at - 6 - CHi 1 c I ^ j ^ - c//* . c/f. Cj: (3 t CH~ 'pu- - C-C4f3 c ' O c C- 0 C- iJ 7y- This would have given theoretically the bromo-camphor- quinone ultimately, but when the reaction was tried out, it v^as found that the bromine and nitro group were broken off to give the unsubstituted camphorquinone . In other words, there was no evidence of the formation of the trimethylene ring aa was the case by the removal of hydrobromic acid from the 1 ; 1-bromonitrocamphane . An interesting summary is given by Forster (9) comparing bromoni tro camphane and bromonitrocamphor and their respective reactions . I f y *: «■ - * • ■> ... . ' V ^ •« ' ' f>‘ ■*'-> "/ ' ^V'' ‘ y-'-'-^^' '?V->^ '^'1 Ji. xiut rol.n4 3*Ar iL-*S. l^■^l;<£^i}(j|^7^‘tt ' r ' ' , .'■/'"n*. -' . i *tf. ,,^ Atr \4 i 1 «» -t'ittn ct 1 i ti b 4 i iij i^’Xii ^ 0 e o^s 'E, ^ *riii> "loWir nl >"'■■!, .;, ■■■ , ';Vv>; • jtty ,io 4% ij.‘. ’tc'i ^«*n.y '>'• C*j \V • ^* 1 ! ' 5 »^ '**■;•' its • i ■- • its ■* ’I, ■, '' 'f '' , ' *’ ., .’puj* ' H ^ \t 1/* f ^ fV': Tt«,r 't'; > ''^ Ji»Vtl «/ ^ 6 ' » - I.T l!l , t;j»'.-i «»^-i j *. -m \... w • '..- > "Hf'V 4 'r .■■.Ji'^jfer ., 'vi!; <• - . '•‘If I i^• :t ~ -jsytjiiif: I'"" Bi.'.n Jiim;'’iiuii.i - 7 - III- THEORETICAL. Taking the mass of evidence as a whole, that is, the compounds derived from bromoni trocamphane and the reactions involved to produce them , there seems to be some doubt as to the exact position of the bromine atom in the molecule. The main evidence in support of the fact that the bromine atom is on the same carbon atom as the nitrogen atom, is the fact that bromoni tro camphane behaves like a tertiary nitro compound. Forster in one of his papers on these de- rivatives (8) isolated a bromine derivative of para-cymene with the bromine atom in the ortho position to the methyl group, thus showing that the bromine atom was on one of the two upper carbons (if bromoni tro camphane is written with the methyl group on top). This bromo-cymene derivative was produced as a decomposition product from the action of concentrated sulphuric acid on bromonitrocamiahane . Oxida- tion of the compound bromonitrocamphane should indicate definitely the exact choice of the above tvro possibilities. This was tried some time ago (10). Although oxidation under many different conditions, with nitric acid and also v/ith a mixture of nitric acid and silver nitrate, was tried, there seemed to be no definite evidence as to the production of either camphoric acid or camphoronic acid. These oxidation experiments have been repeated under still more widely dif- ferent conditions and more positive results obtained. The main trouble seems to have been that the oxidation was not strenuous enough. Gwinn heated over the steam bath with the -in "caV ^riJivii'. K ttJf r»N3/tW»i'Vw.. ♦*', : ^ jJP <■! f ! .- M if 4.1 V Ci l^i i . << <\ ♦ V *» « 'V 1 />L^ , if >l;r *iK^T[Cf Pw< iUcl #.i- lO.f. « tl '. ", «i/®- .■!» i v » ii«^A citkiS%^p «jsiri^« &il^ xic irJ^ ^ ' ■■ J'' ' w .1 #iii£ «?Ai*Aw«[»0<>*t4‘«i;^oxjii>’Xcr i'- ■’ *•■ .*♦ ••■ •,«• ■ • •> ■ ‘ '''J’';Vr 1^',‘Y, > -i ■ ‘. . . , j . ■.-> V> "w5^” ' , IS ■'ii' Httv^ nc r: '•V ■ ‘ j,ap» ^^“SJ jfn ‘.I" *<( ■j*^ 8»4 lo ir^'. V o (-S } 4»Vi^jt»vit " • ' '■?! iv- ■ 'i. IvdiirCir; vaJ" cJ iTa>.f'’ir’o« -*»>},- ^ ■‘ '.i . V' >'T^v. - .. t*ajj '»* BiU •.^I'a Av L f ; rf. • u,- iv* . T-' ■’'* d;i. rx**xJ*tv^ -i tJ ixvoflioid tiv ' ^ ' 1;^:: '■ ->#■■-■/. ov i-'Ay!!-? 4 »t"' oi;>, , •.<;,oJ fio,- , '*.‘r • i» • * V^ ' ' *1 ' ^ '''.?'^i4 ', *J4f4 >iU >tgi,^ ,itfti-^jt‘i*i xioX4 iflOs.T ‘ O* f>*ox*ib>C«|r^.<^ » i _ I ’ ^ -f>bl^i} .mA xto blow J^obaco ' '■ ■ ' ' ' ■' ' ’■ " ■ ’ .'■ .• 4-' , ; N£ ..* /, -. i y . t O'*,! I9VOOV ftA- t® Bt> Lc Ao' itjfixn ^xi4" ^ ^JCC uaucff^/w. 4 ■ ■» I ©Jlitf* ;■ ■ ' ' ■ ' ' .• ':l' ' J* ,- , . *'■ *.'. ■r ■ ; r ' ■ ^ * ■( ?'Jt-T. unl-^ bif*> i>Xiir> ilJfytK ^arr ^ ‘ '.f/'i ^ ' 4 ' o-.&xfj ' -4i>li 'iWi'i - ' *v tt. ; , ., I.'" ” .\'i Ujii*-' ( ♦Jlaitol. OA 'J, '.'. f. ' ., ' ■ ■■ ■ J V c ■ • ' • ■ '; ■; ' ‘ ^ ' r ^ ■ ;v ^ ~ '4 ai«5:*s*w5a;fc- : 4> i-*fV - 6 - oxidizing agents for varying lengths of time with the result that there was almost alvrays some unchanged bromoni tro camphane remaining in the condenser. This probably contaminated the oxidation products which indicated falsely that a bromo acid was obtained by the oxidation and further indicated that the bromine was in the opposite position in the molecule of bromo- ni trocamphane . Accordingly, the oxidation has been carried out by the use of dilute nitric acid and constant refluxing for approximately a week or more in time. From the long time oxidation, camphoric acid has been definitely identified and also the barium salt of camphoronic acid separated from the mixture at the end of the oxidation. If the oxidation is carefully controlled under certain conditions, it is possible to isolate considerable quantities of pure camphor as the intermediate stage in the oxidation. All these oxidation products go to substantiate the formula for bromonit rocamphane which has the bromine and nitro groups attached to the same carbon atom. This is to be expected from the synthesis of bromoni tro camphane from camphoroxime by the action of potass- ium hypobromite. In ^he last analysis, the formation of bromonitrocamphane by the action of potassium hypobromite on the cor re spending oxime is rather unique. Bromonitro compounds have been made by the action of potassium hypobromite on nitro compounds and bromoni troso • compounds by the action of bromine and sodium acetate or pyridine-on oiimes, but as can be seen, the syn- thesis involves both bromination and oxidation in order to I 1 , V- -■ •(; . -.i. •% / , ,■ "-i-at, . ' >■ I S'^'^ > i V V»% ■\UiiCrl4&dt .' PT'- -/ ■ ^ ?LA’ ,^t»i/7 M/U/ it' 4S»? tit; X 9'Jt^ . 1 t tr (jhskOi 01>M % i tyr Wi I ■..s.-iu* 3^fj ^ ^ r . i. t<' M>*' ‘>1^^ *;■. ‘ ;^--.3iV.,,' ^ ; ,, r«i‘.-li v*A».'C I ~ 1 'tf 'j- 4 1 ^ » ! ; gj - .,, ' ' i . -f = *' . ' ^ ‘ "’i '’t' i >, ', J ' «r». cn.t._ . , v*>.' I 9 .. ^ / 't Jg-: - ; . • ^ (- t, 'Td ■ ' ^:slt '\»oi •s^T**' is call “ , '4V ’'^’»V'^ ^ \ -i'Jii, 1. \-c i ol 'VI •liArj.ii: f’44. ' 6fi‘ .‘* t'oJr ^ '1? rj \ I ', : ' ■' ‘ *" • ■‘'■3 y . & ■ . V" ' ' » Vv‘^ •oi xVf /»' /.fi.'i, ^nTiAa^'^<^ - vcj t>i./.4j%,:*oi»' -»ii'J* ' ■ ■*.■>*» (iWai '“ ^ * V ^ , « ,-. i-v: : , ' ■ ■ ■ ,, , jm ;, m ’^ '' vW«yw V\ Lh^j / V A. •*,■;.•. • . - ijb 1 d :.Va ») (ail. X ■'■/• ■>>/:-.ii.,. ■ - 9 - produce both the bromine and nitro groups on the same carbon from the oxime group. Forster, (') who first synthesized bromonitrocamphane , suggested that the oxime is changed first to the bromoni t roeo- camphane and then is oxidized to the bromonitrocamphane . Since a green colored compound is invariably produced on addition of the potassium hypobromite, he suggests this green compound is bromonitrocamphane hydrate which on exposure to air loses water giving the final product, bromoni tro camphane . In view of the fact that this reaction is so unique and it produces a compound which is the nucleus of many other reactions, it seemed desirable to investigate in detail exactly as to the mechanism of its formation. The first thing obserived was that the supposed green bromoni tro camphane hydrate was unaffected by the most vig- orous dehydrating reagents. If the impure green mixture produced by the action of potassium hypobromite is taken and treated vvith concentrated sulphuric acid in the cold and then finally steam distilled, a mixture of camphor and bromo- ni tro camphane is produced. Simple warming and steam dis- tillation always yield some camphor along with the brononitro- camphane. Phosphorus pentoxide and phosphorus pentachlo ride in a boiling solution of the green compound in toluene, ben- zene, petroleum ether exerted no particular action. All of these facts united probably shov/- no hydrate to be present. It was next conceived that the green color produced might be due to an intermediate bromonitro socamphane , as the green ^ r;^ataa^■^w^a;^- ,>a»ars ‘ 4i/7> >:mm JRC<^ t ' ‘Mft j " <• ' ^Vl ’ 'f; j!» .' ■ ' .:iA^ « >ii's <-. i^vA'i f i JC)« '<■•' J "V tf Iau*.' K Sir t v'o-#!-, QirtJ nii i'i»J6Jo • a /ii eci^ji(^ib4'';Ot^T54'^ii'vfcoid’ .fkit^.sri . ■^ ,■ » ,» Bju; dis4' Xaniji tv#A< 1 od^* *'?f ■' >- ' -.' - . ■ i ; ' 'I ' '■?•'« J-i' ^ f uoif'0^4*-. ^-iwcav '4$ <- *4' '- ). »I -> odx »'l ,riwtZ^*f' .».._ k ".Jl ■ -- • ft I JP >■ '" aih _ .JWl- V « : ; fliO xij; r»»* f%'* ■' ' 'ji '*■• 1 i'''''is- ■'riP'R''? X ■■".'; ■ '!> . '' . \.-v .■:V-'i ... ;^‘\iki«,-. J iHtio'X,, /.>#«<(. f;fti?e. a/A' : 9 0 (t^ 'J--T:7r^^ 2i±'* yi» ni'.' Jj«2 t' '4* «/ i4fcs;i!w4rCr -.'i AVI ' ‘ / I?- t 'i» t»i i/ J^ ^ z j 4> irl'a, L f« 1^ •; OJ If , (., .. itf '.. ■ ^^« .■’ ■■ '*fl!- ‘ rt-CUA lJc/’ ♦Vij' *0* a ^*lX «t^*uo0i‘q * / ^ * < A * 'll* ‘ -f?!;,ctid luj If*. -.J-'t r-r '#S^. 11 If*.. ‘in iHu>'KJU- i» , 7dSl = 4'i^4 Xb, „nl V -tJXJ- ;'■ itAlo '-:r.' . .i/. ; uW ‘ ^ ■■ . ... V';'" '.,.''3 ■' ^ • '■' -L-'v -ftlAiTcixi v'Moif* ofJ»rf^ . V» - 'Skfl.'*^ ' V/'- '■'.••V .'' ' X/ xU ^ 0 'tij >>nvo/->»<.o aci-9«t.j^; t?^4 ^*t;c <»*:■ * • I* 6 •/ cf . 8 ^ fc4'4 itfta "V '■ . ‘ \ •’ - -V ■'■ ‘ ’ \ ' • I .'-ft J'V ttiXci <* '■ >» J - i ifiX . r 9 *i^ . '{% gi'.J r a' ^ >***^.. iLii fida ce V ■; '/^v . ■'. ^ r 'ki lNw ■ >’y. ' -’ — - 10 - color is characteristic of these nitroso compounds in this series. Accordingly, attempts were made to isolate or prepare by some manner or method the intermediate. Piloty ^11) prepared bromonitrosopropane by the action of bromine on acetoxime in both sodium acetate and also pyri- dine, So similar experiments were run to prepare the bromo- nitro so camphane but there was no action observed. The next attempt to prepare the hypothetical bromoni tro so- compound v/as by the use of the theoretical amount of potassium hypobromite necessary to brominate but not to oxidize. Al- though the reaction was carefully controlled, >.he final result was that approximately one-half of the camphoroxime was changed completely to bromoni tro camphane and the other half remained and was recovered unchanged. This would indicate that the oxidation potential necessary to take the bromonitroso compound to the bromonitro coigpound was less than that necessary to take the oxime to the bromoni tro so ' compound . The final evidence which led to the abandonment of this line of endeavor , i . e . , the isolation of the intermediate bromo- nitroso camphane, was that obtained by the quantitative obser- vations on the course of the reaction between potassium hypo- bromite and camphoroxime. It was hoped that the course of the reaction might be the immediate formation of the bromonitro so- camphane and then the slow oxidation by the remaining potassium hypobromite. Quantitative amounts of the reacting substances were taken and the course of the reaction followed by the re- moval of aliquot parts of the potassium hypobromite solution, addition to potassium iodide solution, and titration of the V. T/ATV -I- ' ■ ' ■ .•. ‘»T- JWW *, ■' .*; » i 5 » * 1 - I ■ - ’ M hf.J si.!:' e-. 0^ o¥o'f w o<» ■'*1^4 / <■ t 0*4 ■ ■'— : tj, ■‘t K '■ ;> • * 4 *) t'i oi^: ■ ,1 *■ ‘V ■ I •- m' . . , ‘ " ' k M * i ■T'., , an'i* . vUi. 4 j.OA Xo (# 4 l 0 e , 1 CP ■ ,’:■ *;* '1 ■ ® ■ ..■ „ •-■. „ /., V ' vl •■»'< "-■ >- « “it ' . a'»f ■ -* J-,j 4 ( 1 ; ; i « t, i^'i/ii ji xofoaf. ' i I II . ij-ovi M»c 1 ;, ’ . ' . ' 1 ..i Vv-? i r 'JMl!. Ito uii/ro#J^ i’ * - ^■:'•'■ I, i '^.'' ''ivi itf- '. vXJ t) .rn/k i» ■6 m-h aul^i> 4 » 01 ^v«cl 4 '4-v, Vf% f^■^- ?'• t'-ic.' l»tf IH^ *c *4.^ » 'UlU t^^iU V .«4.> ■ t. r wa*''4r,s./.t'.CT^JiitV'VOX'l->oS •#^ ••' 'v ' ■. '**■■ ' •%. , ' ■ • ' '■ , V A. » T[ ■ * ' - 4 ;, ’■• ‘ ■ ■ T>'’ ‘ ' ^ '*^ tr'. ■ 'a li ' * -■ ' -ii . .- P * =H,.f«f4V4 ^c. J^Tv'Crx vi(» \borf CJ t- y* uuiiAiic.’ '9«froja 4-sir 'i' V ' ' ’ ' ■ ’ ■ r M * ■■ < • '• ' - I • B -otK tcj' ■ .'c>3^i 1 0 ^. iHJirl iV ^(. - . of 4- oi-:;^ , . a, i \ x ■'"4 -'3!^ .'• ' ® ff“w " ''" ‘ \J , ‘ '>^ ■' II K. - c-fi’\f!. tr^ 4 oij ^ 4 ;<« o'oi^k I'di lr*4 ■j.-adA .^»jaiTj>CXon^i^-^ •V . ' ' t ^ ' ^ ' . /«' ;v ' ;*1 ' •i^fel-' 2 ^;. J.c-'Mf ic-. 'i ‘ . -.t.t ' " ' ' ' 1 * 5 ^* ' 'y;^ ‘ ,f 1 i^c 44 . 51 : i>o Ti' , ~ ■ . .1 1 ■'■ i'.' ' ’-,*'>*■' » fjt b 'i a ii >4 e cf t» . «» ft* 'T“ 1 .. C ^ M ii , ,vf‘4fc,'-., 'N-v II •Miy'i *rl\i, '•i.f .K^Vn' C J 4^'l $ i ^ m<111 >V. - 4c. v.j.'j, « ..4 rl’'« tw>'<• ♦'i- . r ^ % r '4' •]Hx frv. ■Xj ^> iii J U it I * ,<:ii. 2.- i. f «*: t 4 'J -' > C T* UVi)Tt( [(•; ,#z Ho’i >, . /avftrfr. •■.i«> l6 i' Wt: >-V-^ \ r aV^ VX ' fc«-«i!r*‘|i.„ .' P. Bib — ’ •• '-F' /. . ;» - .i-5 pi* rt- fiaV ♦ ;t,cx4J -n «^«li|'^'’' P-.^ ' ' * ’ ' ■ T ' ' ■ Wj^3 » ■' i * •■ ■' n ■ -j-i-i \'j^S ‘<, ■■$'.* tiin nJ/i&ri-f«v, n ^’€»5■f>* ' ' S [A> ,••■" >* J/.' S'' - ‘bl-C'' Yi axi. t^-%v I. ..'i^x*, Vil'i-^ '*0 ♦^^;|(»M^''Orl^;,V'' 'i4 ^ .,f'. ;■• ^ : S' ■ •..'»d' ' ■ ‘-'^al "?, V-. .V «. . # - i<..^.-»i* ^ ■ ...;A t..5Qii(c, .fv, :> f i o ' iit^, ,.,. 1^' tu'. fe> n.f fU.»JxS. »* * ,.o4' ■ ■' .% • :;' 3 feyl -Mi J-i »•., • wi ' iw -to »47-. ■■ J *■'*' '" • -a'; V’X < r • ■"’ ,<£■ ^': '.t xr^,; »tv ".U'^ ^ '- S';' .', »' .tt ''Vl- .••:'♦ , 'M..#: ...;:4 •4j4^ hc‘.- . ,,\* , - ; ,/ If-. V ' ,’',*A;vA ,, :«';h/*u-^»uxn ijj3. .'.inazf ' .,; 'i X)'.)’- Wi ' ■ • ■ ■■ - ' ' vitSr-rm i.wV.' J,i ^W'ila r»'Aj-«iiri& i" *:■ " J" .'. K '±tK. . '■ liUoH f ukiQ^ti nJiuvj^ Y,<.' >il- i>#4i ijr>i'«iV'> «: #i ; " ' -• -y> ■ T. J ' , ./ .. ^ ■’■iui“^. ,r „j|' «. - 12 - positive nitrogen atom in the nitro- camphane and this would hardly be expected. The actual facts from the experiments bear out this expectation that the change would not take place. Oxidation by dilute acidic potassium permanganate and in another instance by alkaline potassium ferricyanide produced in both cases an hydroxy-nitroso camphane which was first prepared by Forster (12) Furthermore, neither bromine nor potassium hypo- bromite would transform the hydroxy-nitroso camphane over into the bromonitro camphane , This eliminates all paths by which the camphoroxime could be oxidized and then brominated to give bromoni tro camphane , leaving the route whereby bromination takes place first and oxidation last. Knowing the above fact , it was possible to so plan the reaction conditions so that the en- vironment would be suitable either for the choice of one route or the other. In no case has it been possible to so control the environment so that the potassium hypobromite acted solely to brominate or to oxidize, but it has been possible to make either one predominate according to one's wishes. By suitable regulation, it has been possible to produce an almost pure white product by the action of potassium hypobromite, with only a slight trace of the blue due to the oxidizing ©ffect. Or, on the other hand, it is possible to make the oxidizing effects predominate and the greater part of the product will be the hydroxy-nitroso camphane. It is evident from the above data, that the supposilion of Forster that a bromoni tro camphane hydrate is produced is incorrect and that the green color produced which he observed was not due to the hydrate but to a side re- '•ia- ■ » < 7' ( ■ */* 'ij. :i^y ■ ^ .■'.;sj'! 'I * P ► i «« a r ^ * 1 ^ :S‘ t' j,-,t.*ff'*w>'5a>»ii(i ‘‘'S *-■-' ‘7*r '* X^Kv'‘4 •oCiT i j*f :*-« 1^4 ■ '^ ‘ '■* " ,1 V . •■ r -fi- i.., •• 't < ' yi>ir« : J ;AnA^./' . i;'>ft.*I*v *‘ 1 * '■ *• . ' " f, . i ii» ,:• ■ ?•■ • , '.'%^<» . iiWsv •• '>••■.... v%ayigii4»j:0c -},<^ I v; 4.' fit fell t{y ,it,‘Tf tii,- ec ’'^y * ♦ Icfiaapq ’.ioy' ^ ‘ .. ^' ■ ' ''.‘'ivu f " ' ' ■ ' tV^v I 1 < ■ jf’A' * ^■^-' o.Af> I4: tptclifi '♦rf^‘ rri vy»t>’Zo .Hf..(frr«of I ‘ , ■ %■ ;-. ', '.11 ‘ •.. I' fi" 1 >'•/ ui'i I i tJa fi cX, - i Z a®' ^'ii. -. />u ■ o«i)fr ^htt itJ . •* * i#dF#- 1 ' • . • ' ■* L'^" • ' '* ff 'x* - ’ \lmtoA bp ^ \ Jl W ’ y ,’i.v.l^ ; «V-’<4 /i. .1 l«O0<< wSV.J . ^'.i.4 ,w'i. ‘ ■ k'.’^ ' ‘‘ ' \ pX^A.Ui, a'" V.3 te'.up^- oJ' i;a4ir..xciaiti onfV^y JnpiaU n-' »t»i}* o.. ,;.. ^idlaapt*! utAtT a A 2L^, ^ ' "- ^ ’■ . i . . ‘ r' '1- XTr,t' i^XIv •:ij- •'. j <^.^»v tii/j:.ti u<^' io ••44^’ C’l X4’' ''' . - . -■■■• ' '*> ^ ' f! * Jtrv v*;C laKi • V , ’‘rt'J' '“14 ^ ^ V „ - ~ ' ' ' '.''"lir ■ VI o« o 1 Mtiibstd >* ! ’. rfi. o-i ,£Jfn ■r4. ^ t Af*.'X.5 i.ic.1.1. X;Vi».^-£t.'»..8'i , 4 r .f’lri'iw f ;” ‘ . '‘M-'T . ' '.->' ,' ,w-' ..'. ‘srt *» JjUW 1 Cf«OX^'4b>SfApii>^4 -- f '^'■1 !i aoZj , I *|/v*" * ' ^r*J| '"SC ' " 1. 1# 0 Ji *' ft *1: a 0 , ^ ^ ^ ^ ‘■■' '■ '■ 9 . ' ■ ■ ‘ 'j-:.;"'' V. y?»clr.‘"«4’N' * ^ i>i J'ijti 4 pa itisn?. .9’ '*4 - 15 - action, the simple oxidation of camphoroxime by potassium hypobromite and no bromination of this side product. In the original work on bromonitrocamphane and its many co-related compounds, Forster prepared a compound which he named inf ra- campholeni c acid and this was made in turn from inf ra- campholenenitri le . The nitrile can be prepared by the action of concentrated sulphuric atid on bromonitrocamphane to produce an anhydride of unknown structure which with alkali breaks down into the inf ra- campholenenitri le . Although the structure of this unsaturated nitrile seems certain from the facts as presented by Forster, it seemed desirable to subject this compound to oxidation and examine the products so as to have additional evidence as to its structure. If the structure is correct according to the formula proposed, on oxidation and hydrolysis, it should give: The unsaturated nitrile has been subjected to oxidation by potassium permanganate first in neutral solution to make the di-hydroxy addition product. Acid oxidation can not be used as mineral acids cuase the double bond to shift down into trie ring. Accordingly, partial oxidation was effected in the cold by the neutral potassium permanganate. The mixture was acid- ified and boile.d to complete the oxidation and to hydrolyze the nitrile to the acid group. The ketonic acid obtained substantiated the formula originally given to it by Forster. hydrolysis oxid. and C/^C'C//3 ZzO r t li : ‘ ■ i >. iU ,i . 1“ 1 ,'3r, j vJ > • ! *-t •,' .' Oj’J 3:..: C'.f T i-i' .• ,^l.rij../ :ti , '•-1 i '* ad- Jr' ^ j '-.'r/i'. p« **5"U Cvl .ri n ftu;» ;.i, . ,f ..^ i‘ X . ' ?.o. .o :i;i.(,': r,* w '''K' i’ tt ,!■'• J >; ' - - ft i 1 1 « ^ w:»- v ,v (*; ;,• > ! • v ''•■• v," • • ’ ■ I' . ,f .t i V. (iJ ' ' • ' '■ : ■ i .:•.••• i.r . J''**™ . <. «; -i. • ••' .■ t. '■ , -f i • 'TO'; c' ' (?■.;' ' \l iii.'i t 0 ^ J \i I Xa t < * ' w . t'- ' ■*Xf ;. ' ; . ’ : n bt . .. 3 •> ■ , ’■■j' r ^ ■ r( t»/.i . '■ f^HV ' .1 % j V ■ ; J J 1. j i I i 'j r - ‘ ■. c'JUiC^us: ...' A study of the preparation of the anhydride was made as the synthesis given originally was rather crude and accompanied by many side reactions. Peculiarly enough, the anhydride can not be produced by the action of phosphorus pentoxide or phos- phorus pentachloride in an inert solvent containing the bromo- nitrocamphane , even after boiling for a long time. The only method seems to be by the action of concentrated sulphuric acid in the cold. Forster ran it under charring conditions with poor results. The reaction has been modified with ex- cellent results by dissolving the bromonitrocamphane in an in- ert solvent as low boiling petroleum ether and allowing this to flow into a well stirred, cool, mixture of the concentrated sulphuric acid and the inert solvent. An attempt was made to prepare the Grignard compound with magnesium of both the bromonitrocamphane and also the anhydride, with the ultimate view in mind in the first case to synthe^ ze ni tro- camphane by a new method and in the second case to open a path by which better evidence could be obtained as to the structure of the anhydride. But the halogen in both cases was non-reactive in the experiments and the original compound was recovered unchanged. This behavior was rather to be expected from the general rule that the tertiary halogen compounds are not very reactive toward s. .magne sium to form magnesium organo- halides . The question as to the correct structural formula of the anhydride formed by the action of concentrated sulphuric acid on bromonitrocamphane has not been satisfactorily settled. Empirically, the reaction involves simply the removal of the n ' , *r ■ f ' 'i 'SFl /' ' ' ’if ’rii « (jfjp ‘i©' cv^.tJ ■« ' -j ' ' , II , '• * ' ■'51 -^, • boinRci^'oooJJ b/t» »lriri© *'»< «,« * 3 ■ , ,/\^ . '» t fisio obltiJiiilRV •fill; , .0(U'i;»©iikjX f) it " ' • . ' A’ - - -aruq lo f* w-r ^ At ii c»5 'i -^V ■ i' .. -ftfcg'ift i*4a Sho'fttm ftmm tjjr ni otjf*i©4v*i>t,#.fu -/j* % . ‘ V R m -ni# c ei{*t>'l c^vrt ti‘j i jot’ti ©4'X t'>^ 4'W« « t '*• ' ■ ■■ o F '-tti fl4* Ai fA j I6 oidi ^/TiwciXi" l*ft« iyiIJ’5 tu ttpC*iiii»»q 4aZii\i4' 'd'l tA^ ‘*;V- ■ ’ ■■,,.B'‘ /'.vi ' ^ UiiM p lt;ii ^ dJ'ivr.- Pnijoc}4&iCK4 ejfX ■, ^ n tl^ «ii'’ PriJ ct4ltt ^wiju 't t»ct<2 ttiW‘^4Jcd’’ to VS ' i i*>, ©4 ***»‘^'’ "X i'AXf' tijjiKiJiw »if^ *dv jt'» • • a • ; ; ■ (it^fi. 'j«e«n» btu) jBu oi»> nl fcp# v.oi^ ’^d' .'!■< Ll i.: •idt aj- r.i» ;>a^ii4Jdv iiiT..ca 09 ft4 4»,oii!' IT ■t' 's /I * tto'-*iit> riiorO Ofc t/ljr - 4.t>U . *»t i*\J 44 t d^o.n >4oO'i 4e.^ V *1 f ' • * '-W!'tCI HW 't ._• _ . . ^ ... . ...A* 0^'^’ ii(w/c» »t s t%{lli'J-a onS oiu^ i L ‘ ■ ■ ' s ■a ‘ ■ (i ■.’’■> bifid 4 «... . qrf t.4- II ifdj 4iX 0 aiA :!£ t .: y «fl<.d '* i4? i. • bt 'iJ.ti; tvpd i»*J t. itj? • jjtii i; b/^i/fig^DCtog x-.tj^o i" #4 %«.»i: ; drlJ tsh‘^^r^iii^.--p'ii9‘ «oi t >-'#.• .s. -•.-M'XAxt fliultt.PnjjAtt cJ tit- it t.Ti2oOXiK /rtTy^ .*^^ *^’*'7 '-■ tifl'* otruAtiluB b', %i4i:5C.riair to nb^JO/i \...i t 4i:!%tXTi>x4^ , . , . ■'!..■■ ■ ' ;x> •., " '.' ■ ■"' ' • ' -^-r. . aljr^ae -i.' i‘i;.oxoj»tbi4 .-a at^d 4on «^rt «rJ44^iS6(Mp«tlidodo'ia 4p, ■1 ' ' ■ . ' • ' ^ •■frp, ■ ] *.’ «*U to X=j:aBMa^E03e^t: -15- elements of water to form the anhydride, but, as Forster said, (4) owing to the fact that a nitro group is involved in the dehydration, it is difficult to ascribe a structural formula to the product. From the fact that 2-bromo 1- nitro camphane as shown below in formula I does not yield an anhydride, it would seem that both of the hydrogens on that carbon atom are involved in the dehydration. But the bromine atom exerts some influence because ordinary ni tro camphane doe s not give an anhydride when treated with concentrated sulphuric acid. On first thought, it would be expected that formula ll would rep- resent the correct structure. C//, C/V^- C//- C-CH^ H H cJ- "n £>, , V IT c/v Cl-f^ 3 l . / 1 X Oy- c'C/y^ Jj: c It has been found however, that dilute mineral acids and other milder reagents as hydroxy lamine , alcoholic ammonia, etc, con- vert the anhydride to an isomer which gives a benzoyl deriv- ative. Also, this isomer acts as though it was saturated to- wards bromine and potassium permanganate . These facts with others given later, made it very desirable to investigate fur- ther into the correct structure of the two isomeric anhydrides. Of course formula II is not the only formula that can be ascribed to the first anhydride. Very pertinent to this ques- tion is the work of Wallach ( 15 ^ ”'4) on the action of sulphuric acid on various oximes. He has shov/n that in many cases the first step in the reaction is the rearrangement of the oxime 1 ; '■, ‘ " >■*■ .. jw % ^1 J- I f ni .<.7t^jvnl -a,jfc t'A'«ix i s iitAi l&il «.;l **0 4^0 > ' " »■ ’■ ^ 1S^ Mtf4rt?^5 oJ- U<* J Ji . e.o ..; ,,, -I . ••*. -V*^ ''’ '--^ ,_ ***^ t,'j <>■%(< ■»5», *^1' ^* 6iiJ? * ’u •:f«l 4^ ^ , Nk. . >* . . .. k’* H 1 . Jfi P 4 r '•’iXwil kr-Ah t ifr? V <1^-. u<>^ A v i4'^ »io <>ii 4 , ^ • -. ;■ •,{ ' *'•■ "v ■'■ .’ dsi’To.-di uvJ'fl' »fj!jL4ii<>-V'i''viV/ /'wiS * tirfJ ,fti • ?’ '-{^ J ^ '^' *\ * - . ‘ -■ j' ^i.' iTiiif .bli>n • Jittf fi' lifd I X bSiiXfW alo^^r)\ ' Xtf od Uj'uw^ i I ^ i- • . * 4 S* •, -I ' '* . •«.-- r.t '>ji.TSf*r« ^■im % <' i/'- .h:? ‘ \ M. . «J i . aT 1 :. -i - ••’•' Xf. ;V ■• ,’'. . 1 . r i V ^ i»' j - V. . I *— •‘■ji •) *^- ... . •• Si' V -.a-'’ ':' ' ■ •’'iff '-^1 t-: . 'v ■ ■'■■'■-Ss- ■ ; ,;r . ' f ;i^''^*f_ "*-%0.4 .«,S J'5 . fc JltiiiHUV; '.iJi. Pul 00 l4 . 4il'ia*I 4 » ’ •.•s*Ifc*4Si 'itXil'^ ‘ ' - ■ ' ' ',: ■• • ■ „ . .iSfe -vitpC /^i&.vi>i<*'i n u** rftiljrtr 'i‘t*rtt!L,4if(cui' ot <9hiih%4bifn - &ili-a‘tii4.p's4f r >i.' i' ' Hi' a* it.t&R -s ;-iaoBi Irtf «;'<’<* .f^ * f,. n BDs^ ’ ■■‘• ‘■•. ^ i*" >■■ ',1 lU’Jt’J* 8;r.d4>-!J ' ,-^J 4;lii>| ^niMO'%4 np7i^ 'v\ ■ r- ; ^ ^ ' '’’^t r ; ** " ?'' ^ .X -’tu «• i /’t ^ •.; i b' t'^ - ''?. • '^'1 « / b tt’f 15 . ^f>5’i‘»b'4rtr.-i» aiioaf. nx < ’*rid^ tr 9XirJ^ju^/* A'^\*teii 'iU"’f<>?k| jfli b I Sil' nti» ®aV i c.g ' ». Jlv 'ii^ ’■ 'Y ^ ‘ t >J 3 . 0 , 0^ anaj^ii*tvfr ^jii 7 ,k:. ^ ‘ il- r.^- 'Cr^Z. s. '» t . V.: 'iY ^3 ' ■ - '■ v:y •■■■-'■..• ' _ ^ BV- ■'", ■' ••. , ^ - 16 - to the lactam compound which might be represented as follows; R J C-N-OH ^ R 0 R'' ^ ^^8-NH-R' In other words, what happens is that the oxygen supply from th e nitrogen atom rearranges on to the carbon adjacent to the nitrogen atom and the hydrogen remains on the nitrogen, the lactam being ultimately formed with one more member in the total number of atoms in the ring. It is of course not im- possible that a slightly similar action may have taken place in the course of the action of sulphuric acid on bromonitro- camphane. (see next page for formulas) The first step accord- ing to this mechanism would be the rearrangement of the ni- trogen atom into the ring and the oxygen atoms from the nitro group onto the adjacent carbon. One carbon is blocked by the bromine atom and the other carbon has two hydrogens so we should expect the two oxygen atoms would form two hydroxy groups, (formula III) Then , of course, ^he elements of water v^ould be lost, leaving us a ketone group for that section of the molecule. This is the mechanism shown graphically in the formulas. III and IV. Formula IV explains more reactions of the anhydride than does II. For instance, when the anhydride is treated with alkali, the unsaturated nitrile, VIII is pro- duced. Probably the intermediate is the immediate loss of hydrobromic acid to form the temporary trimethylene ring compound and then this loses carbon monoxide to give the unsat- urated nitrile. It is possible that Thiele's 1:4 partial valences may have something to do with the loss of carbon mon- I '*■ Pi, ifi ^,^J . o«o- iTjV , ♦ »tt.i!r-^ ■ *t fitdi rtf ’■ v ’^V'P:' ■**' W g '' 'i'il ' 1 1 'ift'jr.ii ^ ■■ . . ^,, ,„ ^ V ;i7r |r ($4J- /r .V4k«t>i>^- a-:-'-f-lA»!>_^iy ..c./ 4 c. , r * '"'•CTT ■ jJMJW jf. oa’jr •#> '3;!'4? jto*' a ni^3tT«tibx‘1^^' ■ <- \' ■ '^- ■' ... , ^' , ■*:^!^' ’S n V'^ ^\. "iiMiV^^ ft • '■' > ■ ^ . j A: • f ■ i|Wi' L ,, -* i ’'^u i^'xtc o *3t« • i. x,.(i o^j- it i, ' ^»cjrj(t ^'0-!M»dtsi^ii:<>T4^0>4} ^■- ■ r . " '■■ ,, ' to _■ »06'.^'»';^^ BViitl Him I'O ’.,'■»> .'•Iuil«i» ■■'ni.Tfl9ij^ll-4 Jil'll^ »itll»BI.4 1%. f.,c *^^-n * ■ ' .’1 I« , : ■> * W |:TI ii*,, fldx *Jtt 5 (;, «ff'j' 0 ^' •.J'S, i '''-,. ^ ' *. •"■. ■•-«.«- L^' '''VV^ wff ' ‘ V' as'”' "'f V '•'”' -N4’ ":T<* “•«< oj(.; to7i aitfOi^ 4 ’'ji,«4'f4'r^ #fl4; o ^a'iw.‘Vf /' : ,, , r "*■ / ■ . ; " . _- * , ■• _, . i,. *; - I - , ' X:' ¥^' ' ,;'d'ii>.'^ 0^-.. .;tI.i: t Iii(>t; omou'M ii <.»JK »iiV . 'M- ' ’ %. to'? ' '■' •‘•'■■^to ^i‘Jir» r 'i: / 1 * I «!!-.• ^ . Xji » ff^A'S . ttl \ )•• ^ ,i B<(9scii%^ ^ I. ■ ',.ii*lt''.’''k!lif, ' _ 8 't' i\n;.f,n: 3 jy' ^fu'. .•• j!)i, jU,; I- ' ■ '’’to .; ' . '* ?v ;'^/. ; --'•" a.(f.r »4 ^ n (' ,:0iuik0l ’* ' *'■■'.• ^ !-?L- „ W y to -.VX ct V«tJ X’ll 7 -> ', . ".-” ’'V. -I,.. ■ H‘«riv‘, ■. ».s /iiiV: ♦■•' rs'i "f.r.:a 4 ) a f% n i . 1 X» --ft T, .. ... • .‘»t^. ;i',-.' •■ -’^ r.'ii. ® ■ ■^- k .4 , . " -■^;.‘ m: . ' ?tf* >J I. f i n ^ ' t ,1^ *1'. .“* i , "-" ^ -

iyj »2; 4 ■■ '.j ' ^ 1 ^ 1 . - V— - . N^''...'.?f J 5 J,. ■ . '^ . ' .■®' ^ ^ '■ I *i}7>Mcu «.-■> .if^ l'a%i SXti'J'' '.-..Y » -' t* '. "i,: “i I, ' i': ' a'"'*/* <*■•'<* X.« ii) y*rf' 5*(»lM,iii,y o*i J}' ..ftXH'ir Jii»' ■ '. . "'■ ''””i :to^' :^s-^ vi'-;s*e*r?»>,'*sj ' s- ,. ;i * '-1^^ '^‘ g#^'*’.- ''IJ. ‘ ft. . , .« ,, 'I ■^SBI* V.' '/ - 17 - oxide is rather remarkable and yet in another way, it is not so surprising. Consider the formula IV. It might be said to be a ring compound of a substituted inner amide. This same grouping is present in a strained condition in the intermed- iate, formula VII. It is a common fact that amides in general lose water to form nitrides. Perhaps it is then not too far fetched to say that a slightly similar reaction takes place in this case, the carbon on the nitrogen joins with the oxygen on the other carbon, formula VII, and carbon^xide is liberated to give the unsaturated nitrile. Forster proposed the formula IV for the anhydride but was unable to prove that it was actually the correct formula. If the ketone group alone is considered, it should give the reg- ular ketone reactions with such reagents as hydroxylaaine , pheny 1-hydrazine etc, but Forster obtained a hydroxylamino compound by treatment of the anhydride with hydroxylamine . If the ketone were present, it had evidently rearranged to the enol form and reacted as such. He was uhable to prove that the ketone grouping actually existed, although that seemed the logical formula with vrhich to represent the anhydride. The main trouble lies in the ease with which the first anhydride rearranges ,l'- ^^rL-'V-^. :'i'-!. a; ■>«.* -f- ^ 'il i,-. ■. -, , '''T %e»HwrA-v-'^, \.-/'\i^A , '<)»' :*'vl!V.i 7 , . ■ ,v>' '•”*' li-r ** . - ■ *sr» - 18 - in this case, methyl magnesium iodide, and the comoound formed decomposed with water giving a new compound or derivative of the anhydride. It is easily purified in beautiful crystals and analysis indicates that the molecule has gained the equivalent of one molecular weight, ?^hich is to be expected if the ketone group is present. From this and other data given later, combined with the fact that this compound yields acyl deriv- atives v/ith acylating agents, such as acetic anhydride, benzoyl chloride, the structural changes should be represented as So the correct formula for the first anhydride should be that as shown above and the isomeride probably as the enol form of the ketone. After having orepared the derivative by means of the action of methyl magnesium iodide on the first form of the bromo- I ni tro camphane anhydride, it was conceived that it might be inter- | esting to know the result of the action of alcoholic sodium | hydroxide on this compound- (formula II) Accordingly, it was | treated with alcoholic sodium hydroxide and the following changes took place:- bromine was lost from the compound, prob- ably forming sodium bromide, the nitrogen atom was lost in the form of ammonia, which was detectable by litmus upaper in the alcoholic vapors, by the formation of ammonium chloride, and by the use of Nessler's reagent. The product was an acid f o Hows : j: ■' 'Sf ■ w ^ > ' t ■ ^'^1. '‘f‘ ,1—1 fZ' ■ 1 ^ ■4' ‘ .' // \-.^'’'l'f. 1 ^1 * ’ ■■ 4 ' i,J • At-. ^ ’ -■■■■ 'Wf! C4^, ^4,*J.i „ .ty",' - \ r . »f' ■M sm , ^.; 2 ,,, . >■*• ■. '4^; ■> i,^- %-'y tv '. t t. 'it'f'*.. v%m;I^‘. .0 41^ fyr i'H' . 1 ■ ^ ' I** m* ./ ' s ^ » f^«> ' .a, 4 > ?. W\f T* ‘I V . ^ . 4 ^ i A b , " ■ • I iJ V . i/m ■ *'' *' i f ■. . « ■ J ,■ 'W .. »^J/«t- ''Ifl r . , .4 Lr:^;^ iC'- r""'' -.4 «*'iL7’ *' ■ ■ * 1 4 ^ ■ %■ -^ic '.,'**■• ‘i .If ' ■!.f1 ,K:4l , j ’ • J; » -r ‘■'’'* ^ t ' • ' *'i'* ■* - i %’ r*- ' , r f*'? ^ ; • ' ,v' . ' f ■:'w «• ; .•isVT'l •-•'»■ t" *’t‘. ■• -• 'fi-, jJlK '■ >. '•• > *K‘ r^'1^UuCf.y.t: .;:v !l; ' ■ ■ - > ’ " '"i I ft. . A^i,.Je . . -. :1.4-. _ rr.' 'Z ‘ J '• ..Ji:/ ‘ ..^' '.‘‘if » >: r 't ‘ ^ < t.<* V 'A '•.'». T ^ • “ ^. i A /jtf . 1 • , ; ' _lii' j^ .. 1 '^_ jSHi-L ^ ^ di^ ’7*^^' *>4nwt' ’-T ^ '.'SW' •* I '■= \ A^^.». %h'A-r. -19- which gave the iodofora teat for the grouping -00-CH^ and melted from 67-70 degrees C. The logical compound that would be formed v.rhich has a place here is the following methyl ketonic acid which has a melting point of 68-9 degrees G. The structural changes involved could be represented as follows; This furnishes even more confirmatory data for the inner substituted amide formula for first form of bromonitro camphane anhydride. In other words, it completes the proof for this structural formula for the first form of the bromonitrocamphane anhydride and supplements Forster's data for the isomeric com- pound, the enol form for this same anhydride. ■ -I'"' , ■••i (v'tV ' .V,/f .■ , jfM. !jr^ ^ J ■ ' «i'®jj!rW.j*»'.-M^ *'*' '•■■ '-'W.i'' *f;4^.'.‘> ir^V-'VjM Pfc’-i. » ■' ' Z! . : ' 1/ * - ^.T»r7 , ■ _ V- - ■ -v./itifc :■ IF, [i ‘'MC' ■ ’, V- «•■' * »•* 2; .-, • * . '‘47 ^ ^ A; ™'.-i -.i .■•'••■' iJ ' I ' 5 ,%>:Sl -’ \vr--- .: ^ ailrf ••'•^^4 tiiv. '*'4?. >' vHr.V-rta ^^ ■; I vfe 4 < -r5 ■: .'■^';:,,H'vfi I/* bF ' ; ' , f t , ' ^ ' ■'*?> : ;.^ ■ • I ijm I 'j-' > I- N ' •. ; ■ a ■ •• - ,'• .. . ■ ■ . .. ,. i . ■■tri ^•■.- -l.vr-" ■■ ■ . '■■ <' •;'/:/; ; t :.-'s'^ ' . .- ' ^ ^ -«-■ *» ■4 ’■■«; VT' 19a- Chart lY 1 - Prepar ation of Camphoroxime . Material s • • 150 grams of camp ho r . 70 g ram s of hydroxy 1 amine hydro chi ori de . 2 D 0 grams of s 0 d i ua acetate • 2500 c c . of 95 % alcohol. 150 gi’ams of pu re camphor are di ssol V ed in about 2 500 GC of 95 alcohol and heated to boiling on the steam bath. 200 gra ms of sodium ac e tate are added to this hot soluti on and just enough water tha t the who le forms a horn ogeni ous so lution. Then 70 grams of hydrox ylamine hydrochlo ride are di ssolved in the leas amount of wate r po ssible and add ed to the a 1 Coho li d so lut ion in p 0 r t i 0 ns and th e whole soluti on re fluxed for ab out two or three day 3 1 0 c omp lete the react ion. At the end 0 f th is time , the alcoh 0 1 is di s tilled off on the s team b ath and the re sidue diluted with cold water to about 5 liters volume v/-hich precip- itates out the solid camphoroxime which can be easily filtered off with suction and dried. If the pure oxime is wanter, it can be crystallized out of ligroin, m.p. 118 degrees C. Yield if the pur e hydroxylamine is used. hydro ch lo ride should be used yield of the oxime considerably. during the rea( 3 tion should contain Bible to f orm i 1 homogeneous sol- ut ion. 2 - Pre p aration of bromoni tro camphane . r 'll ^ : i I * ' , i ’ ’^. 'iJrJ - V .)' #- t A ■ vi '7 . . " ‘1 , C»fi- -V rf - ^ ... 9 JS ' y ■ ;': T >“'^>^ *ir ‘ • L * ^ r j ‘ • ' o'. 3 lv^'* ^’ Hjj ».'' J |'-^* l ' i ':‘, * iy ^ < k ^ fj 4 |^‘ 4 - ifj 4 . vS . ‘S' * ^ ' ' .- ;■'' . f •. .’ • ■ V r 'V • '■■ft f,K' ''.,• •■.< P.- ''iiiif f-n-'‘ t.tii/r ;-'A*Vf *,'>iii ■ 1? J-e« • ii.U^ 4fn^ ^ ' « '. vVl. ,'a* ',• *L! . ^ •'H ■^■^'vV. *'?■' "/Wi H ' I ^ 4C J‘y iy JJBW ,J '■ V. ' ' '' % i'^sSBr ■• ■'' I ^ ^ '■’»■' * ' ■ ■ . mV- ’ I H- j jfc • .■•,•■-< ''» 4 n <-.*' : V »* * '• ViiJ -' t * j , r / #*/ tj4,^yi' i>. ;.'*v '-> A/c^i- *'»n’'a',, ^r**'© :.i‘ . S'.- 'Fi • ’•' ^ . T 3 wr?.ri ^•'^1,, Pf->i ■ .'•'■>* Vi-iJ’»f^ • '# -.,4 . ;^, fi; -:?:,' '•' i> .ij'”»ji1'', [■*.,. , ' .^-■•r'*^'' "■ ' V. , * ’ ' ■* ■ ■ ' ^ ’ '■'■ x . rM '/; O.I.. i -.' ■; i <''. V «^«-’ c / yi '| il »' ■ • .'•■• ' - V ' ■ ‘ ■ ‘ ''o •*■'“• ■ ' J '-.’/ i #^- * ’ -M '- ■ .' 7 !* H ' ' '" •' JSrVit ** ■■' “*■* •*'*' i 1 i * Si ' f ‘' v ' A *. ' ijj , . ' " • V ’ y ^ .• • •'■• ' •''•■■■■ y fy .'■ I’SI r . ^ ^ ''■ { ''■'^ "-<■ ''**■ ^ w,ifov •'*■'• ffjy V '>--ilt.A> 4 l* .,,/'^V^.f,.*r 'fcl. - 21 - (The method used, with slight variations, is almost identical with that used originally by Forster (2) to prepare the above compound ) Mate rials: 600 grams of potassium hydroxide or 5'^^ of sodium hydroxide. 800 grams of bromine. 100 grams of camphoroxime . Pro cedure : 600 grams of potassium hydroxide are dissolved in about one liter of water in a 5 liter r.b. flask fitten up with a rapid mechanical stirrer and cooled to below 0 degrees C. Crushed ice is added to the potassium hydroxide solution and a thin stream of liquid bromine is allowed to run in from a separatory funnel, care being taken that no local heating takes place and that there is always some excess ice in the solution in the flask to insure it remaining at or below 0 degrees C. As soon as the 800 grams of bromine have been converted to the potassium hypobromite solution, 100 grams of camphoroxime in a finely powdered state are added in email portions to the well stirred liquid containing suspended ice. The mixture is allowed to react under the influence of vigorous stirring for several hours and at the end of this time sufficient water is added to bring the water up to 5 liters and the bromonitrocamphane is filtered off v/ith suction and dfied. When dissolved in hot cnncentrated alcohol and cooled, the bromonitrocamphane crys- tallizes out in white fern like crystals, m.p. 220 degrees C. The yield is practically quantitative. r , f • v' K •j ? I f r,< ! ■; ■ -0 V, *' 7 it I h.'i» ?• . ' f ' tk •- : ■f.M ^ c '»: a . 1 X 4 . j » t .. , i» ^ I ^ t At' '>.‘X 4 ‘ 9 I* I ■ V r TV -*;,*.y. jy'tjC ■ui ' . • *i ^T. H- ri ' ^ * ’ - / • » - . r.v . <:■ i.. 4 iVp.( A ! f \xrt f(4ai . 12 >. .’• * ; I C .. ' * Jrt. ': J 'i i- i' jti j .j r. i ; -j ' • f S ' 1 / t>|-t ■ i'. ' ' * e * ii 'if '1 i 1 '■a-fd .^. 1 ’, ,' *1X <• # .‘i jf ’ . < t ^ ■■-• iii t Ik '1 iXrt t: ';l ;> ) ■ hi ...! cftm r^"'' l! »!' 1 * . 'tWJ t ' ti \ (*■ ’■ ■-: - |«4 t • ' - ^.v»4 . '.p V * ^ 4 ' '• t :' tb i . Jf <• ’1 "T I'.r .X r ‘■- ' '■ ■' v‘ o‘SAnp:i V L I '.n 1 ■:• /f * i •' n I 1 % ^ ,4 'j f. •f,v .^C- •« . x'Vt ^'/..X- ei . ■ - • '-o''' h.'.a: , iiulV. c -3 hi '.. .! •• 7 t f .t - 22 - Remarks : It is very desirable that the solutions should be kept at at least 0 degrees G. to obtain a quantitative yield. It will be notic edthat 600 grams of bromine were used instead of 400 grams as directed originally by Forster in his paper. It has been found that use of the smaller amount shows a tendency to the formation of the green compound, the hydroxy-ni tro so derivative produced by x-he oxidizing action of the potassium hypobromite on the camphoroxime . If the larger quantity is used, practically none of the green nitroso compound is formed and the product is pure /hite, differing from the green com- pound obtained by Forster. As has been shovm elsewhere in this paper, the ^pen compound is not the hydrate of bromo“ ni tro camphane nor the intermediate bromonitrosocamphane but is the compound formed as a side reaction by the oxidizing action of the potassium hypobromi te ^ on the camphoroxime. The same compound can be prepared by the action of acidic potassium permanganate on camphoroxime, and this by further action by potassium hypobromite does not yield bromonitrocamphane, which would be expected if the green nitroso camphane were an inter- mediate of the regular complete reaction. Sodium hypobromite can also be used v/ith success, the same molar quantities of sodium hydroxide being used but of course different actual weight in grams. Oxidation of bromonitrocamphane wi th dilute ni t ri c acid ♦ Material s : 25 grams of bromonitrocamphane. - 2 ^- 200 cc of water. 500 cc cone entrated nitric acid. Procedure : The above mixture was refluxed in a ground glass connected, water cooled reflux apparatus for seven days and nights At the beginning of the oxidation, much of the bromonitro camphane condensed in the cool condenser tube and at different intervals this was v/ashed down carefully with small amounts of ether. After the oxidation had proceeded for a few hours, it was not necessary to wash the tube with ether as the material has assumed an oily consistency vrhich washed back with the nitric acid. At the end of the oxidation, the solution was cooled and extracted several times with ether. The nitric acid layer was evaporated down on the steam bath until an oily semi-solid mass remained which was then dissolved in ammonium hydroxide, excess ammonia boiled off and barium chloride added to the hot solution, a white p re cipi tate , about four grams, being obtained immediately and more forming on further heating. This was presumably the barium salt of camphoronic acid as the original semi-solid mass was fairly insoluble in ether. Identification was not necessary as both camphoric acid and camphor were both isolated later as de compo si tion products. The original ether extract was treated with sodium hydroxide to take out the acids, the acids being liberated by hydrochloric acid, addextracted with a new portion of ether. This was evap- orated almost to dryness on steam bath, treated with acetic anhydride and a drop or so of acetyl chloride to convert the camphoric acid present to the anhydride. After heating this n ■ ! ^ f T ‘V-*' ’ ‘I •f '4 f. « v: ;W#fc -;i^ ,^; ' '■ ' ■ '■ ' '*viKt ' - ‘w ■' »■•' ■ ■*■ il'sm: '' I '■) y;V , o : >i'T^A& 0 ox 5 ^i; V'.r '> • ' . -■, '^' ' '^ • ' V /‘rS j.V^v . ' ,. - . ( y--'^ ../tofn-Ji' 4 wi^a, p% ^ 4 »• ^ ‘^Sl |i^i •; ‘.’ '• 'V'i?' -.n ■■^- ■’ ‘-> ^ ^ \ Va !" :'■•■#,/ ■ ■ '_V'i 2 •■ B ’ w-„ • .' ' ■ . f '‘^i ‘ '•‘^* !' \ O i- V ••'•. *■•, ' • . /■■r?^ . ; ?• t •• ^ . ar^rjf l , /{ ^ a I 4.' *tw% t* u :#>?> 'i- 9 .\'i- • -■ -94-7 , ^(«r X ' .-tj-'o’ ^ .' C'i . H . • i t •,' ^' v». »• 'Jr- t, -^A .i)^4*J t , iiii.- M'B 4. '4Cfij^i^ J '■ ■ '• ' ■' ■ ■ ' "■' ^'' i' ■’ V ’■’^'^tr ^’ ,Y V k '• -t' • / V ' ' ¥. rsyuk ' V'i"- '■ f-' ^ , ■ ■ J ‘V . , • ; ,v'V,:!- ' '•• 5 ?I;C ■ . :|] M Uy <: ^'i 3> + ?j 1 <» vj^x4 - r'4 o4T . *» ttfiils {,»• ^ . t -fv.!if^', ■ O o^i .By L-. • ^ . • •,■"■■• ■ ■ ' -' ■ i.'- ‘*- 4 ^. ^«Q-K f) c. ,i»^jr <^e^■+i■»■« ii ^xll" r t .. ^4 1 ?u^;, o41J^ .' '" • >. / : . .-riti»5'.x ‘yy */ kt • 64v-XB-y:B46 r-.*< *•' - ' V ' ' <•• ', f y ' *'N V*// ^ i f m ■ ’ ,^. ('i }• 'il5 » V' i:5r»K: • X 4 •^* ” '■%■ *• '' ^ • '' ' •' '’'*’ V- *' t'*™. ’ ■ a 4 ^#' ♦fc 4 i 4 ;‘rAc; - '■S' 1 - •JI &1 ■ ^ ■ -:"f .,„ 1 , ■■ ■■' .-."'X. ... ' -.' .»'v. — Z^t{ . u J :44 4 ' i I, aylj- ‘ |i¥ „ ,»»^iif- 4 .;^ »x 4 r 4 e. 0 '■ 'f . ^ ^,. .■ ' ' /'■‘; ’ >'') ' *'■’■ ^* -f ■ ' ' ' ' •■'■' I • ''-i ‘j’Tl' ■ ly'.'-^^; 4 ‘^.i;»jS)^^ ' 0 : ■■ 9.4 1 ^4,^44 nyWr Mf y^«g '' ' » 4* "iH > * » « ■■ '■■ ' ' L—l.—— '—.-Ji*ill ■».■.■ '!^-.^iLr‘il‘^-^v'. f - A-, t i rri - | - | mri' nir i "' ■■ l iii. r- i i ' >if A .tMTir .^K,j *'^ '■ , , ' :• ; i -24- for a short time, it was cooled, diluted with water, extracted ViTith a large volume of ether to take out the free organic acids and anhydrides, washed thoroughly with cold sodium carbonate solution to remove the free acids leaving the anhydride in the ether layer. The sodium carbonate was washed out of the ether by water, the ether solution dried, and this upon evaporation almost to. dryness with as little heat as possible to prevent any hjjdrolysis back to the free acid, and the residue dissolved in hot concentrated alconol gave one gram of fihe needles, m.p. 220 degrees C. on cooling the alcoholic solution. Mixed m.p., no lowering. Hydrolysis of the camp-.oric anhydride obtained, changed it to the free acid gave crystals melting slightly lower that 178 degrees 0. probably due to the ease with which the free acid changes over into the camphoric anhydride during the m.p. dete rmina tion. 4- Oxidation of bromonitro camphane to camphor . Materials : 50 grams of bromonitrocamphane . 200 cc. of water. 500 cc of concentrated nitric acid. Procedure : In this experiment, the same procedure was followed as the one where the camphoric acid or rather the anhydride was isolated. As usual, at first, the bromonitrocamphane con- densed in the cool water jacketed condenser tube, which was washed down with ether. After a time, the bromonitrocamphane mrnrn : ^ ^■\tt^r^\*^ir^4^ ,^:jtr-Ki .wUK? •|»vJkXJtfe ;Uoii9s>’*,fSS. ^ i *:c^l..ff' F-, i .'■" t V _ »w ;■ ■ V. .. ,.. li. ; ^ ' .-, ■ ^,^*j| -,.jr n,; ^ V ff. fe'icr '(HJk .- ' If. -•", ' ' ',>■. ■ ’• ■•"*'“ , ,. *, _ S^‘ ^ -V - ^ y ... . ..D ■ — „ I. ^ iiti t :t)^ t c a f t r^a . C'. -,,.. 1 . ■ V ^ ph\i.rh\(^tiM wi'ico. '--Ji'' a '\ ■/■''■ '\ ' i.‘ ■' ?■■ .'‘>t ■ . • ■■•;'■ .', , ; • ■’ ■ ’■ ' «,'. *'; 't* ,Tf ' . a;-v‘ iS tAl ■ ? ■fc '' ■ ' ,?.^tlt.. ' -I.. ^ ^ ? S '. iJ* o’ - , ■ ., • '■>*': ^ ’■ ■ ' .'V;'^%' - ’ *; ■• r..’ v.?-*!.**.^ '■'}( • . ..■,^„ •’ • f»<‘=r ifc-rfif ri'iOk. o4■4^^4^4^ '.f^V , 7 ’ 1 ' ,' ' ■'**■'*' '-Os'. '■ ■ ^ ||| «j|. ■ ..? 4 .^ ■ ■ h: ’■xv . ■,'^^ ?; ■ 7i3S '; . ' ’ ‘ ',at -. Ui, ifi- i i ««!•' iLvfgtc 5 Sr* ' w V . i- * a 6 ' '■• :? t * VI £'.VJ ai=*«r==« .,;v -25- ceased to condense and an oil seemed to return to the flask instead. Then in its turn, a white solid collected so much in the condenser that it became clogged. It was suspected that it might be different from the original compound which prompted the disconnection of the condenser tube proper and the washing out of the solid with ether. When this white solid was crystallized out of alcohol, it gave crystals melting at 176 degrees C. the same as that of camphor. About 7 grams of camphor were obtained . at tthi s step in the oxidation. 5“ Inve stigation of the so-called "hy d rate ” compound . This green compound, produced during the action of potass- ium hypobromite on camphoroxime was supposed by Forster (5) to be the hydrate of bromoni t ro camphane . If so, and if water is lost by drying in air, then the ordinary dehyrating agents should dehydrate the hydrate giving the plain bromoni tro can phane . The action of cold concentrated sulphuric acid was tried (by the same procedure as given under the preparation of the bromonitrocamphane anhydride) on the green compound and both the anhydride of the plain bromonitro camphane and camphor were obtained This is no daubt due to the fact that part of the green mixture was present as the real bromonitrocamphane and part as the nitroso compound as proven later on in this paper. An ordinary solution of the green mixture produced by the action of potassium hypobromite gives both the bromonitrocamphane andcamphor on steam distillation. Warming of a solution of the green compound causes the color to turn yellovf and then this by distillation with steam ,j.£. ' ^;V’. ‘ ■' : .' w4ksi^ •■' ■!^'' ./ ■" ' ,r ' i\) JmK < ?i^'•'' '' ' ^•" ' - ' ■ r, i»Mv) ■'. .v).' '.) y 'k' Jl? 'Ktl. .,%;' 4 r,., >'-V '^-r /ilO ^v., ■. .- y*‘ y- ^ ' \'-' 4 '^’* ''■ ■ • '•“ 'yy,i _*iOij(;-i/^ r .fi^ f r.; . J®v4?k4^.^ •H $ pmf.LjC'i* . ■ » - ■• i'--^!'. .'. ■ V iJ£ s\i '.'vi ' ^..... ., ■ ' . ’ '&■ K '.V ■ ■ . ’..*4 A^* '‘Vf-VA^i. • .? ; ^ *,<,r.rtm(';f K, i.v ';?r?v ' ,j,v ., ■ ' \ j*'\ . ■■ .•.. ‘ 4 .*.*■' ■) 9 '‘'^y0jt. ■ ■} I ^ ^t,r.mrS^ K.. kX 'i?nv « V '■'■ 4 ' ' \" '■ I '< '>' : ; • ■ ■ '1 *■ . ' * '; ’ ' . ■ ■ ' •i' ■ ■ <■ '■- i ■ 1 .S^'';v:;,v''' i - '-if- ^>. ■ f ''v cV, ■ r. . -V^ I ♦X • ^ ' 4 1 ''•imt.ik&Z iti&^-hXsL ^ • r.*‘ ••■.*5.- ^mo •:v4fiil)y’ i)? c>-*^< g?» 5 i: ; Xfi i-l-^;V*:U' pt ' fi , V •« 1 , • 'i • ■ 'T J .; w*i 4 ,■*»<*!! /'^ 4 i', ]'U j : f 7 \ A cull ; i*. ri-:;^i’ 4 XA C a f' :.' . 1 ■ > * ■ ■ ■ ;■: ■ ;, v k.Ur M '• •a...' « * "' ■ '' ■ '" \ ’ ■4^W>., -K*. ■: ■ „ XI V •■, .Wilf : VM ■ o?^’;.' 4 , iv,' i*’ '%o i|' -4 .. ' ..' w ' ''^f ’ 'S#' '-'‘ ’ ' ‘ -9iit Ir /Ije<* J4C.^ t> s:Tj^'».4,«fc-4.v; ^tc'yrjilu IV • ft : ' •• j; jf, n 'ICJ /.I, ... .•■ , . V •,'-i^ v^: •^” ' ..., ■’ . A fit 0*1 ^ «■ -,■ ^;j , f}:>7a: ■•'’ If- Jr- -- • .i»...i-— r . mU :•• *v ■ ' • ♦ *. ". ff' rVf f. ' 'I s r. '■rt , ' •■' ‘x'V’f ’ ]§■'• ■ '’‘: ■ • f "'iM- fA ■ 'k^. •'t ■ iiiiSfa^ ■ '.;‘v ' ■' ' ■ ’ ^ f?. • ..t ■ y ■• ■ '^‘ " '^■^'^''■■'v\ m ' Viffljf jj™ ^ *■;*•.." :•> ' 'N^' ! yppi-mf'. ^ • «»:« 4 i|i 4 i.' ‘^ 4 . ’H ' ^r'l'-Vy; Vvv^/' .y' /Ckkjy.^^^ i-ri'f Vt ■ ,/^V. ..I -’V*' / Zmi? * , 5 tiT - 26 - yields camphor. B romoni tro camphane is always present when the green compound is produced by the action of potassium hypo- bromite on the campho roxime . The green mixture obtained by the action jf potassium hypobromite was also exposed to the action of phosphorus pent- oxide and phosphorus pentachloride in the cold in inert solvent of petroleum ether, toluene, benzene etc, both in hot and cold solution. No action was observed in the cold and the action on heating was only that which is also noticeable when the pure solution in the inert solvent is also heated up. If the green compound was an ordinary hydrate, it should have formed the bromonitrocamphane very easily by these dehydrating agents. 6- Attemp t to prepa re the bromo-nitroso c amphane by the act ion of bromine on the camphor o xime in glacial acetic acid and sodium acetate . This attempt was more or less the same as the expetimeat or attempt of Forster to prepare alpha-bromocamphoroxime by the action of bromine in acetic acid. Sodium acetate was used in this experiment to take care of the possible halogen acid liberated but no action was observed. 5-55 grams of camphoroxime were dissolved in glacial acetic acid (50 cc.) and about 10 grams of sodium acetate added and 50 grams of bromine run in slowlyto the well stirred sol- ution. But no action took place and the camphoroxime was re- covered unchanged a" • V* 1 T L-. •» i-. f.' ■^ * (■! \ ^U'-J 'I»l'‘- M f •, c. : ;. y . . <’. - > -4:.': r '.ilii!' i ■; ; 2 - ^ *. I. j 1 1 .- ■■*' ' 1 • r ,, ff.2 J* I ,t tn.':, i; f.ib / ' i.' ...>^ • i' . ■ .■ r. u‘ 7 . • j-'i - •. , ; : <, i , r A V ■ ad : i 4i, • >e * *>1^’ 0pr\a,v ’ ' > -V«N ■ ■ • ••* y’l.’ •' 4 ? - _ g > V * o A ^ ^ J «■> f. j -j f. .I •>' .'■ ■ ;■ ( - - A t 2 'i i?: y » . -.f: '.'C iKKlj.' ' •'■• '•• :« 4 'Jov : ' ••• / •' % T>r i V ’ . : . i/j 'r -27- 7- Attemp t to synthe si ze bromonitroa o campharxe by the action of bromine on campho roxi me in p y ridjne so lution . This atte,£ipt was modeled after the procedure used to syn- thesizeuthe aliphatic bromonitroso compounds. (11) 6.66 grams of camphoroxime were dissolved in about 20 cc. of pyridine in a one liter flask with mechanical stirrer, cooled to a low- temperature below zero degrees, and about 7 grams of bromine added slowly by means of a dropping funnel. The first action was the addition of the bromine to form the deep bichromate redtcolor of the pyridine addition compound but this on slight warming decomposed to give the pyridine and bromine again. But the mixture was v;-ithout action on the camphoroxime. The reaction mixture should be characterized by the deep green or blue color of the nitroso compound which is such a valuable test for the ketones etc in the aliphatic series. The tendency for the bromine to add on to the double bond between the carbon and the nitrogen is very small nor will it add with glacial acetic acid and sodium acetate as shown elsewhere and also by Forster originally . 8- Attempt to prepare the br omonit ro socamphane . Materials: 55*5 grams of camphoroxime. 16 grams of bromine. 40 grams of potassium hydroxide and also 10 grams. Procedure: 10 grams of potassium hydroxide were dissolved in 200 cc I'iJ- — r “ i» . < rti* -'<4.. f. T' ■ - — , - -r- -V.s ' i C' ^ U ‘ / ■ ' . k , r .,r*: -* . •' *i'i N,. s vii vJ '' ' ; » ^ *> <• » t> 1 * A'i ,«i 7 ' : I f ’i'-i l i ‘ r.\ ': 4 J-i. K' >. • ■* •} ' h .■' ij I ■ :• : :n. \ i r-i .. . Jr, r' 4 vlv" I t I ' ^ » ■' ; ' r.)‘, e .. . ^.00 'tt* ' i' ; •;v -26- of water in a one li oer flask, r.b. and about ^00 cc of ether containing 55*5 grams of camphoroxime were added on top of the potassium hydroxide solution. The flask was fitted up with a stirrer and the mixture was cooled to about -10 degrees C. Meanwhile a potassium hypobromite solution was prepared by add- ing 16 gramsof bromine to 40 grams of potassium hydroxide sol- ution contained in;^ 1^0 cc of aqueous solution. This was cooled to the same low temperature. The the potassium hypobromite was added slowly to the mixture in the flask with crushed ice to insure cooling. The ether layer was finally separated at the end of the reaction and steam passed through an aqueous solution. Received 27.5 grams of the br omonit r o c amphane by distillation, or ^6 % theoretical for the complete formation of bromoni t ro camphane if plenty of potassium hypobromite were used. Then about 10 grams of the camphoroxime were recovered from the residue and pre- sumably the rest was lost through the alkaline solution of also through the formation of the green compound which has been proven clse'where to be the hydroxy-nit ro so camphane. From this exper- iment, it would seem that if there was an intermediate bromo- nitroso camphane molecule formed, that is is immediately oxidized by the action of more potassium hypobromite to the bromonitro- camphane instead of more of the bromonitro socamphane being formed by the potassium hypobromite. The quantitative observations in the next experime.nt show fairly conclusively that this is the case. -29- 9- Quantitative o bservations on the course of the action of potassiun hypobromi te on campho r oxime . Working on the theory that possibly there might be an in- termediate bromonitroso compound formed and that accordingly there might be a definite variation or break in the curve of the utilization of the potassium hypobromite, the following set of experiments were run to determine whether any sharp variation took place in theeaction of the potassium hypobromite. It might possibly be that an immediate addition of one mole of potassium hypobromite takes place and then a slow oxida- tion of the bromonitroso compound to the bromonitrocamphahe by the action of another mole of potassium hypobromite. Accordingly, exactly 6.70 grams of pure camphoroxime were taken in ether solution, and put in with a rapid mechanical stirrer with 10. 50 grams of bromine in 200 cc of potassium hy- droxide, the temperature meanwhile being kept as close to zero degrees as possible. After 15 minutes had elapsed, a sample of 2 cc of the potassium hypobromite solution was removed by means of a graduated pipette, diluted, 10 cc of potassium io- dide solution ( 100 grams per liter) added, and then 10 cc of dilute hydrochloric acid to liberatethe hypoiodous acid. This in turn acted on the potassium iodide, liberating iodine and it was titrated vifith standard sodium thiosulphate solution^; using starch as an indicator, to the end point. By removing suitable aliquot parts at various time intervals and titrating the oxidizing -power of the potassium hypobromite remaining; in the aqueous solution, the gr%ama of unutilized bromine remaining :j ‘ ‘ r.n i-i j ! - 0 -; .-li^ r.„' , ■'A’f . .*-, »J '■ C. • .* Ui, J ■ iu . ■ .. V' ■ ,( d7*i ;ii» ; ’ , *'t f f ,“,f i n ■ •* k;' jpF'i ‘ . ft.»n '• in v'lf.t:,. \ - ' i. V . ■ . ’v , •• li j’ t : cr-v r \ ; i ^ f ¥ D n I • V ■*> •. J ; I i > ». : < o / 1 .' . ■ ': I- ' I iJ/r- tr\: ' r :-A . 0 ■ 1 C’-L .'T «4J\V E J :< ' - r, hi- ^ ■ r ... i!w'^ X - ‘ ' -- '■■i'O ■ ■ '• J r? *7ilw &tfn fj !. % . :■ ’> • t ■- '-y X-'J -.rt :.i'. . i:0 VI. •; , 'i>s j <,sl' yy.yc I'n'.o r.yn-.^j Ji '-fi:- - i Jxi-i: • if ■•• i !■ V* <. •; ; ’.to , ;t ve»r;./ !:I-, ' *> ., 5*00 If . • •- M'.;’: ti ;j, •I'i^ '. , ■! .* J •■f. t v' 4 Jfl' ;x*’ 5 ’:«•*' i-- 4 .' • ' » ' I. t . ■: n :ij '. f .' Jj'. i.j’; ■.■■■.' ,. > n, *.’ •* 1 c- *) vX’l. _ ; c.j ; *nc It .i ■•■::; . i".; . V i ' ' V ' ' .>r:ui: j.v .1 . r i' .E j: v^Jt .. / ‘ ‘ 4 .t ^ W •t •:; 7 •,. ^firi o i.l • « ■/(-•ij ..• i i . ' J ' O'it < J* :> ■ *; r> r .V , •; .'. V' ; : n f v > i ' c,-: u; •• ■•- o , f 1 t..; ■ 'io C/0 t 'Jvr :.i; ^ . .} > ■, j / ■-• ■ , '■ '7'.? VI L ’’ '•r>o n;f. < ri o ot> !0 ':c ' ; ' f *ic • ’ ( •. j..- :; I o. '.C. i.t.,' c I,..- .'.1' ■’ c > .'■f> ur ; ■ rtv V u •; 'j : : I t . ■ i. : ;3..:v r!. ■ ; .v. J" .i; ; ' ? ' ’. c ,^i>y S' *.u-rr V *-v 1 wOC »,v' n/ Trw 'v, I : /r i , iiTfJ., /t V "v' (i? *£• , •'! f w" - r.' .' J .- -1 • ;t i • . ‘I 1. f , ’ fi I 0 . ■j' t: ■ * t ’ J f ^ J ^ J > • U i ll - it vi* t« J ^ . ; Xj . i .ir.-d t V J j, .. - .0 . i;t' 4 '. i vHv J .1. I 7. ' '-tr - ’ ■ ■'. ' *iv rM I* ?: ,'!P ‘J - 50 - could be calculated. Then this can be easily interpreted so that ultimately the grams of bromine used per unit time can be ' plotted against time. The curve was plotted (see under theoret- ical) but there was no sharp break in the curve. At the end of two hours and one-half, the curve was assiiming an almost parallel course with the axis so the temperature was raised and so the reaction v/ent to completion. Interpreting the curve, the oxidation potential required to oxidize bromonitrosocamphane to bromoni tro camphane is less than the oxidation potential for the oxidation of camphoroxime to bromonitrosocamphane. There- fore as soon as any bromoni tro so camphane is formed, it is im- mediately oxidized to the nitro componnd before another mole of camphoroxime is changed to the bromonitroso compound. These quantitative results thus discouraged effectively any further attempts to isolate the intermediate bromonitrosocamphane. 10- Preparation of the hydroxy-ni tro socamphane by the action of acidic potassium pe rmanganate on camphoroxime. This reaction was first run by Forster (12) and the pro- cedure used here was essentially the same. An attempt was made to see if the green nitroso compound produced by the acidic oxidation of camphoroxime by potassium permanganate could be converted into bromonitrocamphane by the action of potassium hypobromite , but it was found that camphor was regenerated. Bromine in acetic acid and sodium acetate exerted no effect on the hydroxy-ni tro so camphane . 1 . fJu.'ir.r - .'1. 1 rft*'jp •• •. c '.' >s.' - i. i- f • ' . I -i Ji-' C. K* \ , .iKti.t6V' i ■f- \ • . • r V !,> : w-;;. 1 .J * I. f w » '■ 3 t tyj “ ►' P { * I ‘V*, .. ' .^ . jAvr-Ni**. ..i: '■'' ' ■ i. .-flL'- fe' .. . 1 . o ' visi. . • -. - - A. .'■•Ti :a-:i » "• V .'?a|.*t V.-; 0, .' f'- ^''"i ♦, i. # ‘ f f ^ ^ ^ 'V '#\ . , r.i ■- . > ' u :.■ jrwf ». ,|,*r;o J ^ - .'*. ”vv'i"i w ; i' ••.a -j ^ J f ' ■ '■■/.'>':•. i:..j ' , :f • djl?: n .A uq!i*f.* i4 . ■'. \ o.i ‘ ' 1 -ii t c'.-' i ■' <.■:! •', ■)w’' LU-. ■ - J «9v* .. N J,i»6 ‘■'5|l fif;?" ■ I ' ' ''•' •’ ■ '■ i ■ ^ • * .-m*' • I 'V.Ot fc .lai t ) . I > 1 - 51 - From the above data, it appears that the green compound is neither the hydrated nitro compound nor the intermediate bromonitroao compound but purely a side reaction from the main route . 1 1" Action of potassium fe rri cyanide on oamphoroxime in alkaline solution* 505 grams of oamphoroxime were dissolved in about ^0 cc of concentrated potassium hydroxide, cooled to about 0 degrees, and an aqueous solution of potassium ferricyanide ( 15*2 grams) added drop by drop by means of a dropping funnel. Almost im- mediately, a white flocculent precipitate began to form which turned to a bluish green color The rea.ction was allowed to proceed for about one-half an hour when it was diluted to one liter with distilled water and the bluish green compound fil- tered off by suction. Dfied on a filter plaice, it gives the same unstable hydroxy-ni tro so compound in almost quantitative yields as prepared originally by Forster by the acidic oxida- tion with potassium permanganate. However, this is a much better method for the preparation than by the oxidation with acidic permanganate. 12- Control of reaction with pot assium hypobromi te to produce the hydroxy - nit ro so camphane as the main product. The conditions of the reaction of the >potas sium hypobromite on the oamphoroxime can be so varied so as to give pure bromo- ni tro camphane or to give primarily the hydroxy-aitrosocamphane. , ^jjn wC . ' , ^ iie . I . r. w ^ ^ .•; .-i .. v v ^ •' -» •■ 1-: I'jn-lc Mv , , ){ f u' i V. «» ■ ' » I i . ■ ‘ .0*; ^ i, J ., I. .1 'I t, ' : 'j .‘*1' I'k.-'’ ~i r -i d 3 .' '' ' ' ' * 'f -ll ' 't ' ■ . J .', :,'i , ; . tj i ' ' ': • ■ ’ ■'<■. ' ' i . . ■ ^ ' n*. - ’ “ ; . g^j ‘ :,;i .■* . ‘ ' • ' » rSf; ; r. c, .. :,i. l»V,i T' ■ c ' i./ ' “k ■ :t ^ V'J ^ " v' ; . v' ; 0. . i , ■’■ •. •> ■ •».*' ''-ir. ■ ' ,1 \ 'i ■ - :i‘Vr ^ 1 ■'■ * 1 !» J O u/jr ;<1 :-i V (ij fi' ! V '.•'t .1-';; , _ •■',7 ,() ,, , >• . >■'. -mr ' k., ' < 1 - ' • •’: C ■■'■ V {■ ■)■ f * /•. ' • i J’ £i ' ■'i c ' w «»; •-^••. .' »• i> '.I r,- litff. t’3 :; - S *-♦ , ): < - '•■ ‘ ■ ■> '■■■ Jr : 'io ' ;> ikit ;LJ6 ^ :• c ■) 0 3 . : ' ** ^ ^ ^ ^ '1 ’ -• ■ C' i ' . 1,6 ■ 'r. •; J :r ■■ / J - 52 - For the preparation of the pure bromonitrocamphane with practic- ally none of the hydro;cy-ni t ro so camphane , an excess of bromine and addition of the dry powdered camphoroxime is essential as described in detail elsewhere in this paper. For the production mainly of the hydroxy-nitroeocamphane, by the use of potassium hypobromite, take the following pro- cedure:- Take 5*55 grams of camphoroxime in about ^00 cc of ether over 200 cc of aqueous solution containing 40 grams of potassium hydroxide and added the bromine slowly to this well cooled solution. The ether so lution immediately begins to take on the emerald green color characteristic of the hydroxy-nitroso- camphane. Some of the bromonitrocamphane is of course produced, but this modification above has a tendency to cause the oxidation effect of the potassium hypobromite to predominate and assert itself immediately on the camphoroxime. 15- Oxidation of inf ra- campholenOni tri le by the actio n of potassium permanganate . About 20 grams of the inf racampholenenitrile were taken and placed in a one liter flask equipped with a mechanical stirrer with about 600 cc. of water and ^00 cc. of a ^ % solu- ition of potassium permanganate run in slowly. The flask was kept cool for the first part of the reaction in order to cause the production as far as possible of the di-hyd^xy compound of the nitrile. Acid oxidation at this point can not be used as strong mineral acids cause the rearrangement of the double bond down to the corresponding a Ipha-campholytic nitrile. 1 -.i' j 1 : 1 ,.i -/ r I ' -'■* v ‘ ^ .: I' ■- J ?. f* . A 4 * > i- ®!r - * • ■ I* M. .(; ‘.!0 >:i- r o • ^ ^ 'i i. -. .i ; J i .• '/!' -.: *.. .• CA-'Ce. «!...■ ■'^ ■ ' - ’ ( '^ . j ^ i, .' ica^Ti ; 4 V, • '*. ' ■ 'fiVf ; ".ire 5 ■,■ --5 0 At flic. [';.' .7lA,V' ’ ■•*-.o.;Sv.. 'ic.-V. • , "■* -’.A l-.«j 'J ‘ u 'j h i >; viil (-1^ . , -V. ■. A i • >3.^^ w"i , ’■ • T ■•■,.* V ; ■ :. 'fu.'j' .5 4: ,. . ii li - • * f -f ‘ ■ ' >, , .».• ♦ J ... - ^ V ' '. M, ^ ■ t C T ' 'i' 'l: ,1 X' ; jvri" ' ft ■ 4 i ->■'. c ... ' J ■, • ’■•r- .« -*■ - 1 .-^ i .;...■; -V- .V i' - . • :: ^ ... '4 v‘ ; .^' -»vcr>.N'’ . x^■■i,Zii■i. : 2f.bQa''4-Ji'0 ' !}■ , V ' , '■ ■■ '■'■ ■ a?..*';.;' '^wJ : ' 9 *T^ ,iU r . .'v '\ I n ■i, I »• 'xt.< ' at ', -^1 ^.-.x " N. fJV-' ■ . iT mt*. ,f) i ;;• >^.a ft ('■ %. !?-■'.' t ;,■ ••; ■ ’ ‘i v -s su <.» ;, ^ . C*. ■ v ^ ' o *f. A 71 : i i:- ....;• a £>iytv : .. y •.? . *r'>, ■ 1 iVf i:-i' V ■ -V.' ■■•' -V . - ♦'♦' •’'>/■; ‘*■<•4 4 1 . ',' 'v' ,'j'k .'I;.:, "(.■.;!• 'lJ:Z - ' ■' '* - ■ •‘ - ‘ •' ''-.'I .jUsiLi . . Y,.r nl nm • 'i.i •' ■ » i til' '1 ro»3A''4t|o „, .' ’ >■ -P A'A-- ,'■ •.;■ .•,c'r:4 -i't . rKiJt 'Jc t * .•• .; . t ^••i: V C’XJ ; •.; : l>\ it :4 1 j . : . ’ . ' ::!■„ •■ jM; It' '■ ■'•'*' ^ ^ rnt" .> ii '• •’ • RlWI? 6 WlBl i 4 1 V i y. > , .V .* ■’"•‘'v . •■> v.i3j; t-vtt' 04 ^'- ,". ^ ,-^yn:' tu 'W- . * . ■ ■ *'*■•! iJ i . / f !» ' 1 - ' foil-: 'vW;- ,. ' / • , . n • \t • \ 1 -.. . It 't % l)Utt 4 ‘ wm. |f ,..'M '7 ’ <“■ ' ■’ f •■* ‘ 'tf •.■.4.f‘''V ...V , »> , i.-*. .1 Iff w «: ' .J ' , '- I.' r .•' t,' ,*> : ;• »- ■ ;• J ' j'i. i ■ •• '■ • r . ' " .J J ^ ^ U V '.J t'.- /‘X *!' ■-’. iii.j ,' .: .'X • N ' tu'i '* ^ ■' • ■ '* ' <■■' i-'- • /f ''^ • •'• ..' *> ,r'. ,«i;r- ‘ bfti-d •; c ..r r.. t'. X : i/ ’ I,.' . ^ V 1. i>H X -v^; ' * *• V V"* \ •- ■; ^%-ff V : 1.' !. ■' i: , ■:. i>4v >■ . . ..■'" ' ', 'I H .. c t . ■ v , . {': V f ' ' c i: ' I'C V 1.. 1, ’ ' (.'4. iiJ - 55 - traces of the acid, washed again with water, and the ether removed Ly evaporation on the steam bath. The residue can then be crystallized from concentrated hot alcohol to give an almost quantitative ( 70 - 100 % yields) of the bromoni tro camphane anhydride , Remark s : Forster in his paper used almost the same method except that he added his bromonitrocamphane compound directly to the concentrated sulphuric acid with the result that he caused considerable local heating with charring and under these charr- ing conditions, a lot of undesirable by-products were formed. By the use of the above method that I have described, athe de- hydrating action is toned down, so to speak, so that the heat produced can be controlled and the dec ompo si tion products are eliminated entirely and the product obtained is almost pure ■white without recrystallization. When the petrol ether solu- tion of the bromoni tro camphane is added to the mixture of the sulphuric acid and pure petrol ether, it seems that the bro'mo- ni tro camphane is almost immediately taken over into the sul- phuric acid and dehydrated at once. Considerable heat is produced by the action of the sulphuric acid on the bromonitro- camphane but this is compensated for by the ice and salt bath aided by very vigorous stirring so that the temperature never rises above -5 degs 0 . Any greater rise of temperature during the addition of the petroleum ether solution of the bromonitro- camphane decreases the yield of the anhydride. The main point about this modification of Forster's method is that it enables the operator to keep the reaction 'well in I . • '•. ’ / • .- ' * .1 ' , y •:« »r 'A ' ;,,^h . '''i!','' ,?!S» «j /* . v« '.'j. i : c :•(', t " c ti ” r. . ^ IcK ': U i . • ... ■ ; ■ ;j .-■^.: I i J“ : :■ '. i, .. :2V.i ■ ‘> iq M ‘ J-. l •»fj H'-f, :': ? ^ •' ' '■ j :,-rf : , 5 . ■•r sf jr»j’.*v: :]y, I'i; .; , ■ >A I „ ' : : ';/n <'./ 'tf ' ' r , J. &».'Xv ’■ '. *y *' :j '.• S '. .'. ■ .i ‘ • O ■ t. : ,' ,f 1 1 u I ‘ «r T ‘ , t i •' ' ' '. 1 V .-fj "i Z J V, )'•■ • c t' 'i J) ; ttft; ’n . , /V’A V w. *• .■• ••' . * n \ *iXt \..i' .• :f • • ■ 1 -•' ..V .’W/O * :' t f T ■<. (A- • ' I ^ f k.* I ■jr r I! ,1. :*r . . -.. T Im '*»*•' r» « *& • .• fi '- r. ' tr' ' c' 2 r.^i'i'frW ' / . 4 .. - ;.i .. w - . ' - /’ • i • V.:.. O »'.• C .-.i.' i i ■ -• •■' ' ',!• > i'1 ' ’r'. J.',; -■ ' ■" " .■’. ■ t/ I T. ‘'i . • •' *• J 4 * \\ i '0 fn . ' : • >• ' 7 ” '■ a" i J jri' I j t i. • j; ‘ j ' j j_' . / i* lu »."<>•* •• 4 • ■' rSi’Cl.. '. ■' '. I* > ' JC • . "V A - 56 - hand and prevents local heating effects and subsequent decomp- osition. ^5“ Attempt to prepare the organo -magne s ium c o mpounds £f the bromoni tro camphan e a nd als o ^he bromoni tro camphane a nhydride . The attempt to prepare the magnesium halide compound of bromonitrocamphane was mainly in hopes that it would furnish a better method for the preparation of ni tro camphane . The regular procedure for the preparation of Grignard reagent was used, suspension of magnesium in ether with the halide compound and addition of some iodine as a catalyst for the reaction. But the bromoni tro camphane would not react under any of the conditions tried even under long refluxing and also after the addition of a small amount of methyl iodide. The original compound was recovered unchanged The non- reac ti vi ty of the halogen was more or less to be expected since it is a tertiary halogen and the tertiary halogen compounds in general react with difficulty with magnesium. The same regular procedure was tried with the first form of the bromoni tr o camphane anhydride and the same results were obtained, the halogen being also non-reactive in this compound. The idea here was to furnish some means by which the true structure of the anhydride compound could be more clearly eluc- idated. 16- Action of the Grignard re agent on the bromoni tro ca mp hane anhydrid e . Methy l? magne sium iodide being used . I -57- Matorial 8 : 10 grams of broraoni t ro c amphane anhydride. 20 grams of methyl iodide. 5 grams of magnesium turnings. 250 cc of dry ether. Procedure : 5 ^rams of magnesium turnings are immersed under 200 cc of dry ether in a one liter flaslc connected to a reflux con- denser with air tight connections. A small amount of iodine is added as a catalyst to the flask and 20 grams of methyl io- dide added in portions so that the vigorous reation is well under control until all is added. The solution is refluxed until all action has ceased and ??hen there is only a very small amount of magnesium left in the bottom of the flask. Then 10 grams of the bromoni t ro camphane anhydride are dissolved in about 50 cc* of dry ether and added in small portions through the top of the condenser and this mixture refluxed for several hours 'vhen the flask is disconnected, and small amounts of water added cautiously to decompose the Grignard compound. Then after the main reaction has ceased, some dilute sulphuric acid is added. The whole is stirred well, at least for several Minutes and the ether separated off by means of a separatory funnel, washed with water, sodium carbonate, again with water several times, dried over calcium chloride and evaporated down almost to dryness over the steam bath. At this point, if the liquid residue is allowed to cool slowly so that the last portion of the ether evaporates off spontaneously, the derivative crystall- izes out in large lustrous transparent places, m. p« 1 17-8 degs.C. -58- It is insoluble in acids, and alkalies, soluble in ether and alcohol but insoluble in water. It isconveried readily into the Co r re spending acyl derivatives. Analysis of the compound formed by the action of methyl magnesium iodide on bromonitro- camphane anhydride; • 1705 gas. gave .12^0 gms. AgBr or .0524 gms bromine. Found for the % Br 50*75 % Theory, G^iHlSONBr 50.75% By treating the above compound with benzoyl chloride and sodium hydroxide according to the Scho tten-Baumann reaction, a benzoyl derivative is obtained fine crystals out of the hot dilute alcohol, m.p. 115-4 degs 0. It will also crystallize from ether in star shaped needle colonies. Analysis of this benzoyl derivative of the first compound gave; .2l4l gms gave .10^4 gms AgBr or 21.75 % Bromine. Theory for the tompound CijqH2202^®^ 21 . 90 % Bromine. 17- Action of alcoholic sodium hydroxide on the compound pro - duced the Gr ignard reaction (seel6) . To observe the action of alcoholic sodium hydroxide on ohe compound produced by the action of methyl magnesium iodide on bromoni t ro camphane anhydride, about 5 grams of this derivr ative were dissolved in about 25 cc. of ethyl alcohol and 10 cc. of concentrated sodium hydroxide added and the mixture or solution boiled for a few minutes. A strip of red litmus wetted and suspended in the vapors issuing from ohe flask was turned red, while clouds of ammonium chloride were produced when an hydrochloric acid bottle was brought in proximity, and jJ, i' -■ '£ 'J if ;> OJ n T ,, f ' ; • h/~i ' \ l "S .*’.<• > 4 c‘,0 *< T' *' ■ 0 ^ • "I £' ’.'. -‘t '■’’• i’.t ' .. . * I. v>r •_ . .’ y '■•• ' j ci f ♦;.• K y___ f> Vt wf;.' M i • .1. . ■ w \ V'* i- .: I . ■■»<'■■ • : ■ '.J i’NwJ, •■■ ■ ; -oY^jr . ■ , :. ; '.' ■ ' : . ' (i.t > * I' ':' '' ' '’ < f . . ■ 'lijj- . » < ■ ' • • N • / - •• -lO'., J 0 c {.rc, fin OP* •;'. w >■ f>.K^ Ci : «. , i H ■ "a N' ."l \ ^ ' i. ■y.-'-.i X ' .'i /' I J' l.'. V : ’ '3 '•■. fe. j- • ,.L ' '■. <•.•“« , . ::.i^ '• ■' . 1,’ r • \ "v " 1 3A-: ■ ci£ l\ '^Iv ' .»• Kl' 4 y , "if I n i' ■ J. ;j c! ' ’ ' ; : ; '-8 a '■I- V - f'f ‘T-'^., ' Yx^.'rb V.'' ■»• V i 1 '■ {> ci: ■■'a'v C / %'ii , #', *■ f ,,/Cvy ,f, f r/ '» » ' ■. .. ,i.‘ff/,4*£ one -y .;,4 .’s i*.'*/ •• • ^ .A . n'?.*.. \;i;.. • .••. -i*t' .'. f . , ■ i.. ;; ,i » . 'i <>;" n f. ;j c.i oliUvi. . ti't-tf • :..i, r ■ ; *. f<; o ’' .1 ' ■ , 1 :.. ;; v - - 59 - the vapors turned a portion of Nessler's solution a deep car- mine red, all showing the loss of ammonia. The alcohol is boiled off, the residue taken up in ether and water together, acidified with acid, extracted with ether, the acids extracted from the ether with sodium hydroxide and the acids again lib- erated from the alkali by acid and removed to the ether layer. This v/as evaporated spontaneously the rest of the way, whereby slight yellowish crusts separated out, which are soluble in alkali, but insoluble in water. A sample of Lhese crusts when tested according to the iodoform reaction gave a heavy precip- itate of iodoform. Melting point gave 67-70 degrees C. The wide range of the temperature was probably due to slight im- purities as the quantity was too small to purify as much as desired. The compound gave negative qualitative tests for halogen and nitrogen, It was undoubtedly the methyl ketonic acid that would be expected if the structures of the preceding compounds were as supposed. T I “^> 4 =: '.■■w-*'^! t 'jfiJtftjr n ?.J ! a ''vifl^' V' ■• ^ **^*'!l" V^lnb;n, r iiiv^ < 4 4 *,l^ h :»4 „ ,A*^:-.' ^ - ,,, , ' . v'- . ^ X :■ '^e':': ^ ■ ■ / - , / '‘""e, .,1 1 ^A>*7 ,^ it?f -»i v^' i««» ciiSP : .' " *' ' ' ’’ ' • -’"®i ' ^ ''W' rtt >f'-?s, Tt 0 ■t=y-‘Z'' ^;'“,iW,>p/'fctt;^Vji^^if' ^a. • -. - . .' ''■ ■■ - '''"’” I i’C .,»■< ■* " ' ,-(j /■■ -■ ' '''’ ','»' '-'r'^i , 1 ^m 4 , .' •^ 4 '^'^< ^ ■ ' *■' ■':;: " vrLi J t " ■ ' ' 'f ■'■ isL D &R..iS’«i < Kv i .# .'.^i /ji j.‘«__' . yi.;. ,:5'*.. .V'.. ‘S *-k: ■' . ,C', ,Y*'- ■;>■■'';■ , . , .. *'"' t' ''■ ^ ‘ 'i'’*’ i'^ ’’it'* i^'it *‘ ' .V ■ ' *'■*■ -n ■■' /*- ■•. '' ■ r'"X "•' 1 , 1 . . . tfg ■ r/'i; ■•% Ai"»-j XX ... X ^xxx^’ ' ^ ■■ X^Xxm X:XX / . ,pfe .;■ ■■ X:^.;yXr^ - 40 - V- SUMMARY. 1- Broraoni t ro camphane on oxidation with nitric acid breaks down successively into camphor, camphoric acid, and camphoronic acid. 2- The course of the action of potassium hypobromite on camphoroxime has been found to be brominatlon of camphor- oxime and then oxidation to the bromonitrocamphane . No bromonitrocamphane hydrate is formed as was supposed by Forster. 5“ Potassium hypobromite may also act as an oxidizing agent on camphoroxime to produce hydroxy-nitroso-camphane , 4 - Strenuous permanganate oxidation of inf ra-campho- lenenitrile and hydrolysis ultimately yields the correspond- ing ketonic acid. 5- Bromonitrocamphane anhydride has been prepared by an improved method and the structure of the anhydride eluci- dated by its behavior with the Grignard reagent, methyl magnesium iodide. Since the structure of the anhydride is now an established fact, a logical explanation is provided for the unexpected transition from bromoni trocamphane to inf ra- c ampholenenitrile . , ,, ;.j .”'¥¥ ,1 :L . I ■'U, ■■.; : aJ| ■•w . M f i *(ti " 'i't^if.'.^ j^i'i'ff.'ttl&.ti-ttt'^f) .•■*fi»«■■,?'» (IB l•*|!^i^ i.-i t}j.<-UiTi,.ti ♦V (x<* /tA JO*- N-' ■a .. • ilud **0 « »>T ^ fc/Jt !<' / av ''a# tA ' ^»k': j?a» L«x\, ■■ , V'- X --1 ^aa av ■V. -T *» 't 1« ► lT Mf|p I ^A'i& i ?'a '.•.<»^’wit lii I'V»4- 4<5PI^' &■ \ ' Al- > ’ ’ ' -y ' v’i’ ., '.A-. -*.,' ' . s' >■ ■.'r!'"■‘|:^V^V 'i« Ai'LA»i: r~~ ^ "^z 4,;.v..'^Tr-^- ~ "- 'y- ~.„',*7'.y --■' s, .j,; rj.i-;i ' '. 'm.> ^ ' ' : Si:. ,_j, I, , , L m. . . . ,-.*-■ ... _. ly iw- ' ■ ■ '-■ ■'f >iii“ m 'A*' W- ' i,.l. W 'IJi-vv't.,.* ,.i.' ‘■‘f u. t fi ■ *'■ ■ A'.'. •' ' ‘ . : ■' i -Ifv ‘ S‘k^^SB^m ' A® . ^ Wf - 41 - VI-BIBLIOGRAPHY. . (0 Forster, Trans. Ohem. So c . ( 1397 ) 11 , 1050. ( 2 ) It II It It 11 * 1 i 4 i , ( 1399 ) . (^) n It II II n u> 251, (1900). ( 4 ) n II 11 It 655, ( 1901) . ( 5 ) n It n » I 2 » 108 , (1901). (6) II II n II 12 . 644 , (1901). ( 7 ) II II II II 12 . 264 , ( 1901). (6) II II II It 12 . 1005, (1901). ( 9 ) II II II II 865, (1902). (10) Gwinn., Thesis, University of 111. (1920). (11) Piloty , Ber. d. Deut . Ch. 5099, ( 1902) . (12) Forster, Trans. Chem . So c 11 , 199, ( 1897 ). (1^) Wal lach . Anna lien. 122 . 1 ( 1899 ) . ( 14 ) Wal lach . Annallen, 112 . 171, ( 1900) . Forster, Proc. Chem So c . 28 > 515, (1912). Forster, Tians. Chem Soc . 11 . 78 , ( 1905). Pope , It II ^71, ( 1895 ). Forster, n It 11 11 . 987 , (I9OI). Armstrong, Lowry. Proc " 11 . 162 , (1901). Kachler & Spitzer Proc , ” 11 . 217, (1901). -42- yil- VITA. The author was born on the 7th day of April, 1897# Columbia, Missouri. he attended several grade schools, finish- ing the eighth grade at Macomb, Illinois. Then he entered the Western Illinois State Teachers' College Academy and grad- uated from there at the end of four years, 1911 ~ 15 * In the fall of the same year, he entered the University of Illinois in the regular chemistry course and graduated with the B. S. de- gree in June, 1919* Graduate work was begun in the same Uni- versity and the M. S. degree received in June, 1920. From that time to the present, the author has been doing further graduate work here. The writer taught quantitative chemistry as Graduate Assistant during the year, 1920-21, in the University of II linoi s . Publications:- "Syntheses of Chromanes and Coumaranes" j Journal of the American Chem. Soc. Vol. 42, 157# (1920) by R. E. Rindfusz, P. M. Ginnings, V. L. Harnack. Fraternities and Societies:- Gamma Pi Upsilon, Phi Lambda Upsilon, and Associate Member of Sigma Xi.