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'.

,,

. BOBINSON

S]TNTEESTS
Na CO"

ON' TR,OPNTONE.

763

762

ROBINSON :

SYNTIINSIS

O}'

TIi,OPI)iOI{E.

Tropine
ol ol =-l

t"IY: \ '",

Tropino'e ": .: = : =
e ry'-'Jl'opin
o

Tropinont:c:irboxylic acid
l: I_
t: lt=
l :

a'pesitive eatalyst, by redueing tr'c-Vm, increases /c, bttt decreases rllogkf tl'l', and vice versli ior a negative cataiyst. These deductiorrs are in agreerrlenbrvitli the expelirrrental rcsnlt.; b r o u g h t f o r ryarcl in this paper. Furbhernore, in a" recent experirnental pir.per on the i-ihotoc h e n t i c a l c h a r t g e s o c c u l r i n g i n a c l r . t e o us o l n t i o n s o i c h l c , r o p l a t i n i c acids, Boll (.Lntt. I'/t.ry;ique1 , 914, [ix],2, 5,226) ]ras corrclu.lecl frotrt his rvorli thai thela exist int.:rnrecirrte a,ctive nhases of the reactirrg nrole,:u1es. GolclschrniclL ( l ' i t 1 , . r i / i a | -Z l i t ' c / t . , 1 9 0 9 , 1 O . 3 0 6 , 4 2 I ) , f r o n t t h e o r e t i c a l c o n s i c ' l c i ' a t i o i r -a ", lso rlrau's e sinrilar cotrclltsion. I\Ioreover, the receuL lvork by I3aly ancl his pupils absorption (T., 1908, 93, 21t18; 1912, 1O1, 1469, 1475) on tJrt-. sirectra of cotr.lrorincls has exPerirnentally proverl the existence of t l t o s e v e r y a c li i ' e p h a s e s o f n i o l e c u l c s a s i n t c r r n c r i i a l e s t ; r g e si n c l i e t n i c a l r e a c t i o n s s r t c h a s a c ' l v o cta rrl irr this r)ar)er'. f n c o n c l u s i o n ,I o f f e r n r y l i c r r l t v t h a n l i s t o P r o f c s s o r J . C . P h i l i p for his kincl help. atrcl to the Risearch Fuucl Conrnrittee of the Chenrical Societv f ol a glant rvhich nret parb of tire e\pcnses incurreclin this research.
IHprrrrAl C'oit r:r:u or.' Sctuscrr Lg+'llox, S.\'\'. -{N1) Tucuxototlv, Qt,:cCiucd, Jr-rrro 9ls/, 1917.]

lS

'v
=l

?,t \?,

Y r'-Ecgonirre

Atrcrp r n e

Hornatropine

't' l'-Cjocairr,,

l, \ I Il.-,1

of' Syt,tlLe,<i,\

'I't'oltit,orte .

IJv Rorr.trt Ilontxsr.rx. Auosc the ttoteu'olLjrvachie',,'etttetro ts f \\Iiiit'iiit1.cr iu cottnexiotr rvith iris irivestigatiorr of tlic cherrristly of tropine, thero was a greater shale to the fiual solutiou of nol-hjrg that corrlr-ibritccl t i r e 1 - , r o b 1 r . ' n rtsr r c o t t n { e r e r . 1t h ; r r t t h e c l e n r o i r - * t r a t i o r r o f t l r c c o n s t i t r - r t i o r ro f t l o p i u o n e , a h e t o n e f i r s t p r o c l u c e c l i n 1 8 9 6 ( \ \ ' i l l 2,9 , 3 9 6 ; C l i a n r i c i a na r r c l S i i l . r e r ,i b i d . , 4 9 0 ) b , r s t i i t t e r ' ,I l e r . , 1 , - S 9 6 the oxi,.latiori oi tloPitre, aucl la.ter bv a sirnilrrl nretliocl fronr e c g o t i i n e ( \ \ ' i l l s t i i t l e ' r ' ,I ) c r ' . , 1 8 9 , q ,3 I , : 6 ; 5 ) . T i r i s s u b s t a n c e b a s become the ccntr:rl ligure jn the atropile grolrp oI tlie aikaloids, and, as shown belor', rnay be regarcleclas tlie natural st,arLiug poiut in the synthetical preparation of a nurnber of bases of great valuo iu tho practice of nredicine aud surgery.

An exatttiuation of the details of the leeclions irri'olvecliu the abovo shou's tha b it is irnprobable that cocaine rvotrld be s y n t h e s i s e c lf r o n r a r t i f i c i a l t r o p i n o u e , a n t l t h a t t h e f e a s i l ; i l i t v o f the preparation of atropine rvouicl cLcpenco l lr the eial-,orationof implovccl methoils for the lriocluction oi tlopic acicl. On the o t h e r h a n c l , g i v e n r e a c i i l v a c c e s s i L l et l o 1 . , i n o n e ,t h e t e c h l i c a l 1 r r . ' e paration of homatropine and tropacocaine rrould be a conrpalatively simple matter. Bv lesson of tho richness of 'uhe fielcl of chemistry explored, tho synthesis of tropine by \\'illst[tter (,1nnalen, 1901, 3L7, 2A4: i?03, 328, 1) is classicrl, irut the methocl employed, rvhich ib is rlilrlecessa.r'y to recall jri rll its a chalacter to,i,lriii+, of detaiis, appears to be of too corrrplicated developrnent into ar collo,nical process. Ii is first of irli necei sary to obtain suberone, rvhich is then coni.elte,.l throuqlr severai 'into stages cycloheptatriene, and finally into tropidine, ,-'l'tropine, tropinone, and tropine. N e v e r t h e l e s s ,a n i n s p e c t i c , n o f t h e f o i ' r n r t l a o f t l c l r i r r o n , ' ( I ; t i i s closes a degree of syrlntetrv ancl an architectnlc which ju:tifv the hopo that the bass ma.y uitirrrately l-ie oirtaineci in goccl yieltl as the producb of some sirlrple reaction and f rorn accessibio l t ' , ' , . l l o l . r ' - ca js t the lroint:; in,.iitatecl b1' rnaterials. B;'irnrlinaly t h e c l o t t c e l l i n c . s . i h e s , u l-.t r r r i ' , . i n a . ; l ; c r r . c , l . , ' . r i i n t . r : u c c i n . i i aldehycle. rneLhviamitre, ancl acetouc, anLi thjs ol;sel'r-aticn suggested a line of attacli of tho plolrienr',vhich has lesulte,l in a direcL synt,hesis.

I I{,
I

CO ! NlIe crJ2 | | trl I ' \CII-i-CII2 : (IJ

(;,i ' I
/ctl--

- ctlI2

N]le I ul{o I

,''l c H "I

/CII----C

\t\cir{,-\

CO I

I I

: C II' tl(.II ol()"i t -'t f ,

-c: cH. c8}Ir :02: crr'

(r.)

764

RC'E }ISON:

SYNTEESIS

OF

TROPINONE.

'.T..j,:. ,NOBNSON

SYNTEESIS

OF

TROPI}SONE.

765

fn searching for a method of synthesis of any substance, it is ahvays convenient, to be able to recognise the formation of traces of the desirecl product, and in the present instance none of tho derivatives of tropinone already prepared was found to be so suitable for its detcction as the dipiperonyliclene clerivative (II), which does not appear to havo been hitlierto described. \\'Iith the aid of this hiehly chalacteristic cornpound it rvas proved that tropinorle is obtained in srnall yield by the condensation of succindiaiclehyr-lo rvith acetons and nrethylanrine in aqueous solution. An improvement folloived on the replacenreutof the acetone b y a s a l t o f a c e t o n e d i c a l b o s ll i c a c i c l . T h e i n i t i a i p r o c l u c t i s a salt of tropinonedicarboxylic acicl, and this loses tn'o rlolecules of carbon dioxide ri'ith the formation of tropincne rvhen tlie solution is acidified and heated.

ExpERTMENTaL. Dipilteronyliden etropittone (Fonnula II).

Potassium hydroxide (5 grams) dissolved in rvater (20 c.c.) rvas added to tropinone (2 grams) and piperonal (6 glams) dissolved in alcohol (100 c.c.), and ths solutioll \vas then boilecl uncler re{lux during fifteen rninutes. The derivative crystallisecl cluling the courss of the reaction, ancl, after the adriition of s,'ater, lvas collected, rvashed with rvater ancl alcohol, ancl cri'stallised fronr ethyl acetate. Tho yield was quantitative: II:5'3. 0'1139 gave A'2991COz and 0'0543 FI'O. C:7\'6; per cent. C " { I [ , 1 O 5 N r e c p t i r e sC : 7 1 ' 4 ; H : 5 ' 2 Dipiperonylidenetropirtone separates from ethyl acetato in briglrt yellorv needles melting aL 2140, and is sparingly soluble in most organic solvents. If it is rt. irberl on the sido of a test-tr-rbe and sulphuric acid addecl, tho substanco acquires a coppery lustre into an intense loyal-blue soiution. This beconres and t,hen pas-ses green and finally vello..v on clilution with 'water. The salis of the s u b s t a n e e a r e i n g e n e r a l s p a r i n g l y s o l u ] - . l e ,b u t t h e a c e t a t e d i s solution. Yellou', solves readily in rvater to a bright orange-1'e11on' crystalline precipitates of corresponding salts are obtainecl on the addition to such a solution of hyclrochioric, hyclrolrrorni.. nitlic, strlphrrric, oxalic, or picric acicl. The ltttrJrocltloride crvsiallises fronr hot rvater, in which it is sparingll' solnble, in vellorr, nricrol 1 hvclroxvlamine irt s c o p i c n e e d l e s . T h e s u b s t a n c e i s d e c o n r p o s e cb boiling alcoholic solution lvith the fonnati,.rtr of pi1-rer'etralosinc', ancl presr.unably of tho oxirne of troiriircne. Tho fortnation of tlie dipiperouylideno <lerivative selvei as a ureaus of detection of the rnerest tlaces of tropinone, arid the test . may be applied in the follorving nlanner. A solution r'.-hiclrit is suspected contajns the base rnay {ilst l-,c acidifiecl ancl e',':i1.,or:rtel'l i n a v a c u u n r i n o r r l e r t o r e t t t o r . ep c s s i b l e v o l a t i l e u e u t r a l i n r p u r i ties, such as acetone. Alcohol, arl c.\cess of pi1;elcnal, ancl p o t a s s i u m h y d r o x i d e a r e t h e n a d d e c l , a n c . lt h e s o l u t i o n h e a t e c l o n the stearn-bath for ti.vo or threo miur.ites ancl ther-r ponrecl into e t h e r . T h e e t h e l e a l s o l u t i o n i s r v a s h e dr v i t h u ' a t e l a u c l s e n a r a t e d , If and then agitated u'ith a little dilute hydrochloric acid. tloyrilionp is present, the hydt'ochlorirle of the derir':rfi'.'e is so obtainecl in a crystaliine conclition.

/cFIO C,H, |
CHo

+ NHrlIc

-->

// I cil,
I
I

/c}.l.oH NlIo +

c IIr.CO,ca

I
OO

\-

'{"I
-->

->

\c so
,'' I c F I2 I N l I,r I C II2
! \ l

\,jtt.ot

cHr.cr),ca ,/,cI1--cH"
/

/?IJ--c

rr.co,c,,,
CO I + :H C l

CH, NlIe I 0I{"


\r

* CaCll"

\cH--c

I I. c , , r . u

.\ \oH--cil2

CO I i

+2COz

Tlol-'inono \\'as also obtained by ths hvch'olvsis of the producf of condetrsation of succinclialdehyde rvith ethyl acetoneriicarbo-xylate atrd rrreth.ilatnine in alcoholic solution. When nlore rnateriai is available it is hoped to institute a. series of experimetrts with the object of defining tlie optirnum conciitious of ths synthesis, ancl it rvill then be possible to state rvith nrorc exactlless the maxinlum yield obtainable. florvever, in spite of the smail ex1;eriencs s o f a r g a i n e d , a n e x p e r i u l e n t i s d e s c r i b e c li n l v h i c h tho yielcl of dipipcronylidenetropinone fronr succinclialdehv{e rvas 42 per cent. of that theoretically possii:le. The methocl of synthesisof bicyclic basesrvhicjr has been developed is probably of general appiication, and an attempt rvill be made to synthesise r/-peiletierine by the condensation of glutardiaidehyde with rnethylamine and a clerivative of acetorro.

766

R,OBINSON:

SI'NTIIESIS

OF

TROPINONE.

R,OBINSON: A

SYNTHESIS Otr' TROPINONE.

767

Syfihesis ot' ?ropinone from Succitrdirrlrlr/t.ycle, tr[tt/t,!/rtrttirtc, ctrtl A c e t ot t e . In this reaction, rvhich has nr.'t yet been suflicientlv invcstig a t e d , i t s e e l n e c lt h a t t h e t l o n i n o n e c o u l , d o n l y b c c l e t e c t e c la f t e r the expiration of a brief pericd froin the tinre of addition of the inethr-larnirre. If the leaction rri:ltule \\:iis allon'e,1 to remaiu overtrigirt, other l;asic ketones rvcrc obtrined n'hich conr'lensedu'ith piperona,l anci intci'fereci rvitir the lccoqnition of thc rlc:ilccl pro duct. Succincllal.loxirne(i glarns) suspencleci ln rvater (30 c.c.) \\ri.i.s con'n'erteclinto srrccirrclialrlehvcle lr)' ilrcllns c,f nitrous frtrnes generatecl frorn nitric acirl (D 1'3) ancl arseniotrsoxirle accorcling t o t h o m e t h o d r l c v e l o l ; e r l l rj ' F l a l l i e s ( I | r r ' . , I 9 0 1, 3 4 , I 4 3 1 ) . \ \ r : r t e r ( 5 0 c . c . ) r v a s t h e n a d r : l e r l ,a t r r l t h e n i t r o u s a n r l n i t l i c a c i d s netttlalisecl bi. tneAlrs of an e:iccss of 1;r'ccilrit:rtcd calcinrrr carbonate. After the aclrlition of acctorre (5 glanrs), ancl then m s t h v l a m i n e ( 4 ' 5 g r a r n s ) c l i s s o l v c c il r r s ' a t e r ( 2 0 c . c . ) , t h e n r i r t u r e was allol'ecl to remain rlurittq half alr ]rorir. The solutiol was aciclified ri'ith h-vrlrochlolic acicl ancl testerl for tropinone bv th-e r n e t h c c i d e s c r i b e ' 4 a b o v e . T h e - . na r l i q u a n t i t v o f t h e c r v s t a l i i ne hvdrcchloricle was collectcd, treatc.l r.,-it'h a little acrueor,ls a.rnnrouirr, anil the base crvstallised from ethyl acetate. The vellorv neeciios r t r p l t e r la t 2 1 4 c . a n d a t t h e s a r n e t e n r P e r a t u l e r v h o r r r r i x e r l s ' i t l i r r s p e c i n r e u o f d i p i p e r o n y l i c l e n e t r o p i n o n e . T h e c o l o n r r e ac t i o n s o i the tti'o speciitretts i n c o n c e n t r n t e c ls u l p h u r i c a c i r l s ' c t ' e i r l e r i t i c a l .

Syntltesis of Tropirtone from Su,ccirtdiulrlehyrle,trIethylttntine, ancl,Calciu rrt Acetonedicrtrbonylate in, AqueoLts So/utiott. Succirrcliaido:<irrr (e 3 ' 5 g r a r n s ) r v a s c o r r v e r t e d i n t o d i a l c i e h y C ei u tho usuai utanlrer, ancl after the neutlalisatiorr rvitlr. challi the solution was tnarle up to 40 c.c. and mi:iecl with acetonecl.icarbo x y l i c a c i c l ( 4 g r a i n s ) c l i s s o i v e ci t r w a t e r ( ! 0 c . c . ; a n c l n e r i t r a j i s e c i by the acldition of caicirim carbonate. IIetirl'lanrine (f rom 8 gratns of the hi'circchlc',r'idc)in rvatcr (i0 c.c.) r';as thcn gracl'.tally added, and the rvJrole allon-ecl to lentain at the orciinary teurpelatule cluririg 1ifty ho.rls. The liqLiid u.as fi1te1e,,1, :rcidirreci with hydrochloric a-cid, ancl concentrated in a vacullnl, usirig a l a l g e f l a s l i o r r a c c o u n t c , f e : : c e s s i v ef r c t h i n g . T h e l c . s i r i u e r , \ ' a s then rendered alkaiiuc x'itlr. socliurn hyclroxicle arrii ciistiliecl in a cttrrenf of stearn until tho tiisi:illate rvas ucntra.l to litnr'"rs. This solution rvas then aciciifieclriitir ]rvclr'cchlolic acid, conccntratccl in a vacurlm, and, after the addition of soclinnr hydroxide, repeatediv extracted n-ith ether. Thc conrbirrecl efheL..al esttacts rvere driecl or,'er Potassinnr hr-dloxirle, sonrervhat rapirlly in older to avoid tho fortrtation of salts, arrrl the solvent lemor-erl by distiliation. llhe resiclue grtcltrally crvstlliised. oily irirl;riliiies u'er''-. r e r n o v e c lb y c o u t a c t r v i t h p o r o i r s p o l c e l i r i n , a r r c l t h e s n l , . , t, , i i c e\ t a s :. Long, recrystallisccl frotn light petroleur;r (1r p. .-10--60t flattenccl, poirrtcri, coiotti'icss reccllcs ri'elc o"btaine,l rneltiirg at .1!o, hn e q r , i i : i c l u a n t i t v a n c l a , t t h e s a u r e t e n t p e l a t u r e r i ' l r e n r i i i ^ r . e , 1 . r i ' i ta of tropinono rvliicir haci l;eeu obta.inecibr. tire oxiclubiou ci tlopirre. u'ere irierrticai. Iror ftirthtr' In evely lesircct the trvo srpecirr-Lens cottrparisorr the lricrate was lli'epzrrecl. It clv.;ta-llised irr-,ttr r','ater s r e l f i n g a n t l c l e c o i n l , o s i n ga t j 1 , i - * l l u - ' i n c a r l r l y - y e l l o , r n e e c . L l en alone .rr rvhen mixed r.,'ith tlopilone 1;iclate, rvhich ha,i irr this oi,tain. J.by tlic o:,i,lrtion ol' ccgrr11j11s. casc bc,-'rr rc-,rn b a s i ' w a s r e c o \ - c l ' . ( .f 1 Thc oil scparaterl frour the cr1'si.allirre the plato by c.':tractiotr *'itir ether, atrd after lr.tnor-rl of ths solvent. piperonal, a1coiro1,anii potassiunr hycli'osirle v,'erc aclrlecl a n c l t h e m i x t u l c h e a , t e c lc l u l i n g f i r r e r n i r i r i t e s o n t h e s t e a r n - b a t h . on ths acldition of rvater l'z,s collecterl, Tho preciiritate obt:rirre,,1 r v a s h c d l - i t h a l c r r h o l , a n c l t h e n c r ys t a l l i s e c l f l o i n e t h - ' ' l r t c c t a t e . Dipiperonl'liclcnctropinonc rnelting at, 214c n'as thus isciated. Trr the abovo experirnett{; thela is sorrte rincertairttv as to tho staltecl f ront, siuce thc author, no arrtount oi succittclialrlehycle doubt throngh lack of plactice, has never been able to obtain the In high yield claimed by Ilarries of frorn 70 to E0 per cent' order, therefore, to gain some idea of the yield of tropinono from succindialdehyde, the following experiment was made, but the H II'T

, \ r y r t t / t c . < io .; f Trctpinonc frotn,\ttcrirr,l.:rrlrIrh,title i,Icthylcttttirrr', i l. a n r l / i t / t y I A c e t o n r r l i c a r i i r t .t i 1 ! 1p a - S u c c i t i c l i a l c l e h v d e( 1 g r a n r ) a t t c l e t h y l z r c e t o n c d i c a l h 6 y l ' 1 2 1 s ( 2 ' 5 g r a r n s ) r v e ' r ec . lis.;c-,lvc ir ,1 r a ' l c o h o l ( 2 0 c . c , . ) ,a r l 1 1 ,a f t e r c o o l i u g in ice-'tvatef) a solution of rnethvl:rrnirrr_ ' ' j grarri) in alcohol (10 (0 c.c.) rvas gracitrelly aclricdduring arr horir. Afttrr rernaiiiing over.night at the orclin:rry tctttlteratttre. tfte alcc|ol \\:ir"s ltllpc\:erl l,rv disiillation in a vacutun, ancl tlie resir.lilc boile.,l rvith ciilutc sulirhnric a,:icl fol half ern ]rour ancl then evapolated iu a irigh vacLrrir]r to srnall Luili. Potas:.iurn hyclroxiclc rva.sthen adclcd in o-\cess, and ths mixtule clistiiled in a crlrrent of stcarrr. flhe distillate \-,'ase\actl.1' neutlaliscci n'ith hych'ochlor.ic acir.l, concent i : a t e d , a n d t h e t r o p i t r o t r , :c o i t t a i n c c l r v a s i d c u t i f i e c l a s i n t h e f o r m e r exanrplo by convelsion into the dipiperonyliclene derivative, as described abovo. rn this case also the identity of the synthetical product rvas establishecl b; the method of nrised melting points.

768

BOBINSON : A STNTEESIS

ONt IBOPINONE.

TEE PIINGENT

PR"fNCIPLES OF GINGER,.

PABT I.

769

cond-itions of the synthesis aro stiil under investigation, and it is hoped that even better results may ultimately be obtained. A solution of succindialdehyde containing inorganic salts was first prepared in ths usual rvay and then clistilled in a curreut of steam. The distiliato rvas concentrated in a high vacuum until, as ib later appeared, aboub a 10 per cent. aqueous solution was obtained. Ten c.c. of this solution were diluted rvith rvater, and ths dialdehydo was converted into the dipheuylhydrazone, as described by Harries (Ber., 1902, 35, 1188). The solution contained 0'96 gram of succinaldehycle. Tiventy-fivo c.c. (contaiuing 2'42 grams of ths dialdehyde) were rniried with & solution of acetonedicarboxylic acid (6 grarns) in water (75 c.c.) to rvhich a suflicient excessof precipitatecl calcium carbonats had been aclded, and after cooling in ic+'water, metb.ylatnine (3 grams) irr rvater The reaction was allowed (10 c.c.) was gradually introduced. three days for completion, and the liquid was then acidiliecl to Congo paper rvith }iydrochlonc acid and cotrcentrated in a high vacuurar. The residue was dissolved in alcohol ancl the tropillono converted into dipiperonylidene derivative in the usual manner. The product rvas collected, rvell rvashed rvith rvater and a little alcohol, and dried at 1000. Ib weighed 4'I grams and rvas freo Tho substance \\'as identilied as from inorganic impulities. dipiperonyliclenetropinone, ancl the above data shorv that the yield of tropinone frotn succindialdehyde in this experiment was 42 per cent. of that theoretically possible. Tho possibiiity that tropinone miglit, resuli frorn the condensation of sttccindialdehydeor a derivative'n'ith acetolle or a derivative and rnethylamine or by the adclition of rnetlivlamine to a r'.irlohe1i+"adienon oe ccttrrecl sinlultatteor-rslt'to I'roiossor A. Lapl v o r t h a n d t h e a u t h o r , a n d a j o i n t r e s e a r c h r v a s c o n t e n i p l a t e c i ,b u t Dr. Laprvorth's preoccupation rvith rnoro urgent investigations did not allorv hirn to undertako this fresh experimental u'ork.
I]xrvt--nsmv or LrvnRPooL. [ R e c e i v e dJ , uly l3th, l0l7.l

Pungent P rinciples of Gitry,:i'. Purt L LXI\r.-Th,: A Neu lietone, Zhigcrone (a-Hydt'o.xy-'i-tirethoxyht Girryer. phenylethyl .I[etltyl Iietone.) occtLri'itt11 By lhnosur Norrun,r.
plinciple of T s n E s H a s s i g n e dt h e n a m e " g i r r g c i ' o i" t o t i r e 1 ; u t r g e n N ginger, and Garnett and Grier' (I'/t,ornt. J., 1907, [i"], 25, 118) clairned to have isolated it. Ilorvever, no accotlnt of au iuvestigation of its conrposifion and constitution is to be found in the Iiteratnre, arrd tho preseut rvork rvas unclertakeu to deterrnirie ths constitution of the pungent pnnciple. The neri' ketone, to u'hich thc llanle " zingerone " is assigtred, was obtainecl by extracting gingcr rvitir ether, follorred by tlre treaLnrent describeC on p. 770, anrf \\ as provecl to have It yielcls mono}renzoyl and monoacetyl tire formr"rla CllIli{OB. derivatives, and the existence of one rnethoxyl groLlp in it rvas provecl. Tlle nrethyi clerivative,C'II16O3, is readily converted into its oxinre, Cr"IIriOrN, by hl,droxylarnine, rviricir points to the presence of oue cariron,r'l group. \Vhen tho metirvl derivative is oxidised tvith potassium permanganate in alhaline solution, veratric acid is obtained, and therefore the nerv ketone nrisL be a 1 :3 :4derivative of Lrenzeue. Since sodium hydrogeu sulphite cornbiues rvith the neiv ketone and rvith its rnethyl derivative ancl the latter is oxidisable r.;ith clifficulty by an amrnoniacal sciution of silver nitrate, the group, CO'CFI', appears to exist in both comporinCs. If this is the case, the constitutional fornrula of thc methyi derir.atirre nrust, be eitirer (I) or (II), and thc corlstitrltion of the original ketone rnust bc Olle OlIe

cotle.CH2.Crr,/ )orto
(L)

colle'clrlre< )orr"
(II. )

(III), (I\'), (V), or (VI), according as the methyl derivative has the constitution (Il or (II) respectively. In order to decicle betrveetr

0IIe Colte.CH 2,eIL"( -\Otr

OH

(rrr')
Colle'CHlIo(

oue
-\911

cotrIe.crI3.cII,< )ou. (r\,.) oH -'


Colle.cI{ Me( \orru \_-// (vL) be used. uHx2

(v.)
bhese, the following two methods rnay

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