1202 SINQH STUDIES IN SUBSTITUTED QUATERNARY AZONIUM CXX X1.-Studies in Substituted Quaternary Axonium Compounds coutaining an Asymmetric Nitrogen Atom. Part 111. Resolution of Phenylmethyl-ethylaxonium Phenylbenzy~propylazon~u~~ and Phen?llBerLzyIallyla~onium Iodides into Optically Active Components. By BAWA KARTAR SINGH. IN Parts I and I1 od this selries od rmearchm (T. 1913 103 604; 1914 105 1972) t,hel a'utholr has deecrib,e\d t,he resolution of t,wo members of a new type of ena(ntio1morphous compounds, R,R,R,XN*NR,, the asymmetry a,nd oonselquently the optical actiivity of whiuh is associated with the presence of an asymmetrio nit,rogen afom. The prewnt investigation which is a cotntdnuation of this work, is uoncwrneId with the resolut,ion of phe~nylme~tlhylet~hyla,zoniurn iodide the previoasly determined value oQ t,he moleioular rotmatory power of which was considered t'o be ra'ther low (Zolc.cit.) in a,dditJoln to! t,hat of tlwo other meimbelrs namedy phenqlb e m ylpopyl-azmiu,m and phenylb e~zyEaUyZazonim~ iodides. Phenylmethylet8hyla.zonium ioldide was resolved with tlhe aid of silver &u-b,romooampht-fl-sulpho~na~te. The IBdA d t being less soluble sepasa,ted in a crystalline form and gave for t'he I-basio ion [MI - 2 3 O tlhe maximum rotation of -3OO' having a h a d y been olbta,ined froim t'he hydrogeln tlartrata (Zoc. c i t . ) . It is thus very probab'le tha,t t'hs folrmer vadus of -30° is the maximum molecular rota%toil.y power of t,he Z-b,asio ioln. Anohher point od interelst is t,hat I-phenylmet8hylelthylazolnium pimate has aJmost identical va,lues of [MI in chlorodoirm and meithyl alcohol solutions (sees p.1206) a.nd it thus stands in note worthy contrast with phenylbenzylmethylaaonium picrate t$he va,lue of [MI of whioh is t,hree times as high in chlolrofosm as in msthyl dooholl (T. 1914 105 1984). This polint,s t'o mole,cula.r assooiation of the la,ttm piorate in chlolroform but so fa'r this view has not been colrro;boil.ated by a detIelrminafio~n ovf molecular weighte in the t'wo solvents. Pheinylbenzylpropylazolnium iodide coald olnly be1 obtlaineld in olne way namely by the1 a,ction oB b.enzyl iodide on phmylpropyl-hydrazine. I n tfhis reaction a very small amount of a hydrioldide was also folrmed as a by-product The action of propyl iodide o COMPOUNDS CONTAINING AN ASYMMETRIC NITROGEN ATOM.1203 phenylbsnzylhydrazine ga,vve t'wo hydriodides mejlting at 146-147' a4nd 162-1 63O respectivealy h i d e s ammonium iodide. No azolnium iodide was however formed in this reaction. The action od propyl iodide thus seems to be a.bnormal and was further studied on two otlher hydrazines. In the case osf phenylmethyl-hydraxine the sole product of t h s a.&ion of this iodide was ammonium iodide and in tha.t off phenylpropylhydrazine at first no product was formed but on keeping the! mixtnre f o r some time a very minute quantit.y of ammonium io'didel was isohted. It' may be suggabd tha,t t'he secondary hydrazine is slowly reduceld t,ol a a amine and ammonia, and the la,tteIr substlanoe combinw with hydriodio acid to form ammonium iodide.The hydriodia a'cid ma,y be produced from the hydrolytic delcomposit'ion of propyl iodide a,nd itl velry prolbably act8 also1 ass the relduoing agent. Phenylbenzylallylazo~nium io+dide was prepa.red from the action olf benzyl iodide on phenyladlylhydrazine. This reaction was quite normal . I& esoll.2~ ti,on. -P henylhnzy1pro;pyl azoniurn iodide was resolved by t'he aid of silver d- camp holr- fl-sul p holn at.e and d-a-brom oomp hor-P-sulphonats. In the case 04 the camphorsulpholna8tes the dBdA sa,lt, being lelss solubmle in a mixtlure of melt8hyl alcohol and ether, first separat,ed out. It hajs [MID +357*5O in met'hyl alcohol a.nd +300.5O in aqueous solution. The ZBdA sa,lt was oib,tlained by recrystallisa'tion fro'm wafer in whioh it is lelss soluble t,ha.n the other cmponelnt' and has [MI - 153'2O in melthyl a h h o l a.nd - 190'9O' in a,queous solution.Ta,king [MI folr t,he dcamphor-sulphonia acid ioa as +53O the! dBdA salt1 give6 +247*5O and the ZBdA sa.lt - 243.9O far the1 d- a,nd I-b'asia iolns in a,quelous solut'ioln re8p eutivsl y. On t-he &her hand if we assume tha#t the sa81ts dBdtA and ZBdA behave normally in rapedl of tlhe a.dditive character of the mole-culas rota8tolry power of t'he two ions in aque'oas sdut,ion the value of [MI, for the d-oampholrsulphonic a,cid ioin is deduced to be + 5 4 * 8 O and that for the basic ioa k245.7O (ses p. 1210). The agreemeIntl be'tween the above figures is sufficielntly dose, and t,he value of [MI for the d-campho~rsulphonio acid as above deduced furt,helr shoiws t,ha<the tlwwol salts dBdA ZBdA ha,vel beebn olbtained in a pure condition.It has adre'ady been polinted out in the case of the camphos-sulphonafw of phetnylbelnzylmelthylaao~nium (T. 19 14 105 1973) thati three cases .may occur when an e8xtlernally compeasated base is crystallised with an optioally a.otive acid (1) the two salts dBdA ZBdA crystlallise separately so tha't elach may be readily isolated; (2) a part'ly r a m i c compound dBZB 2dA may b 204 SINGH STUDIES IN SUBSTITUTED QUATERNARY AZONIUM formed in whi& case resolution is impoasiblei; (3) each crystal which s e p a r a b may wntlain both the salts dBdA ZBdA in vary-ing proportions; in other words the two salts form solid solutions, one in the other and resolution is very slow and incomplete.In the case of the oamphorsulphonatee of phenylbenzylpropylazonium, behaviour of two kinds (types 1 and 3) is observed. After some of the dBdA ZBdA salts are separated in a pure condition the r s i d u d salt having [MID about +35O consists of 46 per cent. of the dBdA and 54 per centl. of the ZBdA component. On further crystallisation from water rn well as from a mixture of methyl alaohol and ether resolution proceeds extremely slowly as is seen from the1 rchatioln colnstanta. It is t.hus clear that the two salts have formed solid solutions one in the other when their composi-tion comeisponds with 46 per mint. of the dBdA and 54 per cent. crf the ZBdA component. I n the1 case of the bromoaamphmsulphonabs the 2BdA corn-ponent which melts atl a higher tempelrature first crystallism from a mixture of melthyl alcohol and ether.The dBdA colmpolnelnt, on reorystlallisation is obtained a8 an olil which could n& be Itollidifisd. The pure ZBdA salt! melts at 178-179O and has [MI +71.2O in aqueous solutioa. Phe~nylbenzylallylazonium iodide was resolved with the aid s f silver d-camphor-P-sulphonak. The dBdA componelnt being lelss soluble in methyl alcohol first separated out. It melts a t 147-14B0 and has [MI +190-3O in aqueous solution +2650 in chlolrofolrm sojlution + 285.7O in rnelthyl alcolhol and + 319.20 in ethyl alcohol. EXPERIMENTAL. Phenyhe t hylet hyJazonium d-a-Brolmocamphiw-~-sulpho~at e, PhMeEt (NH,)N*S03*C,,H,40Br. Finely polwdereld azonium iodide (25 grams) was addeld in mall quantities at a time to m e mo~lelmlar proportion of silvelr d-a-broimoicamphor-P-sulpholnate (37.6 grams) dissolved in boiling melthyl alcohol on the water-bath.The1 oontents of the flask were kept shakeln and after the addition of the whole of the azonium iodide the heatling watj continueid for half an hour to complete the1 reaction. The methyl aloohol was distilled off and the residue, consisting of solid silver iodide1 and the syrupy brolmocarnphoc-sulphoinate was extlracted in the usual way with methyl alcohol. On evaporating the1 methyl alcohol an oily rwidue remained which did noit crystallise elven on keeping for six days. It wits again dissolved in almhol and precipitated as an oil by the addition of ether. After some time fine needle-shaped crystals began t COMPOUNDS CONTAINING AN ASYMMETRIC NITROGEN ATOM.1205 appear and a portion of the oil slowly became crystalline; this amounteld to 9.7 grams and melted a t 152-153". The remaining portion of the oil did not crystallise even on keeping under either for six months (Found C = 49.05 ; H = 6.74. C,,H,,O,N,Br requires C=49*46 ; €I = 6.29 petr centl.). The rotatory power* of the salt was determined a t 29O in acqueous solution : Substance. Gram. Time a,. [MID. 0.1738 - + 1.11O + 293.0' 0.1738 After 25 hours. 1-13 298.3 The above camphorsulphonate (8.8 grams) was dissolved in the least possible quantity olf rnelthyl alcohol and preoipitateld by gradual addition of elther with the1 following result: Yield. Substance.Fraction. Grams. M. p. Gram. UD. [MID. A ............ 2-2 154-155' 0.2960 + 1 0 8 6 ~ +288*3" €3 ............ 5.9 155 0.1792 1.12 286.6 Fraction B was submitted to the same procas and the1 rotatory power of fractions C and D into which it was resolved was determined with the following result: (in 20 c.c.) Yield. Substance. Fraction. Grams. M. p. Gram. ab. [MI,. c ............ 2-1 15G-156' 0.2184 + 1-41' +296-2' The rotatory polwer in all the1 abolve cases was determined in water a t 29-30'. The lowest value1 of [MI f o r the ZBdA salt is about + 287O and since [MI for silver &a-bromocarnphor-P-sulphonate (Pope and Rea,d T. 1914 105 809) is +31O0 the molelcular rotatotry power f o r the I-phenylmethyletthylazonium ion is -23O (287-310). ............287.8 D 3.0 154- 155 0.2454 1.54 dl-Yhen?j1912ethylethylcEzonlirum Picrate, PhhleEt (NH,)N O*C,H,O,N,. This salt wa4s obtained from the racemio azonium iodide in the usual way as yellow prisms melting a t 110-11lo. It is veiry reladily sohble in acetone less so in methyl alcohol ethyl alcohol, or ahlorodorm moderately so in water and insoluble in &heir (FoIund N = 18-63. * The given weight of the substance waa dissohed in 19.9 C.C. of solvent, and the rotatory power determination was made in a 2-dcm. tube about thirty minutes after solution. This applies to all the observations recorded in this paper unless the contrary is stated. C15H1707N5 requires N= 18.47 per aent.) 1206 SMGH STUDIES IN SUBSTITUTED QUATERNARY AZONIUM 1-Phemylmethylet hylazoniurn Picrate.The aotivs piorate was prepared by adding an alcoholic solution of the bromocamphorsulphonate of the I-base to an alcoholio solu-tion of picria acid. On concentrating in the cold water was added when yellow prisms separated which after on0 or mor0 recrystallisatiolns from aloolhol and ether mellted and deoomposed a t 114-115°. A mixture of the dl- and Lpicrate melteld at 107-108°. It is very readily soluble in acetone less so in methyl alcolhol ethyl alcohol o r chlocoform moderately so in water and insolluble in ethelr (Found N = 18.14. C,,H,,O,N requires N = 18-47 per wnt.). The1 rotatory-powelr determinatiions gavel the following values : Substance. Tem -Gram. Time. perature. un. 0.2748 (in 20 C.C. methyl alcohol) hr. 27.5" -0.16' - 22.06' 5 hm.27.0 0-17 23.4 0.2977 (in chloroform). . . . . . . . . . . . - 27.0 0.186 23-56 2% hrs. 27.0 0.18 22.08 y* 7 9 28.0 0-17 21-51 32 1 9 27-0 0.10 12.67 The rotatory power of the above picratet is practically identical in both the solvelnts. This is notelwworthy as phenylbenzylmethyl-azonium picrate has [MI three t i m a as high in ohlorotform as in melthyl alcohol (T. 1914 105 1984). This is probably due to assodation ot the molleoulea of the lattelr piorah in chloroform. as-Piz emy 2-a-propylhydmzk PhPraN*NHz. This was prepareld by dissolving sodium first obtained in a fine, granular condition by mellting it under xyleae a,nd vigorous shaking during ooding in thet calculated quantity of phenyl-hydrasinel a t 1 80° under diminished pressure and t8retating the1 resulting sodium phenylhydrazine with prolpyl bromide1 (Michaelis, Bey.1897 30 2815). The selcondary hydrazina wm punfield by ooaversioa into1 its hydrochloride (silky nesdles) which melts at 147O and nolt at 135O as stated by MiChadis (Found C1= 18-89. Cah. Cl= 19.57 per mat.). Phe.n?lI-a-plro~ylh.ydrazirte hydrofe.rrocyamide, ( P hPraN ONH,) 2H,Fel( CN ) 6, is obtained as a white preoipitlake by the addition olf a colncmntlrateld solution of potassium felrrolcyanidet to a ooammtrated solution of phenylpropylhydraxine hydroohloride acidifield with hydrochloric acid. It is suoaeasively washed with a lititle wa;ter alcohol and eltheir and dried in a vacuum deeicoator. It is very readily solubl COMPOUNDS CONTAINING AN ASYMMETRIC NITROGEN ATOM.1207 in watelr but less so in alcohol. On exposing it to t>he air for some tJme i t acquira a violelbblue d o u r (Found FEY= 10.67 ; N = 26.65. (C,H,,N,),_H,Fe(CN) relquires Fel= 10.85 ; N = 27.14 per cent.). dl-Phemylb emzyZprqyZazoniu8m Iodide PhPra(CH,Ph)(NH2)NI. (a) By the Action of Bemzyl Iodide om PA,anyIlrropy2hycFra,zine. -An ioe-cold ethereiad solution of phenylpropylhydrazine (from 30 grams of the hydrochloride^) wa,s a.dded to one imleoulas pro-portioln of an ethelreal solutioln of belnzyl ioldidei also1 coolleld in ic8e. The crude prolduct (33-5 grams) after recrysta(1lisation from melt,hyl a h h o l and ether mellted and delcomposeld a t 125-126". I n some experiment8s the yie'ld wa.8 even be'tter. Itl is very reedily soluble in melthyl adcoholl solmewhat less so in eithyl alcoholl stlill l.ess so1 in wa.t,er and insoluble1 in benzelnel or elthelr (Foand I = 34.61.Cl6€IzlN2I requires I = 34.49 per cent.). From the filtrate on keeping for scme time a very small amount of anckhelr subst,ance se'para,ted. This was noh an axonium iodide[, butl a hydriodide as it gave an oil on trelatmelnt with a solution off sodium carbolnak. ( b ) The Actiom of Propyl Iodide om Ph~zylbenz?llhyd9-a,zine.-The action o f propyl iodide on phenylbenzylhydra,zine did not give the axonium ioldids obtlaiaed under (a) but wha.t appearerd t'ol be a hydriodidel 8,s the produat gavel an olil o a treatment with sodium carbona,te. The! mother liquoa oln ke'eping for selverad weeks, deposited a sma.11 amount od a,nolthelr substance which did not melt, but evolveld ammolniao wit.h potassium hydroxide.It appea,rreld t'a be ammonium iodide (Found I=86.88. Calo. I=87*6 per celn tl . ) . dl-PhenyIbenzy1plro~ytazoYniu.m. chlo*ride, PhPra( CH,Ph) (NH,)NCl, is olbtained in the usual way from the corresponding azonium iodide a.nd mystallises from alcohol1 and &her in collourless prisms melting a.nd deoomposing a t 145-146O. It is very readily soluble in rnelthyl alcoholl ethyl alcohol a,aelt,onne olr watelr but insolub,le in ether (Found N = 10.53. C16H,,N,C1 relq,uires N= 10.15 per cent.). The oorrelspolnding @&nichZolride is a buff -ooloured substanaer It is insoluble in water olr organic media (Found Pt = 22.03. (C,,13,1N2C1)zPtlC14 requires Pt=21.93 per mnt.). The dl-a;nr&hlo&de is first obt~ajned as an oil which on rubbing and allolwing to remain beco'mea cryst.alline1.It recrystallises f r m posing at 151O 1208 SINGH STUDIES IN SUBSTITUTED QUATERNARY AZONIUM hot alcmhd in yellow prisms melting and decomposing a t 132-133°. It is very rea,dily soluble in acetone sparingly 501 in m0thyl alcohol, ethyl aloolhol olr chlorofoirm and insoluble in wa'ter or ether (Found Au = 34-08. C,GH2,N2C1,AuCl relquirels Au = 34.0 per celn t . ) . On keeping for a few days in a stoppelred bottle it decomposm to a dalrk brown semi-solid mass hydrogen chloride1 being evolved. Ph e n y 1 b e m y l p o py l m orzium d-Camphor-8-sullrho~at e, PhPrn( CH,Ph) (NH,) N- SO,*Cl,H1,O. Finely powdelreid phenylbenzylprolpylazonium ioldide (30 grams) was added in m a l l quantities a t a time1 t o one molelcular propor-tion of silver d-oamphor-P-sulphonate contained in iir mortar.Melthyl alcohol containing a few drops of water was a,dded t o moisteln the contents of the1 mortar and the mixtlure was carefully triturated. This procedure was adopted in plaw of the usual one in order to diminish the decomposition which raulteld when the constituents were helated together with ethyl aoetab olr alcohol. The mortar was kept in a vacuum desictcatolr and the soilid residue was extracteld with methyl alcohol1 in a Soxhlet apparatus. On maporating off the1 alcohol 33.8 grams of the camphorsulphoaate (tlheloretioal yield 38.4 grams) melting atl 185" welre obtained. It is velry reladily soluble1 in methyl alcohol ethyl alcohol acetonel olr chlorodolrm molderatdy so in water and insosluble in benzene or eltheir (Foand C = 65.88 ; H = 7.63.C,,H,O,N,S requires C = 66.12 ; H = 7.63 per cenlj.). d-Ph eny 1 b enz y 1 pro py laz omliulrn d - Cam ph o r - /3-su lph on& e . The oampholrsulphonate~ (32-8 grams) as prepareid above! was subjelded to fractional precipitlation by first dissolving it in the least polssible quantity of methyl alcoholl and then gradually add-ing pure. anhydrous ether. The following five fractions were obt'ained : Fraction. Grams. M. p. Gram. a,. CMIW 1 ............ 6.9 187' 0.1727 +0*76O +206-7" 2 ............ 6.8 190-191 0.1 858 0- 145 36.65 3 ............ 16.7 189 0-1 965 0.32 76-47 4 ............ 0-33 186 0.1982 0.307 72.75 5 ............1.7 184 0-1806 0.24 62-41 Yield. Substance. The ro'tatory powelr was determined in methyl alcohol at 30-31O. Fractioln 1 a<fter remystdlising several times gave the pure B d A salt melting a t 190° with tlhe following values for rotatory power COMPOUNDS CONTAINING AN ASYMMETRIC NITROGEN ATOM. 1209 Tern- Time. Substance. Solvent. perature. Hours. Gram. a * [MID. Methyl alcohol ...... 24.0' - 0-1340 + 1.02' + 357.5" Water .................. 27.0 - 0.0963 0.616 300.5 , .................. 25.5 0.0963 0.613 299.0 , .................. 26.0 47 23 0.0963 0.61 297.5 Thus the pure salt dBdA melts at 190° and has in metthyl alcohol and +300.5O in aqueous solution. +357*5' 1-Phenylb emx y Zpropylazoniunz d-Camph or-P-sulpihona<t e . Frachions 2 and 3 (amounting t o 23.5 grms) after several further fractliolnations in the usual way gave 6 grams od salt melt-ing at 189* which was olptically inactivei.The resolutioln in this way however proceleldeld very slowly and as a preliminary experi-ment showed that the ZBdA salt is lelss soluble in water the optically inactive fraction was relcrysta,llised from that solvent. Fraction. Grams. M. p. Gram. a,. [WP a1 ............ 2.0 188" 0.2280 - 0.45" - 92.69' a2 ............ 3.6 186 0-2073 + 0-26 + 58.92 Fractio'n n l was twioe again resryst,allised from hoit water : a3 ............ 0.55 190 0.1202 - 0.485 - 189.5 a4 ............ 0.2 189 0.1836 - 0.64 - 164.5 Fraction a3 similarly p v e fractions a5 and a6: a5 ............ 0.26 191 0.1459 - 0.59 - 190.9 After 20 hours 0.1459 - 0.58 - 187.6 After 23 hours - 0.47 - 167.6 Yield.Substance. a6 ............ 0.18 0.1317 -0.51 - 181.9 -The rotatory power in the above case6 was determined in water The! rotlatory power of fraation a5 was ailsol determined in methyl a t 26-2F. akoholl : Substance. Time. Gram. Temperature. Hours. a,. [ W D . 0.1159 25.5' - - 0.373" - 151.1' 0-1159 26.0 24 - 0.378 - 153.2 Thus tbe pure salt ZBdA melt6 at 19l0 and has [MID -190-9O in aqueous wlutlon and -151O in methyl alcolhol (Found: N=5-81. After the pure salts dBdA and tBdA were isolated there still remained about 15.6 grams of the subst'ance with {MI ranging from + 2 9 O tIa +72O. It was relpeate'dly crystadlised first from water and then from methyl alcohol1 and ehheir. Ultimately a salti with [MI +35O wa,s obtained when the rojtatmy power muld C2,H,,0,N,S requires N=5.93 per cent.) 1elO SINGH STUDIES M SUBSTITUTED QUATERNABY AZONIUM not be changed any furthea.It thus appears from the slow reaollution that the1 two1 salt's dBdA lBdA have folrmeid a soilid solution olne in the other. The1 rottattion cotnstant's indicate that this fraation consists oif about 46 per cent. of the1 dBdA and 54 per cent. od the IBdA salt. The Nolecular Rotatory Powers of the Optically Active Ims in Aqueous Solutiofi from that of the Cavnphossulphmtes. The mo'lecular rolta,tory poitvers of tlhe two carmpho~rsulphonates, dAdB and dAIB in less than 1 per centl. aque'ous solution are tdmlated blow : M. p. [MID. (1) dBdA ......... 190° + 300.5" (2) ZBdA .........191 - 190.9 The! algebraical s u m of t3he molecular rotattory poiwers of thew two1 salts in aqueous solutioln should be elquad tla twice the molecular rotatory powetr of the acid ion and the algebraical differeace should be etqual to twim that od the basicr ion. The value of [MID for the camphorsulphonic acid ion becomes 54*8O and that for the phenylbenzylpropylazonium ioln 245.7O. The agreemelnt between the value of [MI for the1 camphorsulphoaic acid ion as delduced a,bove and that obt,aineld directly as in the following table is fairly close : Temperature. [MID. 20° 51.4" ......... (Graham T. 1913 103 764). 20 51.6 (Thomas and Jones, 30 5 3 . 6 ) ' . ' ' * ' * * . ( T. 1906 89 284). I'h city1 b enay Jp-opy laz onium d-a-Bront o camphor-@-sulphomt e, PhPra(CH2Ph) (NH,)N*SO,*C,,H,,OBr.This salt was prepared by the gradual additioa of finelly powdered azonium iodide (36- 1 grams) to one molecular proportion of silver ct-a-bromocmphor-P-su1phonak.e disolveld in hot rneithyl alcohol. The heating was continued for half an hour on the water-bath under reiflux. On filtelring off the silver iodide and conmn-trating the methyl-aloohodic extraot on the water-bath an oil was obtaimd which a t first did not orystlallisa It wits kept under ether olvernightl when it solidified to colourless prisms (41.2 grams) medting at 144-148O. The compound is vetry reladily soluble in matbyl alcohol less so in ethyl alcohol aOeltlone o r ethyl aoetlate, sparingly so in water and insoluble in eltheir (Found C=57-22; H = 6-62 ; N = 5.27.C,Hs0,N2BrS require& C = 56-63 ; H = 6-35 ; Nr5.08 per cent.) CONPOUNDS CONTAINING AN ASYMMETRIC NITROGEN ATOM. 121 1 1- Phenylb em ylpropyhzon iurn d-a-Bromoca,nzplltol.-P-sz~~ho.na t e. The crude bromocamphorsulphonata (40.2 grams) melting a t 144-148* as obtained in the above way was subjected to frac-tional cryst'allisation as follolws. It was dissolved in the least possible1 quantity of melthyl alcohol and precipitated by gradual additlion of ether. I n several caes an oil separated which increlaseid the difficulty of resollution : Yield. Substance. Fraction. Grams. M. p. Grams. a.. 1 12.5 155-156' 0.1087 +0.54" +272*0" 2 2.3 150-154 0.1193 0.68 3 12.2 Fraotion 1 similaxly gave: 3 3.2 178 0-1183 0.15 69.44 4 5.7 156-158 0- I362 0.742 298.4 Fra8ctmiosn 3 after severa,l mom recrystallisatiors gavel : 6 1.0 178-1 7 9 0-1792 0.22 67.31 After 8 hours 0.22 67.31 After 234 hours 0.20 61.1 The rotatory-powelr dejtelrminations in the above1 cases were made in methyl alcohol at 30-32'.The rotatory po'wer was also determine,d in aqueous sollutioin in the ca,se of fractiotn 5 : Substance. Gram. a,. [MID. 0-0693 + 0 . 0 9 O + 7 1 * 2 O Thus the pure ZBdA salt m&s art 178-179O and has [MI0 +71*2O in aquelous solution and +67.3O in methyl alcohol (Foand N=5*13. C,,HsO,N,BrS requires N=5*08 per cent.). dl-Phenytme t h ylpropylalzmit~m lodkle PhMeSra(NH,)NI. (a) By the- Actiom of Methyb Iodide on as-Phenylpropyl-hydruzine.-Methyl iodide! (6 grams) was added t o olne molecular propolrtion of as-phenylpropylhydrazine (6 grams) dissolved in ether.Within a short time the mixture began to deposit a guinmy mass which o a keeping olvernight became crystalline. Thel crude1 substance (3.8 grams) after relcrystallisation from alcoihol and either sepasated in colourless prisms melting and decomposing a t 106-107°. It. is solluble in methyl alcohol ethyl alcoho3 or w a h r but insoluble in benzene or ether (Found: I=43.26. ( b ) A e t k m of Yropyl Iodide on as-PhenyEmethyt~ydr~z~e.-In CL,H,,N2I requirels I=43-48 per m t . ) 1212 SINQH STUDIES IN SUBSTITUTED QUATERNARY BZOWIUR'I this reaction the corresponding azolnium iodide could not be obtainetd but ammonium iodide was isollatetd (Found I = 87.87. Calc. I=87*6 per cent.). A ction of Propyl Zodde om as-Phenylpropylhydrazine.-In this reaction also the colrrespoading azonium compound (namely, phenyldipropylazonium ioldide) could not be1 obtaineid butl at small quantity od ammonium iodide1 was isolated.dl -Ph eny 1 e t h y lailly la z o niqi T n Zodide PhE t (C,H,) (NR ) N I. Ally1 iodide (5 grams) was a d d 4 to one molecular proportion of us-phenylethylhydrazine dissolved in ethelr and cooled in ice. The1 mixture was kelpt overnight when a gummy substance was deposiiwd which holweves solidifield oln rubbing. The orude pro-duat (2.4 grams) oln recrystallisatiotn from alcohol and either, separateld in collolurless prisms mellting and deoolmposing a t 107-108O. The salt acquires a viollelt. cololur at about looo (Found I =42-09. The corresponding platirziclzloride is obtained in the usual way, as a pale orange prelcipitate consisting of prismatia needles melt-ing and decomposing a t 1510.Itn is very sparingly soluble in oold methyl alcoholl but morel readily so in hot and insolluble in water, acettone ethyl alcohol benzenel olr ether (Found Pt = 25-71. (C,,H17N,Cl),PtCl relquirm Pt = 25.62 pelr oent.). C11R17N21 requires I = 41.78 per cent .). as-Ph emy laL l y lk ydra zin e P h ( C3H ,) N NH,. This is prepared in the usual way by dissolving sodium in a finely divided granular conditioa in pheaylhydraxine and treating the reisultJng sodium phenylhydrazine with ally1 bro'mide (Michadis aad C1a8essen Ber. 1889 22 2234). The secondary hydrazine is however beat purified by leiading hydrogen chloride into a chloroform solution olf the base.as-Phelnylallylhydrazine hydrolchlolride meltsl a t 149-150° and nolt at 137O as stated by Miahdis and Claessm (loc. cit.) (Found C1= 19.76. Calc. : C1= 19.22 per c,ent .). dl - Ph eny l b e n z y lall y laz o m k m ZdXe, Ph(CR,Ph>(C,H,>(NH,)NI. An icecold &hereal solutlioln of as-phenylallylhydraxine (1 9.5 grams) was added to one molecular proportion of belnzyl iodide (36.0 grams) also cooled in ice. Within a short timel oolourless prisms began to1 delpoeit. The mixture was kept overnight. an COMPOUNDS CONTAINING AN ASYMMETRIC NITROGEN ATOM. 1213 the crude substance (27.5 grams) melted and decompowd a t 115-1 16O. On recrystallisation from hot 'alcohol the tempera-ture of decomposition was raised to 116-1l'iO.The substance is very readily soluble in meithyl alcohol less so1 in ethyl alcohol very sparingly so in water o r benzene and insoluble in ether (Found: I = 34.89. C,,H,,N,I requirm I = 34.67 per cent.). Ph en y l b enz y lally laz miti m d - CampJa or- P-sulph onat e, Ph( CH,Ph) (C,H,) (NR,)N-SO,*C,,H,,O. Finely powdered azolnium ioldide (23 grams) was added in small quantitiea a t a time to one molecular propo;rtion of silver 6-camphor-P-sulphonate contained in a mortar. The mixture was triturated thoroughly in the prwnce of a little methyl alcohol in the cold in ordelr to1 einsurel complete double d-ecomposition. It was repeatedly elxtraetecl with methyl alcohol and o n evaporating the1 solveat by blowing air throlugh the mixture 18.1 grams of the camphorsulphonats (theoretical yield 29-6 grams) were obtained.It is very reladily solluble in methyl alcohol ethyl alcohol or acetone less so in ethyl aoetak or water sparingly so in belnzene, and insoluble in ether. d-Phenylb enzyla llylazonkim d-Camphoa- fl-sulpholnat e . The crude camphorsulphonaba (24.3 grams) as obtained in the above way was subjected to fractional oryst'allisation frolm methyl alcoihol and elthelr. The1 pure salt? dBdA melting a t 147-148O and having a colnstant rotatory potwelr was obtaine'd with great elasel. As t;he rotatory polwer of khis salt varies colnsidelrably with t'he nature of the1 solvent the effect od this was s t a d i d on the fraction of constant rotatotry power : Solvent. Ethyl alcohol ...... 9 9 9 9 9 9 Methyl alcohol.. .... 9 7 . Chloroform ......... 9 7 9 9 Water ............... Time. Aft,er 54 hours. Y 9 22 Y ) Y 9 514 1 , 3 7 219 1 9 ,* 96 ,. (Solution slightly coloured. ) After 33 hours Y ) 47 9 7 ----Substance. Gram. aD* 0.1143 +0*78" +319.2' - 0.74 302.8 - 0.72 294.6 - 0.62 253.8 0.0645 0.394 28.5-7 - 0.35 253.38 - 0-30 217.5 0.0971 0.55 265.0 - 0.53 255.3 - 0-51 245-7 0.0983 0.40 190.3 As tthel a,que,otus sol!ut8ioln became turbid on heping no further The1 mean tempelrature ot all the above readings could be takein 1214 READ AND HOOK THE PREPARATION AND olbseryations was 27-29O. There is a mmkeld mutasoltcifion in the case of melthyl aloolhol and ethyl alcohol bui; i t is much less in the ca'se od chloroform (Foand N= 6.28. C,,H,O,N,S requires N=5-96 per cent.). THE CHEMICAL LABORATORY, GOVERNMENT COLLEGE, LAHORE PUNJAB INDIA. [Received July 20th 1920.