J 0U RN A 11 01 THE CHEMICAL SOCIETY 1;~E. J. MILLS. THEfmwiula of Sparccinc the vol;itile hisc discovcretl hy S tc n-house,* in Spartiurn sc(ipurium lias loiig hccu n matt cr of tloitl)t among chemists. 8tcnhouse assigns to this suhtnnce the ~111- position- c' 1,H 1:Pf which cxpression cannot bc reprcscntcrl if the carbon-cquiva- lent (C=l2) be adopted. To avoid this difficulty Gcr1iardt-f proposed the formula- cf 1,I 11p,$ which offcrcd a tolerable approximation to the analrticnl rcsults of St cnhouse witliout liowcvcr dccidirig the qiicstioii 1)y mi appeal to csperiincnt. Tlic opinioii of tl!is illustrioiis clicmist so oftcn tricd arid fouiid corrcct in similar cases has \-cry naturdly ?mnacccpted iii inost Mauuxls. Ncverthcless thc point rcmaiiictl iinsettlcd; and it aIiliearcd of some interest to gain additional cxpcritncntal civdcncc for thc final clucidntion iiot oiily of tlic formula but also of tlic coiistitution of spartciiic.Some results wliich I have obtaincd iii this direction are recordcd in the follow-ing paragraphs In preparing this substance I have essentially followed the pccss devised by Dr. S t ciilio use. Tlic plant was simply * Stcnliousc ,\nil. CI1. Pliarin. (1851) Ixxviii 15. *ICcrhardt. Cliim. org. iv 236. 7 ::((I 6,0= 8 &c.) MILLS ON SPARTETNE. exhausted with water faintly acidulatcd with sulphuric acid. The extract was then evaporated to a smaller bulk and distilled with caustic soda until the distillate ceased to exhibit a bitter taste or an dkalinc re-action.On evaporating the distillate mixed with hydro- chloric acid to dryness on the water-bath and distilling the mass with solid hydrate of potassium-the mixture being just moistened at thc commencement-the thick oily base passed over into the receiver,-long preccdcd of course by the ammonia inwriably present. The substancc vas then gently heated with sodium in a current of dry hydrogen gas hy which means all ihe water was removcd. (It deserves to bc noticed that no other mode of drying succcedcd ; even exposure in vucuo for tmcnty-four hours with metdlic sodium failed to dehydrate the base.) The s’parteinc was now freed from the sodium and again distilled the assistance of the curr,ent of hydrogen being this time dispensed with.1501hs. of the plant yielded about 22 cub. cent. of base. I need not recapitulate the propcrtics of this substance already so well described by Stcnhouse. If it3 high boiling point be considered the idea naturally suggests itself to attribute it dism-monic charnctcr to sparteine. This circumstsncc together with the odour the well-defined narcotic action and other properties tempted me to hope that it would prove homologous with nicotine. In fact if Gcrhardt’s formula be doubled the homology of the two suhstances which arc so closely dlied in their chemical cha- racters becomes at once apparent. Nicotine C,,H,,N,* Sparteine C,,H 2sN,. In this hope however I was disappointed as will be secn from the following numbers :-I; 032475 grm.substance burnt with oxide of copper gave 9.91525 grm. carbonic acid and 0.33375 grms. water. El. 0.4225grm. substance again distilled and similarly treated gave 1.18675 grm. carbonic acid and 0.43625 grm. water. I. H. Carbon . . 76.86 76.86 Hydrogen . 11.42 11.47 Nitrogen . , 9 These results are so closely coincident with those of Dr. Sten-* c = 12 &c. et seq. MILL8 ON SPARTETNE. house that they may be fairly assumed to represent the compo-sition of sparteine which mould thus become a diamine COU-hining-15 *'XiN a formula which is unequivocally eupportcd by its deportment with iodide of ethyl. Thc following table shows the theoretical ralrics of Gerhardt's and Stenhouse's formulz together with the means of tlic analy- tical results obtained by S tenhouse and myself respectively Qerhardt's Formula Stenhousc'a Formula Stcnhonee.Mills. (doubled). (doubled). (Ad*). c16 78.05 C, 76.92 76 69 76.86 11,6 10.57 11.11 1 I -09 11.44 N 11-38 N2 11.97 ,> 99 Sult.9 of Sparteine. Some of these salts am uncrystallizable while others are easily obtained in crystals. The chloride bromide and iodide are amorphobs of' a resinous character and tinfit for analysis. The oxalate T obtained by neutralizing the aqueous solution of the base with oxalic acid and cvaporating. The crystals mere of acicular form and difficult to obtain. For additional corroboration of the formula of sparteine I have examined scveral of its doublc-salts. Platinum-salt.-This salt is precipitated as a yellom crystallinc powder when a solution of dichloridc of platinum is added to a solution of sparteinc in h-jdrochloric acid.It may be rcadily purifictl by solution in hot h~drocl~loric acid fil tcring ant1 reqs-tallizing. With care large crystals having wry hrilliant fnces may be obtained. Analysis furnished thc following rinnibers :-I. 0.475 grm. &bstance dried in z'acuo gave on combustion 0.459 grm. carbonic acid and O-210t3 grin. w:itcr. 11. 0.613 grm. same substancc siniilarly clrictl gam on ignition 0.176 grm. platinum. TIT. 0.1.795grm. substance similarly dried garc on corn1)us-tion 0.47'35grm. carbonic acid arid 0.2280groi. water. IV. 0.45175 grm. substance dried at lo",gav? on ignition 0.1317 grm. pl at'UlUIU V.0.34750 grin. suhshnco clricd at loo” gave on ignition 0.10250grm. platiiiiirn. Thesc numbers lcacl to thc formiila- thc thcorctical values of which I placc in juxtaposition with the cxpcrimental percentagcs :-c, H, N = = = 180.00 32.00 28.00 25.38 4.69 4-11 C1 = 213.00 31.22 Pt2 = 107*40 28-91 0 = 32-00 4.69 682.40 100~00 The Gold-snlt tvns prcl”irc(1 but not analysecl by Stcnhousc. 1 have obtained this salt with all the propcrtics assigned to it by its discoverer. 0.188 grra; snbstmcc gaw ON iguition 0.0605 grm. gold = 32.18per ceirt This iiumbcr agrees with the formda- ~,5N,GN3.21€Cl.:~I~C1;J which reqnires 32.27 per cent. ; aid thus it is seen that the hydro- chloratca of the iliamines are capablc of combining cithcr iiith om or with two equivalents of a metallic cldoride.I have also prepared the zinc-iodide and ziric-chtoride of spar-tcinc. Tlicy arc readily olttainctl by gently heating a solrition of sprteinc with hydriodic acid aid iorliclc of zinc or with liydro- chloric acid and chloride of zinc Iodide of Zinc and Sparteine.-This salt crystallizes in fine needlcs which are apt to become brown 011 cxposure to air. have only determined the iodine in this salt. MILLS ON SPARTEINE. 0.366 grm. substance dried in vacuo and precipitated with nitrate of silver gave 0.4225 grm. of iodide of silver =62.39per cent. iodine. The formula- C,,H,6N2.2H I.ZZnI requires 62-78 per cent. Chloride of Zinc and Sparteine.-This salt crystallizes in niag-iiificent needles which I have obtained half an inch long.They are white somewhat hard and lustrous. The composition of this salt is probably C,,H,6N,.2HC1.2ZnCl. Actioit of Iodide of Ethyl on Sparteine. The process of ethylation unknown at the time when sparteine was first prepared has proved of the greatest service in establish- ing the constitution of this base. When equal volumes of sparteine ordinary methylated spirit and iodide of ethyl arc heated together for about an hour in sealed tubes at 100' C. the mixture assunies a dark colour arid deposits abunclance of crystals of an ethylated cornpound,- sparingly soluble in cold readily soluble in hot alcohol and excessively soluble in water. Well-waslied with cold and owe recrystallized from hot alcohol the substance mas obtained pure and gave the following analytical results :-I..0.5010grm. substance* gave on combustion with a mixture of chromate of lead and oxide of copper 0.7275 grm. car-bonic acid and 0.2895 grm. water. 11. 0.4550 grrn. substance similarly treated gave 0.6505 grrn. carbonic acid and 0.2635 grm. water. 111. 0.5135 grm. substance gave on precipitation with nitrate of silver 0.4656 grm.iodide of silver. IV. 031525 grm. substance gave on similar treatment 0.2861 grm. iodide of silver. These numbers represent the foimula * The substance was in each anaiysis dried in vwuo. MILLS ON SPARTEINE. as may be seen from the following comparison of the theoretical dries with tlie experimental percentages :-Theory.1. Experiment. 11. 111. Iv. C, = 204 39.38 39.60 38-99 , #I H, N2 I = = = 32 6.18 28 5-40 254 49*04 6-42 ¶ , 6.43 9 , , ,J 4940 ,,,)49.04 518 100.00 The formation of this compound proves most satisfactorily the diammonic nature of sparteine.* The iodide crystallizes in the form of long needles beautifully groupcd and radiating from a centre. Treated with a boiling solution of potash this salt remains unaltcred ; oxide of silver however rapidly transforms it when in aqueous solution into the powerfully alkaline hydrated oxide-the composition of which was confirmed by the analysis of its p2ati-num-salt. This was prepared by treating the iodide with chloride of dver and tho chloride thus produced with dichloride of platinum in the cold.In this manner a semi-crystallized precipitate was obtained soluble in water alcohol and more readily in hydro-chloric acid. Dried in vacuo over sulphiiric acid 0.227 grm. substance gave on ignition 0066 grm. platinum corresponding to 29.07 per cent. The formula requires 29.26 per cent. * Note. In the above reaction’between iodide of ethyl and eparteine,a secondary product is found in very small quantity in the dcholic wa,ahhgs from the mono-ethylated di-iodide. The substance ie wsite exceeeively mluhle in alcohol almoet insoluble in cold sparingly soluble in hot water. Crystallized from the latter solvent it apperm in the form of small well-defined almost s~uarerhombohedral crystals. I determined the iodine in this substance aa well as the platinum in the platinum-salt obtained from it ; tbe numbers were respectively 36-25 per cent.(I) and 27.95 per cent (Pt). It will be perceived that these numbera present ;.-discrepancy ; and I much regret that I wag unable t~ procure su5eientl ~*:bs+ance 4t.i a determination of the carbon and hydro- MILL8 ON SPARTEINE. The dichloride corresponding to the mono-ethylated di-iodide is less easy to obtain and crystallizes also in needles. It forms with chloride of zinc a beautiful acicular double salt easy to cryst dize. * Action of rod& of Ethyl on EthyESparteine. When the hydrate of this base obtained by the action of oxide of silver on the iodide is digested with alcohol and iodide of ethyl in sealed tubes at 100”C. for a short period there is obtaind on evaporation of the liquid a crystalline iodide always contaminated with free iodine which differs essentially from the iodide of the mono-ethylated base.If the evaporation be conducted in a stream of sulphuretted hydrogen gas the separation of much of the iodine is effected and the subtance rendered considerably purer. The ncw iodide crystallizes from alcohol in short minute crystals and is very soluble in water. Treated with oxide of silver it yields a powerfully alkaline solution Boiled with chloride of silver the iodide is converted into the corresponding chloride which is deli-quescent and not easy to obtain in crystals. The latter treated with dichloride of platinum furnishes a very voluminous platinum- salt of light yellow colour and crystallizing in radiated aggrega-tions from its solution in weak alcohol.It is very soluble in water ; a mixture of alcohol and ether fails to precipitate it entirely. On analysis 0.213 grm. substance gave by ignition 0.0610grm. platinum = 28-64 per cent. Want of material here prevented me from perf‘ormiug these expe- riments on a more extensive scale. The natural interpretation of the above observations would be to assume that the action of iodide of ethyl upon the mono-ethylated sparteine produces the di-ethylated iodide which with oxide of silver yields the caustic hydrate of the diammonium- Compare Dr. Hofmann’s ‘‘ Notes of Researches on the Poly-ammoniaa” No. XIV. ‘(Diagnosis of Diarnines.”-Proceedings of Royal Society vol.xi p. 978 BENCE JOXES ON CRYSTALLTBED PHOSPlIATE OF fiirniehing lastly by treatment with hydrochloric acid and dichlo-ride of platinum the platinurn-salt-This formula requires 28*10per cent. of platinum. The analysis above gives as much as 28-64 pcr cent. The salt was probably still contaminated with IL minute proportion of the mono-ethylated compound. The results of this inquiry prove unmistakably that sparteine is a tertiary diamine of the formula C,,H,,N = (ClSH2JViNZ. Further investigation is nccessary to afford some insight into the nature of the-complex atom (C151126)v1 which assumes the place of six equivalents of hydrogcn. The above experiments on sparteine were cnrried out in Dr H ofm ann' s laboratory.