232 MORLEY ON METHPLATED DIOXETHTLENAMINES. XVII.-On Methy luted Dioxeth ylenamines. By H. F. MORLEY M.A. IT is well known that the discovery of the oxethylene bases is due to Wurtz (Ann. Chem. Pharna. 114 51; 121 226) who some twentj years ago showed that oxide of ethylene unites directly with ammonia to form the following bodies :-Oxethylenamine. Dioxethylenamine. Trioxethylenamine. C2HaOH CZHdOH >o CZH4NH-2 >o c2H4gg2 >o C2H4 CSH4NH MORLEY ON METHYLATEU DIOXETHYLENAMINES. 233 He also showed that glycolic chlorhydrin is converted by ammonia into the first two bases and that when heated with trioxethylenamine it yields tetra- pent- and even hept-oxethylenamine. It was even then suggested by Strecker (Cowzpt. rend. 52 1279) that his choline might be related to these bases ; but it was not until five years later that Liebreich's neurine which Dybkowsky (J.pr. Ghem. 100 191) showed to be identical with choline was converted by Baeyer (Ann. Chem. Pharm. 140 306 ; 142 322) into the iodide N(CH3),( C2H41)I and thus proved t o be trimethyloxethylenammonium hvdrate :-OH c2H4N ( CH,),CH,.OH' a view which was shortly afterwards confirmed by Wurtz (Ann. Chem. Pharrn. Suppl. 6 116 197) who produced neurine chloride syntheti-cally by heating glycollic chlorhydrin or ethylenic oxide with a solution of trimethylamine. The corresponding ethyl-compound derived from trie thylamine and ethylene oxide and oxamylenamine a base isomeric with neurine (Wurtz Ann. Chem. Pharm. 7 SS) complete the list, as far as the fatty series is concerned of known members of the group under discussion,* but no one has sought for the intermediate mem-bers :-OH C 2 H 4 ~ ~ ~ ~ , OH C2H4N(CH3)i Accordingly at the instance of Professor Hofmann I have examined the action of mono- and di-methylamine on glycollic chlorhydrin and have found that in both cases a condensation takes place almost the only product of the reaction being a homologue of CzH4(OH)OC2H4NH2.~ononLethyZdioxethylenam.ine. 1 7 grams of glycollic chlorhydrin (prepared by Carius's method from chloride of sulphur and glycol which yields rather more than 50 per cent.) were heated to 100" for several hours with an excess of methyl-amine in aqueous solution. The reaction is as follows : 2CzH$!F + 2NH,CH3 - NH2.CH3C1 + C2H40~-C2H4NHCH,HC1.In order to get rid of the methylamine hydrochloride the content's of the tubes were treated with oxide of silver and freed from methyl-amine by boiling. The solution after being acidified and filtered, yields on evaporation over the water-bath a non-crystallisable syrup ; to remove the last traces of silver chloride i t is necessary t o redissolve this in water which produces a slight precipitate. The syrup ob-* Demole has obtained oxethylenanilin oxethylenetoluidin &c. (Bey. 1873, 1024 ; 1874 635. 234 MORLEY ON METHTLATED DIOXETHTLENA11IIKES. tained by evaporating the filtrate was dissolved in absolute alcohol and precipitated with a concentrated solution of platinic chloride ; ancl the semi- fluid precipitate was dissolved in water and part.ly thromll down as an oil by adding alcohol.On further adding alcohol b!-small portions at a time and at the same time stirring the liquid :I mass of small crystals was obtained. These were dissolved in water, and alcohol was added till the liquid became turbid. On standing. the liquid deposited a mass of splendid orange-red prisms which gave by analysis the following results :-Calculated for CloH2sN,04PtC1,. Foniid. C . . . . . . . . . . . . . . 18.46 18.82 H 4.31 4.65 K 4.31 4-34 P t 30.31 30.15 The crystals therefore consist of the platinum salt of methyl-dioxethylenamine. The oily precipitate gradually became solid but nevertheless melted below 100" (which the crystals do not do) ; it contains 29.89 per cent. platinum so that it consists principally of the same compound as the crystals. Dinzethy ldioxethylenamine. The product of the action of glgcollic chlorhydrin (20 grams) on A solution of dimethylamine at 100" was treated in like manner with silver oxide. The hydrochloride of the new base is also a thick syrup ; out of its alcoholic solution chloride of platinum precipitates a solid salt which may be obtained by crystallisation from hot dilute alcohol in the form of small yellow crystals whose analysis gave :-Calculated for C12H3,N20,PtC16. Found. c 21.24 20-99 H 4.72 4.95 N 4.13 4.42 Pt 29.06 28.71 agreeing with the formula for the platinum salt of dimethyl-dioxethylenamine :-PtCl,. (.2H9g C,HaN(CH,)zHCl I 2 It is there'fore homologous to the body previously described