36 Proceedings of the Royal Irish Academy. 



to 50° in order to decompose any of the unstable white solid, and a current 

 of air was drawn through the apparatus to carry over the last traces of 

 ammonia. Titration of the acid showed that almost 90 per cent, of the 

 nitrogen of nitrogen sulphide is liberated as ammonia by the action of 

 methyl mercaptan. 



7440 gi'am N^Si gave 0-2434 gram NH3, or 88-5 per cent, of the 

 calculated amount. 



1-0004 gram NiSj gave 0-3697 gram NH3, or 89-8 per cent, of the 

 theoretical amount. 



On fractional distillation of the residual liquid obtained in the experi- 

 ment, a small fraction was obtained at 35°, which was obviously unchanged 

 ethyl mercaptan. A trace of ethyl sulphide distilled at 91-5°, but the main 

 fraction was collected at 150-153°. On further fractionation it was found 

 that this consisted almost entirely of ethyl disulphide (b.p. 151-5-152°). The 

 distillate on reduction by zinc and hydrochloric acid was converted into 

 ethyl mercaptan. Nitrogen sulphide, therefore, reacts with ethyl mercaptan 

 mainly in accordance with the equation — 



I2C2H5SH + N1S4 = ecCHO^S, + 4NH3 + 2S.. 



The action of sulphur chloride on a number of organic bases was examined, 

 and the derivatives formed appear to be characteristic for the different types 

 of bases. Thus sulphur chloride when added to solutions of the aliphatic 

 bases in chloroform or ether gives white precipitates of the hydrochloride 

 of the bases, the sulphur compound of the base remaining in solution. 

 This reaction has already been investigated by Michaelis' and his collaborators, 

 and dithioamines have been isolated. Diethylamine, for example, gives 

 rise to dithiodiethylamine S2(NEt2)2, and piperidine is converted into 

 dithiopiperidine. 



The alkyl substituted aromatic bases approximate to the aliphatic type, 

 giving white or faintly coloured precipitates on treatment with sulphur 

 chloride in ethereal or benzene solution. Derivatives of such a type have 

 previously been isolated, dithiodiraethylaniline, MesN.CeHi-S-S-CsHiNMes, 

 being prepared from dimethylaniline.' 



The primary aromatic amines, on the other hand, give coloured precipi- 

 tates when a few drops of sulphur chloride are added to a solution of the 

 base in ether, chloroform, or benzene. (The precipitates are actually colour- 

 less, being the hydrochlorides of the bases, but appear coloured on account of 

 the tints developed in the solutions.) The results obtained with the bases at 



> Berichte d. Deutsch. Chem. GeseU., 1895, 28, 165. 



- Merz. and Weith, Berichte d. Deutsch. Chem. Gesell., 1885, 19, 157. 



