66 Royal Society : — 



course applied to tolylamiue, cuniylamine, iiai)hthylamine, and all 

 primary nionamines. 



"Action of Bibromide of Ethylene upon Aniline." By A. "W. 

 Hofmann, Ph.D., F.R.S. 



While engaged in some experiments on the action of bibromide 

 of ethylene on ammonia, a short account of which I have lately 

 communicated to the Royal Society*, I induced Mr. Henry Bassett, 

 then working in my laboratory, to study the deportment of the same 

 bromide with aniline, a characteristic representative of the class of 

 primary monamines. In the following pages I propose to submit 

 to the Society Mr. Bassett' s observations, together with the results 

 of a series of experiments which I carried out myself after Mr. Bassett 

 by circumstances had been prevented from a further continuation of 

 the inquiry. 



A mixture of 1 volume of the bibromide of ethylene and 2 volumes 

 of aniline, when exposed to the temperature of boiling water for an 

 hour or two, solidifies into a crystalline mass of more or less solidity. 

 This mass is chiefly hydrobromate of aniline ; it contains, however, 

 hi addition, three new organic bases, partly free, partly in the form 

 of hydrobromates. These substances are formed in very different 

 quantities, — a beautiful crystalline body, difficultly soluble in alcohol, 

 being invariably the chief product of the reaction, while the two 

 other bases, the one solid but extremely soluble in alcohol, the other 

 likewise sohd but quite insoluble in this liquid, are found to be pre- 

 sent in much smaller proportions. 



The preparation, in a state of purity, of the principal product of 

 the reaction presents no difficulty. The solid mass obtained by 

 digesting bibromide of ethylene and aniline in the stated propor- 

 tions is mixed with water, and submitted to distillation, when any 

 bibromide left unchanged, together with some unaltered aniline, passes 

 over. The residuary liquid is then mixed with a strong solution of 

 potassa, which separates all the bases existing as hydrobromates in 

 the form of a semi-solid resin. This is washed with water and then 

 again submitted to distillation with water, when, together with more 

 or less water, an additional quantity of aniline distils. The residuary 

 mass, when treated with boiling (methylated) spirit, leaves the in- 

 soluble base as a white, flour-like powder, while the other two bases 

 dissolve. On cooling, the solution deposits a beautiful crystallization 

 of white needles, while the more soluble base remains dissolved in 

 the spirit. The crystals are rather difficultly soluble in alcohol ; 

 two or three crystallizations from this solvent render them absolutely 

 pure. 



Tims obtained, the new base, for which, in accordance with the re- 

 sults of analysis, I propose the name cflnjlcne-plienylamine, is a snow- 

 white, inodorous and tasteless crystalline compound,of nacreous lustre, 

 insoluble in water, soluble in boiling, less so in cold alcohol, soluble 



* Proceedings of tlip, Royal Society, vol. S\. page 150. 



