167 
Mr Hill, A Series of Substituted Bromanilines. 
culty was experienced in obtaining suitable derivatives for this 
purpose. A crystalline hydrobromide could only be readily 
obtained in the one case mentioned above. All the bases, how- 
ever, gave crystalline compounds more or less readily with methyl 
iodide. The melting points of these quaternary ammonium 
iodides were taken, but they all lay within a comparatively small 
range of temperature. 
An attempt was made to obtain the platinichlorides, but with- 
out. success. 
The picrates were found to be readily obtainable. Alcoholic 
solutions of the base and of picric acid were mixed, and, on allow- 
ing them to evaporate, the picrates separated. They crystallised 
well from alcohol. Here again the melting points were in some 
cases very close together. All the bases readily formed crystalline 
compounds with allyl and benzyl iodide, giving rise to the two 
series of asymmetric nitrogen compounds which are the final 
object of the research. 
The next problem, and one which proved to be of considerable 
difficulty, was the fixing of the position of the bromine atom. 
This was first attempted by the action of potash on the methyl 
iodide addition compounds. It was thought that dimethyl brom- 
aniline would result, which could be identified as ortho, meta or 
para. But there was no action, even with the strongest potash. 
Silver oxide was next tried with the same compounds in 
alcoholic solution. It reacted readily and gave a strongly alkaline 
solution of the quaternary hydroxide. This was evaporated down 
on the water bath and then distilled. According to Hofmann the 
group of highest molecular weight should split off when a qua- 
ternary hydroxide is heated. It was consequently expected that 
dimethyl bromaniline would be the final product in each case. This 
result was unfortunately only realised in one case — that of methyl- 
ethyl bromaniline. The quaternary hydroxide obtained from this 
compound gave dimethyl-para-bromaniline. Thus the bromine is 
in the para position in the case of methylethylbromaniline. 
All the other quaternary hydroxides, on decomposition, split 
off a methyl group instead of the higher group, and thus gave back 
the original bromaniline. They could not therefore be orientated 
in this way. Another method was consequently looked for. 
Lauth ( Ber . 6, p. 677), by passing dry hydrochloric acid gas 
over dimethyl aniline at 180° C., split off the methyl groups and 
obtained aniline. This method was tried with dimethyl bromani- 
line. Methyl chloride was evolved, but the resulting product was 
an uncrystallisable mixture and the method was abandoned. 
The only other method of orientation that suggested itself was 
to start with methyl p-bromaniline and try to form the di-substi- 
tuted p-bromanilines from it. If they were found to be identical 
