166 
Mr Hill, A Series of Substituted Bromanilines. 
A Series of Substituted Bromanilines. By J. R. Hill, B.A., 
St John’s College. (Communicated by Mr H. O. Jones.) 
[Read 11 March 1907.] 
The preparation of these compounds was undertaken with the 
object of obtaining from them by the addition of benzyl or 
allyl iodide two series of substituted ammonium compounds con- 
taining an asymmetric nitrogen atom. All the members of such 
a series would contain a bromine atom in the phenyl group, and 
would in this respect differ from the asymmetric nitrogen com- 
pounds described by Miss M. B. Thomas and Mr H. O. Jones 
(J.C.S. 1906, p. 280). The difference in rotatory power caused 
by the introduction of the bromine atom could then be examined. 
In this way the change in the optical activity produced b}^ the 
increase in weight of the phenyl group could be studied. This 
work is at present in progress. 
The tertiary bromanilines described in this paper were prepared 
by the bromination of the corresponding tertiary anilines. The 
latter were obtained from methyl aniline as described in the paper 
referred to above. The methyl aniline was heated with the various 
alkyl bromides on a water bath, producing more or less readily 
the hydrobromide of the di-substituted aniline. The free base was 
then liberated with potash and purified by distillation. 
The tertiary base thus obtained was next brominated. The 
method of bromination used was that employed by Karl Fries for 
brominating amines (J.C.S. Ab. 1906, p. 644). The base was 
dissolved in acetic acid and a solution of bromine in acetic acid 
slowly run in, keeping the liquid cool by immersion in water. 
One molecule of bromine was used for one molecule of the base. 
In this way the hydrobromide of the bromaniline was obtained in 
acetic acid solution. 
In the first case tried — that of methylisopropylbromaniline — 
the hydrobromide was obtained in crystalline form. In all the 
other cases the hydrobromides remained as gums : the isobutyl 
and isoamyl compounds showed signs of crystallising after standing 
several weeks. 
The bromanilines, liberated by the addition of potash to solu- 
tions of the hydrobromides, were oils with one exception, namely 
methyh’sopropylbromaniline. This on recrystallisation from alcohol 
was obtained in beautiful lustrous plates. Five of these bromani- 
lines were prepared. Of the two substituting groups one was, of 
course, methyl in each case ; the other was ethyl, propyl, iso- 
propyl, isobutyl or isoamyl. The liquid bromanilines were puri- 
fied by fractional distillation in vacuo. 
These compounds had now to be characterised. Some diffi- 
