The Orientation of a Series of substituted Bromanilines. 351 
The Orientation of a Series of substituted Bromanilines. 
By J. R. Hill, B.A., St John’s College. (Communicated by 
Mr H. 0. Jones.) 
\Read 25 November 1907.] 
The bromanilines dealt with in this paper were previously 
described in the Proceedings (Vol. xiv. 166). They are five 
in number and have the general formula C 6 H 4 Br.N. (CH 3 ) (R), 
where R is an ethyl, propyl, isopropyl, isobutyl or isoamyl radical. 
In addition to an account of the preparation and properties of 
these amines and some of their derivatives, several attempts to 
determine the position of the bromine atom in the benzene 
nucleus were recorded. The methods employed, however, did not 
meet with much success and the constitution of only one of the 
compounds — namely the ethyl — was proved. It was first con- 
verted into the quaternary iodide C B H 4 Br . (CH 3 ) 2 . C 2 H 5 . N . I by 
the addition of methyl iodide. This was then treated with silver 
oxide, giving the quaternary hydroxide. On distillation the 
hydroxide underwent decomposition and the distillate deposited 
crystals on cooling. After several recrystallisations from alcohol 
the melting-point was 55° C. This decomposition product was 
shown to be dimethyl para-bromaniline (Weber, Ber. vm. 715, 
Wurster, Ber. xn. 1816 and 1820) by means of its melting-point 
of 55° and the quaternary iodide formed on addition of methyl 
iodide which melted at 200° C. Thus the bromine atom in the 
original methyl ethyl bromaniline must be in the para position. 
Since this work was recorded the problem has been approached 
in other ways. In the first place dimethyl para-bromaniline 
(M.P. 55° C., Wurster, loc. cit.), prepared by the bromination of 
dimethyl aniline in acetic acid solution, was mixed with equiva- 
lent quantities of the iodides of the five alkyl radicals mentioned 
above. It was expected that the corresponding quaternary 
ammonium iodides C 6 H 4 Br . (CH 3 ) (R) N . I would result; and 
then if these proved to be identical with the iodides prepared 
previously by the action of methyl iodide on the bromanilines, 
the bromine atom in the latter would be shown to be in the para 
position. This result, however, was not entirely realised. 
The reactions were extremely slow in the cold except in the 
case of the ethyl iodide, where a solid was readily deposited. This 
solid, on examination, proved to consist not of p-bromphenyl 
dimethyl ethyl ammonium iodide, but largely of p-bromphenyl 
trimethyl ammonium iodide. The identity of this compound was 
established by its similarity in every respect to the quaternary 
