Hvan and O'ltroEDAN — Action of Bromine on Diphenylamine. 219 



experiments were carried out there on the bromination of diphcnylnitros- 

 amine. These experiments went to show that the product of bromination of 

 diphenylnitrosamine is tetrabroino-diphenylamine with a small quantity of 

 some yellow-coloured product. 



Preliminary experiments of ours on the action of bromine on diphenyl- 

 nitrosamine showed that in addition to tetrabromo-diplienylamine and this 

 yellow substance another white product melting about 220° C. was obtained 

 under certain conditions. We then undertook the qualitative examination 

 of the action of bromine on diphenylnitrosamine with the following results: — 



(a) It was found that the prolonged action of bromine on diphenyl- 

 nitrosamine in chloroform solution, and in the presence of sunlight, yielded as 

 main product hexabromo-diphenylamine. 



(b) The same product was obtained by the prolonged action of bromine 

 in sunlight on tetrabromo-diplienylamine. 



(c) The first product isolated in the action of bromine on diphenylnitros- 

 amine was found to be tetrabromo-diplienylamine, together with a small 

 quantity of some yellow substance. 



The remainder of this investigation is concerned with the action of 

 bromine on some of the nitro derivatives of diphenylamine and diphenyl- 

 nitrosamine. It was thought that it would be of interest to ascertain what 

 substances would be formed by the action of bromine on these nitro com- 

 pounds, in view, especially, of the fact that preliminary experiments of ours 

 showed that some of those nitro compounds were, to an appreciable extent, 

 volatile with steam, and would consequently be present in the diphenyl- 

 amine distillate obtained by the method of Berger already described. 



The nitro derivatives examined by us were :— 4-nitro-diphenylnitros- 

 amine, 2. 4-dinitro-diplienylamine, 2. 10-dinitro-diphenylamine, 4. 10-dinitro- 

 diphenylamine, 2. 10- and 4. lO-diuitro-diphenyluitrosamines, and 2 4. 8. 

 10-tetranitro-diphenylamine. Of these, the three nitrosainines and the 

 tetranitro-diphenylamine have been observed amongst the products of the 

 interaction of diphenylamine with the oxyacids of nitrogen. All ihese 

 substances, with the exception of the tetranitro compound, react with 

 bromine in chloroform solution, and in each case the only product obtained 

 was a dibromo derivative. The derivatives of diphenylnitrosamine on 

 bromination split oh' the uitroso group and yield the same bromo compound 

 as the corresponding nitro-diphenylainines, thus 2. 10-dinitro-diphenyl- 

 nitrosamine, and 2. 10-dinitro-diphenylamine on bromination give the same 

 bromo compound. 



Although diphenylamine and diphenylnitrosamine in chloroform 

 solution are readily converted by bromine at the ordinary temperature 



R.I. A. PROC, VOL. XXXIVi S15CT. B, - ' ' 



