589 



VII. " On Bromphenylamine and Chlorphenylamine." By E. 

 T. MILLS. Communicated by Dr. HOFMANN. Received 

 July 24, 1860. 



Nitrophenylamine, when prepared from dinitrobenzol (i. e. by tbe 

 indirect method), differs in so many respects from the isomeric base 

 which is obtained from phenyl-compounds (i. e. by the direct method), 

 that chemists have distinguished these two bodies as alpha- and 

 beta-nitrophenylamine * Bromphenylamine and chlorphenylamine 

 have hitherto been produced only by the action of potash upon 

 bromisatin and chorisatin, the indirect method, by which they were 

 originally obtained by Dr. Hofmann ; it appeared therefore of some 

 interest to ascertain whether the bodies generated directly from 



* The alpha-nitrophenylamine (nitraniline) was formed about sixteen years ago 

 by Dr. Muspratt and myself (Chem. Soc. Mem. vol. iii. p. 112), by the action of 

 reducing agents on dinitrobenzol. The beta-nitraniline was discovered by Arppe 

 (Chem. Soc. vol. viii. p. 175), who obtained this compound when distilling pyrO- 

 tartronitrophenylamide with potash. The two bases resemble each other in a 

 remarkable manner; but there are differences in their physical and chemical 

 characters which leave no doubt as to the fact of their having different constitu- 

 tions. I may here remark that I have repeated Arppe's experiments, the results 

 of which I can confirm in every particular. Since the phenyl-compound from 

 which Arppe obtained his substance is accessible only with difficulty, I have 

 endeavoured to nitronate a more easily procurable phenyl- compound. Acetyl- 

 phenylamide may be used for this purpose with considerable advantage. A solution 

 of the compound in cold fuming nitric acid yields, on the addition of water, a 

 crystalline difficultly soluble precipitate, which is easily obtained pure by recrystal- 

 lization. This substance contains 



[C 6 (H 4 N0 2 )]-| 



C 3 H 8 N 2 4 =(C 2 H 3 2 ) U, 

 H J 



and yields, when heated with potassa, the beta-nitrophenylamine of Arppe with 

 all its properties. I may here recall a former observation, which has now become 

 perfectly intelligible. When studying the action of nitric acid upon melaniline, 

 I found (Chem. Soc. Mem. t. i. 305) that the dinitromelaniline, which is thus 

 formed, essentially differs from the dinitromelaniline obtained by submitting 

 nitrophenylamine (alpha-) to the action of chloride of cyanogen. The two nitro- 

 bases, which are both expressed by the formula 



C 13 H n N 5 4 =C 13 [H n (N0 2 ) 2 ]N 3 , 



stand to each other in the same relation which obtains between alpha-nitro- 

 phenylamine and beta-nitrophenylamine. In fact, I have since found that the 

 distillation of the nitro-base, obtained by treating alpha-nitrophenylamine with 

 chloride of cyanogen, furnishes alpha-nitrophenylamine ; whilst beta-nitrophenyl- 

 amine maybe detected amongst the products of the distillation of the dinitromel- 

 aniline which is formed directly from melaniline by means of nitric acid. A. W. H. 



