TRANSFORMATION OP AROMATIC N1TROAMINES, ETC. 



85 



The Transformation of Aromatic Nitroamines and Allied Substances, 

 and its Relation to Substitution in Benzene Derivatives. — Report 

 of the Committee, consisting of Professor F. S. Kipping (Chairman), 

 Professor K. J. P. Orton (Secretary), Dr. S. Ruhemann, Dr. A. 

 Lapworth, and Dr. J. T. Hewitt. 



I. — The Chlorination of Anilides and the Transformation of Acylchloro- 



aminobenzenes. 

 (With W. J. Jones, B.Sc.) 



In summarising his views on substitution in aromatic compounds, 

 Armstrong l expressed the belief that in the formation of derivatives 

 of anilines and phenols, the reagent united directly with the nitrogen 

 or oxygen,' the residual valency of these atoms coming into play. In 

 the case of anilines and anilides the definite compounds, which can 

 often be isolated, nitroamines, chloroamines, &c, were held by 

 Armstrong to be ' a necessary stage in the formation ' of the substituted 

 aniline or anilide, the process of conversion being ' regarded as one 

 of isomeric change.' He suggested further that, as part of the 

 mechanism of the change, ' the centric benzene nucleus assumed 

 momentarily the highly unstable ethenoid form.' 



Later, Armstrong 2 discovered that the chloroaminobenzenes were 

 only converted into the isomeric chloroanilides in the presence of 

 hydrochloric acid. Blanksma 3 showed that under the conditions under 

 which he worked the reaction was of the first order, and the speed 

 proportional to the square of the concentration of the hydrogen 

 chloride. It had been suggested by Orton 4 that all such isomeric 

 changes of the N-substituted derivatives under the influence of an acid 

 catalyst were due to the formation of a complex or salt (I) in which 

 the nitrogen was quinquevalent. This compound was capable of 

 undergoing an intra-molecular rearrangement, in which the benzene 



01, + ArNHAc 



CI CI 



\/ 



AcNH 



I 

 /\ 

 I I 



V 



CI 



I 

 AcNH 



II 



ci 



HCl + Ar.NClAc 



CI 



I 

 AcNH 



II 



/\ 



lull 



A 

 ci 



AcNH 



I 



M C1 



AcNH 



I 



A 



Cl 



+ HC1 



HCl 



1 Reports, 1899. 



8 Becueil des Trav. Chim., 1903, 22, 290. 



2 Trans. Chem. Soc., 1900, 77, 1051. 

 * Proc. Boy. Soc., 1902, 71, 15C 



