TRANSFORMATION OF AROMATIC NITROAMINES, ETC. 



93 



TABLE V. 



The Interaction of Acetanilide with Acetylchloroamino-pchlorobenzene and 



Hydrochloric Acid. 



The effect of the presence of an anilide on the conversion 

 of the corresponding chloroamine — for example, of acetanilide on 

 the conversion of acetylchloroaminobenzene, or of p-chloroace- 

 tanilide on that of the acetylclvloroamino-p-chlorobenzene — is small. 

 In the first instance, owing to the equilibrium, the concentration of 

 the chloroamine is increased and that of free chlorine reduced. But 

 in 50 per cent., or even in 65 per cent., acetic acid, the proportion of 

 free chlorine and anilide is so small that relatively little alteration of 

 concentration of the chloroamine is brought about, but the alteration 

 in the chlorine is considerable. Thus, taking as an example the system 

 made up from p-chloroacetanilide and chlorine, the proportion of free 

 chlorine is 0'4 and 5'3 per cent, in 50 and 65 per cent, acetic acid 

 respectively, but on adding one molecular proportion of the anilide 

 this drops to about 0"2 per cent, in the latter medium. The velocity 

 of chlorination increases in the ratio 1"19/1 in 50 per cent., and in the 

 ratio T22/1 in 65 per cent. With acetanilide, where the proportion 

 of free chlorine is somewhat less, the ratio of the velocities is 1*13/1. 



When acetanilide and the chloroamine of p-chloroacetanilide inter- 

 act in the presence of hydrochloric acid the result is very remarkable 

 and instructive. The acetanilide is alone chlorinated ; the amount of 

 2 : 4-dichloroacetanilide is insufficient to admit of detection. On com- 

 paring the velocities the remarkable character of the reaction is made 

 more clear. In 50 and 65 per cent, acetic acid the reactions are of 

 the first order. (Diagram II., figs. 3 and 4.) 



Table VI. 



hi in 50 A - i in f 5 

 per cent. ! per cent. 



jp-C1.C 6 H,.NC1Ac- 



C 6 H 5 .NClAc + HC 

 ^.Cl.C 6 H v NC1Ac- 



HCl-> 2 : 4-Cl 2 .C 6 H 3 .NHAc . 

 o- and ^-C].C S H 4 NHAc . 



o-and^.ClC 6 H 4 NHAc 



HC1 + C 6 H 5 .NHAc 



00053 , 0023 

 0-00039 | 0-0026 

 0016 i 00092 



In both media the speed of chlorination of acetanilide by the 

 chloroamine of p-chloroacetanilide is far more rapid than the con- 

 version of the chloroamine of acetanilide into the isomeride. In 50 per 

 cent, acetic acid the conversion of acetylchloroamino-p-chlorobenzene 

 is faster than that of acetylchloroaminobenzene. Although the experi- 

 ments on the "changes occurring when an anilide is added to a mixture 



