The kinetics of the reactions of picryl chloride with some substituted anilines. Part II.

Abstract

Arrhenius parameters have been measured for the reaction of 3-X- and 3,5-di-X-substituted anilines (X = F, Cl, Br, or I)with picryl chloride in methanol. The reactions of the disubstituted anilines obey an isokinetic relationship and one may exist for the monosubstituted nucleophiles. The rate sequence for the disubstituted anilines between –30 and 75° is governed by the –I effect of the halogens, but the rate sequences of the monosubstituted anilines are temperature dependent. The effect of the fluoro-, chloro-, and iodo-substituents on the free energy of activation is not additive.