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

Abstract

Arrhenius parameters have been determined for the reactions of picryl chloride with 3-R, 4-R, and 3,5-R₂-anilines (where R = NO₂, CF₃, or SO₂Me) in methanol and acetonitrile. In acetonitrile for all three groups, and for the trifluoromethyl and methylsulphonyl groups in methanol, the rate sequence of the 3-substituted anilines is governed entirely by the entropy of activation. The results are discussed in terms of the electronic effects of the substituents and linear free energy correlations are made. The effects of meta-substituents are additive in acetonitrile.