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

Abstract

Arrhenius parameters have been measured for the reactions of picryl chloride with the following substituted anilines in acetonitrile: 3-methoxyaniline, 3-X-5-nitroanilines (X = CF₃, SO₂Me, or Me), 3-X-5-methoxyanilines (X = F, Cl, Br, I, CF₃, SO₂Me, or OMe), and 3-X-5-methylsulphonylanilines (X = Cl, Br, or I). In both the methoxyhalogeno- and methylsulphonyl-halogeno-aniline series, the span of the rate constants is small and log A increases with increasing activation energy. The effects of the substituents in 3-methylsulphonyl-5-nitroaniline and in 3-methylsulphonyl-, 3-methoxy-, 3-trifluoromethyl-, 3-fluoro-, and 3-iodo-5-methoxyanilines on the free energies of activation is not additive.