Perchlorate catalysis of the methanolysis of triphenylmethyl chloride in benzene solution and its relation to special salt effects in solvolysis reactions

Abstract

The kinetic form of the suppression of the perchlorate catalysis of the methanolysis of triphenylmethyl chloride in benzene solvent by tetra-n-butylammonium chloride has been investigated. This is consistent with a catalysis brought about by a simple perchlorate ion, suppressed by a competition between such ions and alkylammonium chloride ion-pairs for the alkyl halide ion-pair.The results are discussed in relation to the qualitatively similar special salt effects observed in acetolysis reactions by Winstein and co-workers, with particular reference to the necessity of the concept of intimate and solvent-separated ion-pairs in the interpretation of these effects.