Salt Effects on the Rate of Solvolysis of Cumyl Chloride and its p-Methyl Derivative

Abstract

Effect of added electrolytes, LiClO₄, LiCl and LiBr on the rate of solvolysis of cumyl chloride in 90% aqueous acetone showed that special salt effect is operative and there is an indication of slight mass law effect, while the studies in 80% aqueous DMSO confirmed the presence of mass law. These effects are more pronounced in p-methyl derivative. It can be rationalized in terms of hyperconjugative electron release of methyl group through the p-bonds of phenyl ring to the carbocationic center at the rate determining step.