Effect of Pressure on the Rate of Solvolysis. Formolysis and Methanolysis of Secondary Alkyl Tosylates

Abstract

Abstract The effect of pressure on the formolysis and methanolysis rates of representative secondary alkyl tosylates was investigated, and the activation volumes, ΔV0\eweq, were estimated. The values of activation volume for formolysis were found to correlate excellently with σ*. This conformity of ΔV0\eweq to the Hammett-type correlation is interpreted as a consequence of the kc-character of the reaction. The values of activation volume for methanolysis, however, converged to more negative values. The ks-character of methanolysis is thought to be responsible for this behavior. The kc-ks-hybrid nature of the reaction is also discussed.