Influence of the Kind of the Halogen on Solvation Effects in Hydrolysis of 2-Methylbenzenesulfonyl Chloride and Bromide in Water-Rich H2O-Dioxane Mixtures

Abstract

The structural and energy parameters of 2-methylbenzenesulfonyl chloride and bromide were calculated by ab initio (B3LYP/6-311G**) and semiempirical (PM3) methods and were correlated with the kinetic parameters of hydrolysis of these compounds in aqueous dioxane (mole fraction of dioxane X2 0-0.15). The concentration dependences of the activation parameters of hydrolysis of these compounds, which are essentially nonmonotonic and are strongly influenced by the kind of the halogen, were accounted for by specific structural features of sulfonyl chloride and bromide groups.