Solvent Polarity, Hydrogen-Bonding and Solvophobicity Effects on the Nucleophilic Substitution of Benzenesulfonyl Chloride with Aniline in Aqueous and Non-Aqueous Solutions of Methanol

Abstract

The reaction between benzensulfonyl chloride and aniline was studied in various compositions of methanol with ethyl acetate, propan-2-ol and water at 25° C. Second-order rate coefficients of this reaction were determined; those in pure solvents were in the order of water > methanol >propan-2-ol> ethyl acetate. Rates decreased sharply with the mole fraction of ethyl acetate in methanol- ethyl acetate mixtures and showed an increasing trend with water content in methanol-water mixtures. Linear free energy relationship regressions showed that the polarity, hydrogen-bond donor ability and hydrophobicity of the media were the main factors affecting the reaction rate coefficient.