Kinetics and mechanism of reactions between 2-phenylethyl benzenesulphonates and anilines in methanol

Abstract

Kinetics of reactions between 2-phenylethyl benzenesulphonates and anilines in methanol at 65.0 °C have been studied; the mechanism is discussed on the basis of cross interaction constants, ρ_ij. The overall reaction was found to proceed by a dissociative S_N2 mechanism with a relatively small degree of aryl participation. The fraction of the phenonium ion intermediate captured by the nucleophile, aniline, in the aryl-assisted pathway has been shown to increase with a stronger nucleophile, and a four-centre transition state in an intermolecular S_Ni mechanism is suggested for the aryl-unassisted pathway.