Collect. Czech. Chem. Commun. 1999, 64, 1790-1796

Application of the NT Solvent Nucleophilicity Scale to Attack at Sulfur: Solvolyses of Benzenesulfonyl Chlorides

Dennis N. Kevilla,* and Malcolm J. D'Souzab

a Department of Chemistry and Biochemistry, Northern Illinois University, DeKalb, IL 60115-2862, U.S.A.
b Department of Chemistry, University of Wisconsin-Waukesha, Waukesha, WI 53188-2799, U.S.A.


The specific rates of solvolysis of benzenesulfonyl chloride and three 4-substituted derivatives can be very well correlated using the extended Grunwald-Winstein equation, with incorporation of NT solvent nucleophilicity and YCl solvent ionizing power values. In two instances, it was shown that almost identical correlations were obtained after the incorporation of methyl groups into the 2- and 6-positions of the benzene ring. No evidence was found for a dissociative (SN1) mechanism or for a duality of mechanism. All of the results can be rationalized in terms of a concerted bimolecular displacement (SN2) mechanism, involving attack by solvent at sulfur.

Keywords: Solvolysis; Benzenesulfonyl chlorides; Extended Grunwald-Winstein equation; Solvent nucleophilicity; Reaction kinetics.