Solvent Effects on the Alkaline Hydrolyses of 4-Nitrophenyl N-Aroyl-Areneiminosulfonates

Abstract Second-order rate constants have been determined for the alkaline hydrolyses of N-aroyl-p-toluenesulfonimidic esters in aqueous organic solvents. Rate minima were observed with decreasing water concentration in aqueous acetonitrile, dioxane and t-butanol mixtures whereas rates of hydrolysis decrease continuously in MeOH-H2O and increase in DMSO-H2O. Solvent effects, Arrhenius parameters, and substituent effects are consistent with either an addition-elimination or a concerted SN2-type mechanism.

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