Mechanistic Studies of the Solvolyses of Cyclohexanesulfonyl Chloride

In this study, the solvolysis of cyclohexanesulfonyl chloride (1) was studied by kinetics in ethanol-water, methanol- water, acetone-water, and 2,2,2-trifluoroethanol (TFE)-water binary solvent systems. The rate constants were applied to the extended Grunwald-Winstein equation, to obtain the values of m = 0.41 and l = 0.81. These values suggested SN2 mechanism in which bond formation is more important than bond breaking in the transition state (TS). Relatively small activation enthalpy values (11.6 to 14.8 kcal·mol-1), the large negative activation entropy values (-29.7 to -38.7 cal·mol-1·K-1) and the solvent kinetic isotope effects (SKIE, 2.29, 2.30), the solvolyses of the cyclohexanesulfonyl chloride (1) proceeds via the SN2 mechanism. KCI Citation Count: 0