Stoichiometric Solvation Effects. Solvolysis of Isopropylsulfonyl Chloride

Stoichiometric Solvation Effects. Solvolysis of Isopropylsulfonyl Chloride

Solvolyses of isopropylsulfonyl chloride (IPSC) in water, D_2O,\;CH_3OD$, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25, 35 and 45$^{\circ}C$. The Grunwald-Winstein plot of first-order rate constants for the solvolytic reaction of IPSC with $Y_{Cl}$ (based on 2-adamantyl chloride) shows marked dispersions into three separate lines for three aqueous mixtures with a small slope (m < 0.30). The extended Grunwald-Winstein plots for the solvolysis of IPSC show better correlation. The kinetic solvent isotope effects determined in water and methanol are in consistent with the proposed mechanism of the general base catalyzed and/or $S_AN/S_N2$ reaction mechanism for IPSC solvolyses based on mass law and stoichiometric solvation effect studies.