Additional specific rates of solvolysis have been determined, mainly in fluoroalcohol containing solvents, for benzenesulfonyl chloride (1) and p-nitrobenzene-sulfonyl chloride (2). For trans-beta-styrenesulfonyl chloride (3), a study has been carried out in 43 pure and binary solvents, covering a wide range of hyroxylic solvent systems. For the specific rates of solvolyses of each of the three substrates, a good correlation was obtained over the full range of solvents when the extended Grunwald-Winstein equation was applied. The sensitivities to changes in solvent nucleophilicity and solvent ionizing power are similar to values determined earlier and an S(N)2 process is proposed. For 3, kinetic solvent isotope effects of 1.46 for k(H(2)O)/k(D(2)O) and 1.76 for k(MeOH)/k(MeOD) were determined. These are also compared to literature values for other sulfonyl chlorides.
Keywords: Grunwald-Winstein equation; Linear Free Energy Relationships; Solvolysis; benzenesulfonyl chloride; general base catalysis; kinetic solvent isotope effect; para-nitrobenzenesulfonyl chloride; sulfonyl transfer; trans-β-styrenesulfonyl chloride.