Correlation of the rates of solvolysis of two arenesulfonyl chlorides and of trans-β-styrenesulfonyl chloride - Precursors in the development of new pharmaceuticals

Abstract

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-β-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 N2 process is proposed. For 3, kinetic solvent isotope effects of 1.46 for k H2O/k D2O and 1.76 for k MeOH/k MeOD were determined. These are also compared to literature values for other sulfonyl chlorides. © 2008.