Solvent Effects on the Solvolysis of <i>p</i>-Nitrobenzyl and 3,5-Bis(trifluoromethyl)benzyl <i>p</i>-Toluenesulfonates

Abstract

Abstract Solvolysis rates of p-nitrobenzyl and 3,5-bis(trifluoromethyl)benzyl p-toluenesulfonates were determined in a wide variety of solvents. The solvent effects were analyzed based on the Winstein–Grunwald equation. The solvent effect on these deactivated benzyl solvolyses failed to give a single linear correlation with the 2-adamantyl YOTs parameter. The lower response to the solvent polarity and the pattern of dispersion for respective binary solvent series can be interpreted in terms of nucleophilic solvent assistance. The application of the equation gave a low m value of 0.4 and a large l of close to unity for both derivatives. Furthermore, the l value is also comparable to that for ethyl p-toluenesulfonate and even close to that for the methyl derivative, which has generally been defined as the standard SN2 substrate.