Abstract
AbstractSolvolytic rate constants (k) at 25 °C are reported for solvolyses of cinnamyl chloride (1) in binary mixtures of water with acetone, ethanol, methanol, methanol‐d and 2,2,2‐trifluoroethanol (TFE), and also in TFE–ethanol mixtures; product selectivities (S) are reported for aqueous ethanol and methanol: S = [ether product]/[alcohol product] × [water]/[alcohol solvent]. A good correlation observed between log k and the parameter YCl (solvent ionizing power) is improved only slightly by additional parameters (N for solvent nucleophilicity and/or I, an aromatic ring parameter). Rate ratios in solvents of the same YCl value but different nucleophilicities provide measures of the minimum extent of nucleophilic solvent assistance, and the value of 1.48 for [k40EW/k97TFE] Y (EW = ethanol–water) is consistent with an essentially SN1 reaction mechanism. A linear relationship between 1/S and molar ratio of solvent was derived theoretically and validated experimentally for solvolyses of the above substrate from water up to 75% alcohol–water. The dependence of S on solvent composition and the absence of rate depression in the presence of added chloride anions are explained by product formation via a contact ion pair. Copyright © 2002 John Wiley & Sons, Ltd.
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