A kinetic model for water reactivity (avoiding activities) for hydrolyses in aqueous mixtures – selectivities for solvolyses of 4‐substituted benzyl derivatives in alcohol–water mixtures

For solvolyses of various benzyl substrates in ethanol–water (EW) and methanol–water (MW) mixtures, product selectivities (S) are reported for chlorides at 75 °C defined as follows using molar concentrations: S = ([ether product]/[alcohol product]) × ([water]/[alcohol solvent]). The results support earlier evidence that solvolyses of 4-nitrobenzyl substrates are SN2 processes, which are not susceptible to mechanistic changes over the whole range of solvents from water to alcohol. S values at 25 and/or 45 °C in EW and MW, and additional kinetic data including kinetic solvent isotope effects (KSIE) are reported for solvolyses of 4-nitrobenzyl mesylate and tosylate. A kinetic model, explaining both rates and product, is proposed; a general medium effect due to solvent polarity is combined in one parameter with solvent effects on the nucleophilicity of the water and alcohol molecules acting as nucleophiles in SN2 reactions. According to this model, as alcohol is added to water the rate of reaction decreases due to a decrease in solvent polarity, but the nucleophilicity of water increases relative to alcohol. The availability of experimental rate and product data over the whole range of solvent compositions from alcohol to water, reveals limitations of alternative approaches using activities. Copyright © 2008 John Wiley & Sons, Ltd.