Abstract
AbstractSolvent–solute interactions in the peroxyacid oxidations are believed to be specific rather than electrostatic in nature. The kinetic solvent effects reported for the oxidations of organic sulfides, olefins, acetylenes, nitrosobenzenes, thioketones, and aryl sulfines reveal that in each case the rates are fast in nonbasic solvents (e.g., benzene, nitrobenzene, and halogenated hydrocarbons) relative to those in basic solvents such as DMF, dioxane, and alcohols. The rates in CF3CH2OH and aqueous or partially aqueous media are again higher than those in the basic solvents. This remakably similar pattern of sensitivity of rates to changes in the solvent nature appears to be characteristic of these oxidations as demonstrated by the existence of linear free‐energy relationship. The behavior is best understood in terms of cyclic transition states for these oxidations in which charge separation is avoided by intra‐ or intermolecular hydrogen bonding depending on the nature of the solvent. Solvent effects on sulfoxide oxidation and on oxidations by hydrogen peroxide and t‐butylhydroperoxide are also briefly discussed.
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