The mechanism of the oxidation of alcohols by silver carbonate on Celite was thoroughly investigated to ascertain the nature of the transition state and the possible intervention of reaction intermediates. Kinetic, stereochemical, and isotopic labeling techniques were used to differentiate among the various theoretically plausible mechanistic alternatives. The effects of surface adsorption and solvent composition on the outcome of the reaction were also studied. The data were consistent with a concerted process for which a model is proposed.
Silver carbonate on Celite in neutral media effects selective oxidative coupling of hindered phenols giving the corresponding dipheno-and stilbenequinones in high yields. Bis phenols obtained by reduction of these quiñones were also oxidized by silver carbonate. When coupling was not possible due to steric factors, the stable phenoxy radicals were isolated quantitatively. Hydroquinones and pyrocatechols gave the corresponding p-and oquinones in excellent yields. Oxidation of p-hydroxydiphenylamine and o-aminophenol gave the corresponding monoanil and phenoxazone, respectively.
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