Permanganate oxidation of aromatic alcohols in acid solution

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Abstract
The mechanism of the permanganate oxidation of di- and tri-arylcarbinols has been studied in aqueous sulfuric acid. With both kinds of alcohols the rate-controlling step in solutions more acidic than H0 −0.50 was found to be the ionization of the carbinol to give the carbonium ion followed, it is believed, by rapid reaction with permanganate ion to form the ester which decomposes rapidly to products. In the case of the tertiary alcohols the decomposition probably proceeds via a 1,2-aryl shift. The effect of substituents is correlated with σ+ in both cases, ρ+ being −1.02 and −1.39 for the secondary and tertiary series. The acidity function which governs both reactions is H0. Tri(p-tolyl)carbinol is exceptional in that its oxidation in solutions more acidic than HR −2.6 is second-order and is governed by the HR acidity function.

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