Oxidation of alcohols in basic solvents

Addition of bases to alcohols inhibits the chain oxidation due to the equilibrium 

Oxidation of alcoholates yields ketyl radicals [108,109], They are formed in alkaline medium by reaction of the alcoholate with ketone [110] 

Alkali metal benzhydrolate oxidizes in toluene [111] and benzene [112] as well as in f-butanol [113] with autocatalysis that is produced by the K02 formed in the oxidation [113]. The induction period disappears when K02 is added to a solution of potassium benzhydrolate. The kinetics of oxidation of sodium benzhydrolate was studied by Pereshein et al. [111]. The maximum oxidation rate appears to be approximately proportional to [RONa] [02]/[ROH],the activation energy being 12 kcal mole-1. The inhibiting action of alcohol (benzhydrol and t-butanol) on the oxidation of metal benzhydrolates was noted by Russell et al. [110], No deuterium exchange was observed during the oxidation of potassium benzhydrolate in t-butanol. Thus no dianions are produced from benzhydrolate ion by the equilibrium reaction 

Oxidation of fluorenol and xanthenol alcoholates in f-butanol and mixtures with pyridine and dimethylsulfoxide is accelerated by nitrobenzene [113]. The mechanism suggested is 

Methanol is oxidized by 02 in the presence of CH3ONa and cupric phenan-throline complex [114] to form formaldehyde. The proposed mechanism is 

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