Factors governing product distribution in the oxidation of alkenes by manganese(III) acetate in acetic acid and acetic anhydride

Abstract

A systematic investigation has been carried out into the effect of different reaction parameters on the oxidation of oct-1-ene by manganese(III) acetate in acetic acid and acetic anhydride. The most important factor in dictating the ratio of products is the composition of the solvent. In the absence of anhydride γ-decanolactone is virtually the sole product. Even small quantitites of anhydride lead to the lactone being replaced by other products derived from cationic intermediates C₆H₁₃[graphic omitted]HCH₂COX (X = OH or OAc). Further increases in the amount of anhydride encourage the formation of decanoic acid until, in 90% anhydride, this becomes the predominant product. The results cannot be interpreted simply in terms of competition for the alkene by the radicals ·CH₂CO₂H and ·CH₂COOCOCH₃. Decanoic acid formation is also favoured by low temperatures, low concentration of oxidants, and by the addition of acetate ions. A comparision is made of the efficiency of addition when the initiating species is manganese(III) or a peroxide.