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Organic Chemistry Text Book (CHEM 3401 and 3402)

17.2.1 Oxidation of Alkyl Side-Chains

The benzylic hydrogens of alkyl substituents on a benzene ring are activated toward free radical attack, as noted earlier. Furthermore, SN1, SN2 and E1 reactions of benzylic halides, show enhanced reactivity, due to the adjacent aromatic ring. The possibility that these observations reflect a general benzylic activation is supported by the susceptibility of alkyl side-chains to oxidative degradation, as shown in the following examples (the oxidized side chain is colored). Such oxidations are normally effected by hot acidic pemanganate solutions, but for large scale industrial operations catalyzed air-oxidations are preferred. Interestingly, if the benzylic position is completely substituted this oxidative degradation does not occur (second equation, the substituted benzylic carbon is colored blue).


C6H5–CH2CH2CH2CH3  +  KMnO4  +  H3O(+)  &  heat    C6H5–CO2H  +  CO2
p-(CH3)3C–C6H4–CH3  +  KMnO4  +  H3O(+)  &  heat    p-(CH3)3C–C6H4–CO2H


These equations are not balanced. The permanganate oxidant is reduced, usually to Mn(IV) or Mn(II). Two other examples of this reaction are given below, and illustrate its usefulness in preparing substituted benzoic acids.