Alkanes allylic/benzylic oxygenation

When chlorination or bromination of alkenes is carried out in the gas phase at high temperature, addition to the double bond becomes less significant and substitution at the allylic position becomes the dominant reaction.153-155 In chlorination studied more thoroughly a small amount of oxygen and a liquid film enhance substitution, which is a radical process in the transformation of linear alkenes. Branched alkenes such as isobutylene behave exceptionally, since they yield allyl-substituted product even at low temperature. This reaction, however, is an ionic reaction.156 Despite the possibility of significant resonance stabilization of the allylic radical, the reactivity of different hydrogens in alkenes in allylic chlorination is very similar to that of alkanes. This is in accordance with the reactivity of benzylic hydrogens in chlorination. 

Ammoxidation refers to the formation of nitriles by oxidation of hydrocarbons with oxygen in the presence of ammonia (Figure 1) [1]. Ammoxidation is best conducted with olefins, or with aromatic or heteroaromatic compounds, containing a readily abstractable H atom (allylic or benzylic intermediates are formed), although the ammoxidation of alkanes (e. g. propane to acrylonitrile [e. g. 2-4] or ethane to acetonitrile [e. g. 5]) is also possible. An exceptional example is the ammoxidation of methane to hydrogen cyanide by the Andrussov reaction [6]. 

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