Autooxidation of ethers

Reactions that take place via radical intermediates are occasionally also begun by radical initiators, which are present unintentionally. Examples are the autooxidation of ethers (see later Figure 1.28) or one of the ways in which ozone is decomposed in the upper stratosphere. This decomposition is initiated by, among other things, the fluorochlorohydrocarbons (FCHCs), which have risen up there and form chlorine radicals under the influence of the short-wave UV light from the sun (Figure 1.10). They function as initiating radicals for the decomposition of ozone, which takes place via a radical chain. However, this does not involve a radical substitution reaction. 

Organic peroxo compounds are also obtained by autooxidation of ethers, unsaturated hydrocarbons, and other organic materials on exposure to air. A free-radical chain reaction is initiated almost certainly by radicals generated by the interaction of oxygen and traces of metals such as copper, cobalt, or iron. The attack on specific reactive C—H bonds by a radical X" gives first R, then hydroperoxides, which can react further ... 

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