Autoxidation of nitrogen-containing compounds

Investigation of the kinetics of the reactors is sparse, with the possible exception of the production of nitroxides from amines discussed above. What results are available show that the autoxidation of the nitrogen-containing molecule is similar to that of hydrocarbons, bearing in mind the 

Rate coefficients of chain propagation and termination reactions measured by the rotating sector technique 

The peroxy radicals involved in this reaction sequence are interesting in that they possess both oxidative and reductive capabilities. As a result, molecules such as aromatic amines can undergo a cyclic reaction such as [52,55,57,58] 

In contrast, the peroxy radicals of amides show no reducing activity and the stoichiometric coefficient of inhibition for phenols and aromatic amines is close to 2 [56,59,60], 

similar to hydrocarbons, the autoxidation of amines is affected by the presence of metal ions. This appears to have been first reported by Bacon [61], who used Ag+/S2Ol to oxidise primary and secondary amines. Subject to the availability of an a-hydrogen atom, good yields of 

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The evidence that electron-directing groups also affect the rate and nature of autoxidation of nitrogen-containing compounds has been well reviewed by Hoft and Schultze [51], particularly for the oxidation of amyl phenylhydrazines where it has been possible to relate rates of oxidation with predictions based on the Taft—Hammett relationship [76]. Similar relationships have been established with phenylhydrazones, which have been found to oxidise to produce a hydroperoxide [77]... 

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