Oxidation Reactions of Higher Alkyl Radicals

Oxidation Reactions of Higher Alkyl Radicals.—Currie, Sidebottom, and Tedder have photolysed azobutane + O2 mixtures between room temperature and 47S K, and concluded that the m or products are formed through radical-radical reactions. Chain processes are insignificant, but to explain the relative proportions of products, cyclic trioxy- and tetroxy-species are suggested. The important reactions are 

Their results and general condusions are similar to those of Mayo et alf who initiated the oxidation of n-C4Hto with t-butyl peroxide at 398 K. 

In the region 550—800 K, with hydrocarbons where its formation is possible structurally, conjugate alkene is the nu or product in the early stages of reaction, and it may be formed in at least three ways in the oxidation of R- radicals. 

Two reactions similar to (6A) have been studied. Wadiida, Nfartinez, and Bayes measured the steady-state concentration of HCO in the presence of O2, using a photo-ionization mass spectrometer (Method Xm), and calculated kso = (3.4 0.7) X 10 dm mol s at 297 K. Reaction (SO) almost certainly IHroceeds via a direct bimolecular st involving virtually no activation enogy. 

An Ox-addition path to give HCOa would lead to carbon dioxide and OH- radicals as products. 

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