Dialkyl peroxides alkoxy radicals from

Because high temperatures are required to decompose diaLkyl peroxides at useful rates, P-scission of the resulting alkoxy radicals is more rapid and more extensive than for most other peroxide types. When methyl radicals are produced from alkoxy radicals, the diaLkyl peroxide precursors are very good initiators for cross-linking, grafting, and degradation reactions. When higher alkyl radicals such as ethyl radicals are produced, the diaLkyl peroxides are useful in vinyl monomer polymerizations. 

The abstraction ability from cyclohexane of radicals derived from dialkyl peroxides has been reported. The experiments were performed with and without the trapping agent MSD (a-methylstyrene dimer), the abstracting species being alkoxy radicals derived from the peroxides. However, some dehydro dimer yields indicated that abstraction was also occurring by alkyl radicals. 

On the other hand, the persistence of the dialkyl peroxide indicates that it must not derive from a mechanism involving such oxidants. Indeed such dialkyl peroxides are readily formed by metal-catalyzed decomposition of alkyl hydroperoxides and involve alkoxy and alkylperoxy radicals. The mechanism for dialkyl peroxide formation shown below is adapted for FeTPA from previously proposed schemes ... 

In the case of aryl analogs, products may be derived either from the carboxyl radical or the radical formed by decarboxylation. Alkyl hydroperoxides give alkoxy radicals and the hydroxyl radical. t-Butyl hydroperoxide is easily available, and has often been used as a radical source. Detailed studies have been reported on the mechanism of the decomposition, which is somewhat more complicated than simple unimolecular decomposition." Dialkyl peroxides give two alkoxy radicals ... 

---