Decomposition of 4,4-dimethylpent-1-ene in the presence of oxygen between 400 and 500 °C: oxidation chemistry of allyl radicals

Abstract

The decomposition of 4,4-dimethylpent-1-ene (DMP) in the presence of O2 has been used as a source of allyl radicals over the temperature range 400–500 °C. The reaction has been studied in both KCl-coated (peroxy species destroyed at the surface) and aged boric-acid-coated vessels (peroxy species preserved), and the basic mechanism shown to be: DMP → t-butyl + [graphic omitted] (1), t-butyl + O2→ i-C4H8+ HO2(2). Previous studies have shown that 99% of the t-butyl radicals undergo reaction (2), so that the system is an excellent source of allyl and HO2 radicals.