Metathetical reactions of methoxyl radicals

Abstract

The chemistry of methoxyl has been reviewed with emphasis placed on quantitative experiments. The following reactions have been discussed: radical production, combination, disproportionation and hydrogen abstraction. There is very little quantitative information available on the metathetical reactions of methoxyl radicals, and in particular no previous studies of hydrogen abstraction from C2 to C5 alkanes has been reported for methoxyl or any other alkoxyl radical. Three approaches to the study of the metathetical reactions of methoxyl have been described. The first two methods, which depended on measuring the rate of formation of products, had to be abandoned because analysis showed that the systems were more complex than previous work had indicated. The third and apparently successful approach depended on measuring consumption of reactants when methoxyls were generated in mixtures of alkanes between 200 °C and 400°C: CH3O + R1H = CH3OH + R1 CH3O + R2H = CH30H + R2 The alkyl radicals were removed by nitric oxide. The experiments were oerformed in a cyclic flow system and the residual alkanes were estimated by the Janak technique of gas chromatography.