Reactions of methyl radicals with oxetan, 2-methyloxetan and 2,4-dimethyloxetan

Abstract

The reactions of methyl radicals with oxetan, 2-methyloxetan and 2,4-dimethyloxetan have been studied. The overall rates of hydrogen atom abstraction from these three compounds have been obtained for the temperature range 100–200°C, by assuming the value of Quinn and co-workers for the rate of recombination of methyl radicals.

The following rate expressions were found: log₁₀(k/cm³ mol^–1 s^–1)_(ox)= 11.29(± 0.19)– 35.22(± 0.64) kJ mol^–1/2.303RT, log₁₀(k/cm³ mol^–1 s^–1)_(2ox)= 11.42(± 0.18)– 34.04(± 0.62) kJ mol^–1/2.303RT, log₁₀(k/cm³ mol^–1 s^–1)_(2,4ox)= 11.51(± 0.18)– 33.52(± 0.69) kJ mol^–1/2.303RT.

The results are compared with those for other hydrogen abstraction reactions by methyl radicals and the implications for the gas phase thermolyses of substituted oxetans are discussed.