Reactions of methyl radicals with fluoroaldehydes

Abstract

The reactions of methyl radicals, generated by the thermal decomposition of di-tert butyl peroxide (DTBP), with CF₃CHO, C₂F₅CHO, and C₃F₇CHO have been studied and Arrhenius parameters for the following hydrogen atom abstraction reactions obtained: [graphic omitted] The rate of hydrogen atom abstraction from the fluoroaldehydes appears to be independent of the size of the fluoroalkyl group. These results are compared with data for other reactions of the type: CH₃+HCOX→CH₄+COX.

Comparision of the relative reactivities of methyl and trifluoromethyl radicals suggests that the nature of the substrate has considerable effect, with hydrocarbons methyl radicals being much less reactive, whereas with polar molecules or molecules containing a weak X—H bond, both radicals react by hydrogen-atom abstraction at similar rates.