S. Grabovskii, E. A. Markov, E. G. Galkin
Apr 24, 2009
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Journal
Kinetics and Catalysis
Abstract
The products and kinetics of the thermolysis of 1,2-dioxaspiro[2,5]octane in cyclohexanone and cyclohexanone-CCl4 mixtures are studied. 1,2-Dioxaspiro[2,5]octane is consumed via two parallel routes: isomerization to oxepan-2-one and solvent (cyclohexanone) oxidation with the partial escape of radicals from the cage (17% at 25 °C). Under an inert atmosphere, the alkyl radicals formed by solvent oxidation initiate the chain radical decomposition of 1,2-dioxaspiro[2,5]octane. The mechanism of 1,2-dioxaspiro[2,5]octane thermolysis is discussed on the basis of the results obtained. The activation parameters of 1,2-dioxaspiro[2,5]octane isomerization to oxepan-2-one and reactions of dioxaspiro[2,5]octane with cyclohexanone are discussed.