The kinetic regularities, products, and mechanism of the thermal decomposition of dimethyldioxirane. The contribution of molecular and radical reaction channels

Article abstract of DOI:10.1007/BF02495074

The products and kinetics of the thermal decomposition of dimethyldioxirane (DMDO) were studied. The reaction proceeds via three parallel pathways: isomerization to methyl acetate, oxygen atom insertion into the C - H bond of a solvent molecule (acetone), and the solvent-induced homolysis of the O - O bond in the DMDO molecule. The contribution of the latter reaction channel is ca. 23% at 56 °C. The overall kinetic parameters of DMDO thermolysis in oxygen atmosphere were determined. The free radical-induced DMDO decomposition occurs in an inert atmosphere. The formal kinetics of this reaction was investigated. The mechanism of the DMDO thermolysis is discussed.