141665-40-9Relevant articles and documents
Products, kinetic regularities, and mechanism of thermal decomposition of ethyl(methyl)dioxirane
Grabovskiy,Markov,Ryzhkov,Kabal'nova
, p. 1780 - 1787 (2008/02/10)
The products and kinetic regularities of thermal decomposition of ethyl(methyl)dioxirane (EMD) were studied. The consumption of EMD occurs via four parallel pathways: two isomerizations to ethyl acetate and methyl propionate, solvent oxidation via insertion of the oxygen atom into the C-H bond of a solvent molecule (butanone), and hydrogen atom abstraction from the solvent by dioxirane with radical escape from the cage. The contribution of the latter route to the oxidation of butan-2-one at 35°C is 43%. Alkyl radicals initiate EMD decomposition in an inert atmosphere. The activation parameters of EMD isomerization to esters and the reaction of EMD with butanone were determined. The isomerization of EMD was studied by the DFT method. The geometric parameters were optimized at the UB3LYP level using the 6-31G**and/or 6-311+G**basis sets. The calculated energies were corrected taking into account zero-point vibrations. The theoretical results are in good agreement with experimental data. The mechanism of EMD thermolysis is considered.
Chemistry of Dioxiranes. 21. Thermal Reactions of Dioxiranes
Singh, Megh,Murray, Robert W.
, p. 4263 - 4270 (2007/10/02)
Thermolysis of dioxiranes in solutions of their parent ketones or in mixtures of the parent ketone and a foreign ketone leads to the formation of esters.The results are explained by postulating a free-radical mechanism involving H atom abstraction from the ketones.The resulting radicals are converted to the observed esters by reaction with acyloxy radicals derived from homolysis of the dioxiranes.Autodecomposition of dimethyldioxirane in acetone solution at room temperature gives methyl acetate at a very slow rate.When catalyzed by BF3 etherate the same decomposition proceeds much more rapidly and is accompanied by acetol formation.
