- DECOMPOSITION OF DIOXIRANES INDUCED BY DIALKYL ETHERS
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Simple dialkyl ethers (i.e. diethyl or dihexyl ether), in addition to undergo oxidative cleavage by reaction with methyl(trifluoromethyl)dioxirane or dimethyldioxirane, induce the decomposition of these oxidation reagents in a concentration dependent manner.The identification of compounds derived from reactions with species such as CH3. or CF3CO2. suggests that the above decomposition is a radical chain process.Key words: Ether, radicals, dimethyldioxirane, methyl(trifluoromethyl)dioxirane.
- Ferrer, Marta,Sanchez-Baeza, Francisco,Casas, Josefina,Messeguer, Angel
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p. 2981 - 2984
(2007/10/02)
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- Thermally and photochemically initiated radical chain decomposition of ketone-free methyl(trifluoromethyl)dioxirane
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Ketone-free solutions of methyl(trifluoromethyl)dioxirane (1) were obtained for the first time in several inert solvents, which enabled the study of the thermal and photochemical decompositions of dioxirane 1 in gas, solution, and matrix phases. Vacuum flash pyrolysis of dioxirane 1 afforded exclusively methyl trifluoroacetate (3a). Both gas- and liquid-phase photolyses and thermal liquid-phase decomposition of dioxirane 1 involve a radical chain process, initiated by attack of CH3 and CF3 radicals on dioxirane 1 to give α-alkoxy-substituted alkoxy radicals as intermediates; the latter are responsible for the production of esters 3a-d. Matrix-phase photolysis of dioxirane 1 led to methyl trifluoroacetate (3a) and 1,1,1 -trifluoroethane as main products, while gas-phase pyrolysis gave exclusively the ester 3a.
- Adam, Waldemar,Curci, Ruggero,Nu?ez, Maria Elena González,Mello, Rossella
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p. 7654 - 7658
(2007/10/02)
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