- The Reaction of Dimethyldioxirane with Alkynes
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The reaction of dimethyldioxirane with several alkynes gives products which are conveniently rationalized by postulating the intermediacy of oxirenes and oxocarbenes.The latter serve as precursors to H atom or methyl group migration products, as well as to cyclopropane insertion products in some cases.Alkenes, derived from some of these carbene reactions, are partially converted to epoxides.
- Murray, Robert W.,Singh, Megh
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p. 5076 - 5080
(2007/10/02)
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- OXIDATION DE LA METHYL ETHYL CETONE COMPARAISON AVEC L'ACETONE ET LA DIETHYLCETONE
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An experimental investigation in a conventional static apparatus of the oxidation of methylethylketone at ca. 350 deg C and subatmospheric pressure confirms the specific features of the reaction, compared with those of the neighbouring ketones, acetone and diethylketone, especially the very long induction period of the first cool flame.To interpret these experimental results, we propose a free radical mechanism based upon the determination of the primary products of the reaction and the evaluation of the rate constants for the elementary steps by the methods of thermochemical kinetics.Contrary to the oxidation reactions of acetone and diethylketone in wich the dominating chain carrier appears to be OH., in the case of methylethylketone HO2. seems to have a key role.It is well known that HO2. cannot be an efficient propagating radical in oxidation reactions and therefore the overall kinetics of the reaction do not trigger off cool flame formation.
- Roux, E. le,Baronnet, F.,Scacchi, G.
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p. 209 - 222
(2007/10/02)
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