87385-83-9Relevant academic research and scientific papers
OXIDATION DE LA METHYL ETHYL CETONE COMPARAISON AVEC L'ACETONE ET LA DIETHYLCETONE
Roux, E. le,Baronnet, F.,Scacchi, G.
, p. 209 - 222 (2007/10/02)
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.
REACTIONS OF α-DIAZO-KETONES-V; ETHER OXYGEN PARTICIPATION IN THE ACETOLYSIS OF α'-PHENOXY- AND α'-DIPHENYLMETHOXY-α-DIAZO-KETONES
Pusino, A.,Rosnati, V.,Solinas, C.,Vettori, U.
, p. 2259 - 2264 (2007/10/02)
The acetolysis of α-diazo-ketones 1a-d, 2 and 3a, b, c have been studied.The results obtained for 1a-d indicate that migration of the phenoxy group represents an important, alternative pathway to normal substitution only if a tertiary carbonium ion or a cyclic transition state, with the incipient positive charge located on a tertiary C atom, is involved in the reaction.Normal substitution was the only process in the case of 2 and 3a; instead, 3b and 3c gave in addition diphenylmethyl acetate and the corresponding 2-substituted-3-oxetanone, 17 and 19, produced by a cyclic mechanism involving the intermediate formation of oxonium ions 26b and 26c, respectively.
