The rates of oxidation of 4-chlorophenylmethyl suphide, 1, 2-[(4-chlorophenyl) thio]ethanol, 2, 1-methylcyclohexene, 3, and geraniol, 4, by t-butylhydroperoxide and hydrogen peroxide in the presence of V(V) and Mo(IV) catalysts have been measured at various temperatures. The kinetic data and the Arrhenius parameters obtained allow a comparison among the substrates and the oxidizing systems. On the basis of such a comparison, the effect of the hydroxo group on the behaviour of 2 and 4 may be estimated. The suggestion is made that the enhanced reactivity of such substrates, in some cases, is related to the specific interaction of the OH group in the transition state with the peroxide oxygen rather than to the formation of a ground-state alkoxo-peroxo complex. © 1983.
Metal Catalysis in Oxidation by Peroxides. Part 17. On the Mechanism of the Vanadium and Molybdenum Catalyzed Oxidation of Sulphides and Olefins Bearing Neighbor Hydroxo Groups by tert-Butyl Hydroperoxide and Hydrogen Peroxide
BORTOLINI, Olga;
1983
Abstract
The rates of oxidation of 4-chlorophenylmethyl suphide, 1, 2-[(4-chlorophenyl) thio]ethanol, 2, 1-methylcyclohexene, 3, and geraniol, 4, by t-butylhydroperoxide and hydrogen peroxide in the presence of V(V) and Mo(IV) catalysts have been measured at various temperatures. The kinetic data and the Arrhenius parameters obtained allow a comparison among the substrates and the oxidizing systems. On the basis of such a comparison, the effect of the hydroxo group on the behaviour of 2 and 4 may be estimated. The suggestion is made that the enhanced reactivity of such substrates, in some cases, is related to the specific interaction of the OH group in the transition state with the peroxide oxygen rather than to the formation of a ground-state alkoxo-peroxo complex. © 1983.I documenti in SFERA sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
