Articles written in Journal of Chemical Sciences
Volume 87 Issue 8 August 1978 pp 219-227 Organic
The kinetics of oxidation of ortho, meta and para substituted α-phenyl ethyl alcohols by Tl(III) shows that these reactions are susceptible to electronic influences. The negative ρ(−2·11) points to the formation of electron deficient carbon atom. The oxidation of benzhydrol exhibits a kinetic isotope effect 6·4. The Tl(III) oxidation of l-phenyl propyl alcohol, 4-chloro benzhydrol, 1-naphthyl methyl carbinol, 2-naphthyl methyl carbinol and fluorenol has been studied. A mechanism involving the loss of hydrogen atom as a hydride ion is proposed. The thermodynamic parameters of the reaction are also presented.
Volume 91 Issue 5 October 1982 pp 371-375 Physical and Theoretical
The kinetics of Tl(III) oxidation of hydroxylamine hydrochloride in 1·0 M H2SO4 at a fixed chloride concentration has been investigated to make a formal comparison of the observed rate with that of hydrazine sulphate. The reaction exhibits total second order kinetics—first order in each reactant. The rate of the reaction depends inversely on the first power of [H+] and [Cl−] suggesting the possible reactive species as TlOH2+. To account for the stoichiometry of the reaction [Tl(III)]: [H2NOH·HCl)=1·5∶1 and the products of the reaction, HNO2 and N2O, two reaction schemes have been proposed.
Volume 91 Issue 5 October 1982 pp 421-436 Organic
The kinetics of chlorination of aliphatic, aralkyl and alicyclic ketones by 1-chlorobenzotriazole (
Volume 91 Issue 6 December 1982 pp 467-473 Organic
Tl(III) acetate oxidation of cyclohexanol, cyclopentanol, cycloheptanol,
Volume 92 Issue 1 January 1983 pp 107-112 Organic
The kinetics of oxidation of phenylmethylcarbinol and substituted phenylmethylcarbinols by bromanine-
Volume 94 Issue 3 June 1985 pp 467-473 Organic Chemistry
The alkaline hydrolysis of a series of aryl phosphorodiamidates has been studied in aqueous ethanol and aqueous DMSO mixtures. Although the reactions do not show any saturation kinetics with respect to the hydroxide ion, the low solvent isotope effect, the highly negative Bronsted β value, the large Hammett ρ for the leaving aryloxy group and the decrease in rate with increase in the proportion of DMSO in the solvent mixtures indicate that the hydrolysis proceeds by an elimination-addition pathway. Comparison of rate data with other hydrolytic E1CB reactions show that the title reaction belongs to the (E1CB)R category.
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