Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Kinetics and Mechanism of Oxidation of Ethyl Phenylthioacetates by Bromamine-B
Rajagopal GurumurthyKulathu Iyer SathiyanarayananMannathusamy Gopalakrishnan
Author information
JOURNALS RESTRICTED ACCESS

1992 Volume 65 Issue 4 Pages 1096-1100

Details
Abstract

The kinetics of oxidation of several substituted ethyl phenylthioacetates by bromamine-B (sodium salt of N-bromobenzenesulfonamide) has been studied in 50% (v/v) aqueous ethanol medium. Disodium hydrogenphosphate and sodium dihydrogenphosphate buffer has been used. The reaction is of a total second order, first order each with respect to the reactants. A catalytic effect of mercury has been observed and the order with respect to Hg(II) is one. Electron-releasing substituents generally accelerate the rate while electron-withdrawing groups retard the rate. A good correlation is found to exist between log k2 and Hammett σ constants. Two mechanisms have been proposed, one in presence of Hg(II) and the other in the absence of Hg(II). In presence of Hg(II), rate = k[C1][H2OBr]+ and in the absence of Hg(II), rate = k[S] [H2OBr]+

Susceptibility of the reaction to the steric effect of ortho substituents, has been analyzed in the light of application of Taft’s steric energy relationships.

Information related to the author

This article cannot obtain the latest cited-by information.

© 1992 The Chemical Society of Japan
Previous article Next article
feedback
Top