Ramachandra, H. and Mahadevappa, D. S. and Rangappa, K. S. (1997) Kinetics and mechanism of oxidation of alpha-phenylbenzenemethanols by sodium-N-bromo-p-toluenesulphonamide catalysed by ruthenium(III). Indian Journal of Chemistry Section B-Organic Chemistry Including Medicinal Chemistry, 36 (4). pp. 333-338.
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The kinetics of oxidation of six p-substituted alpha-phenylbenzenemethanols (Y-PBM, where Y=H, Cl, Br, NO2, CH3 and OCH3) by sodium-N-bromo-p-toluenesulphonamide or bromamine-T (BAT) in the presence of HCl and catalysed by RuCl3 in 30% (v/v) methanol medium has been studied at 35 degrees C. The experimental rate law is found to be, rate=k(1)BAT](0)PBM](0)(x) RuCl3](y)H+](z) where x=y=z<1, Addition of reaction product, p-toluenesulphonamide (TsNH2) retards the reaction. An increase in the dielectric constant of the medium decreases the rate. Rate studies in D2O medium show that the solvent isotope effect k(1)(H2O)/k(1)(D2O)=0.56. Proton inventory studies have been made in H2O-D2O mixtures. The rates correlate satisfactorily with Hammett sigma relationship and the plot is biphasic. The reaction constant rho is -2.1 for electron releasing substituents and -0.26 for electron withdrawing groups at 35 degrees C. The activation parameters Delta H#, Delta S# are linearly related and an isokinetic relationship is observed with beta=340K indicating enthalpy as a controlling factor.
| Item Type: | Article |
|---|---|
| Subjects: | C Chemical Science > Chemistry |
| Divisions: | Department of > Chemistry |
| Depositing User: | Users 23 not found. |
| Date Deposited: | 01 Jun 2021 06:04 |
| Last Modified: | 07 Jul 2022 07:58 |
| URI: | http://eprints.uni-mysore.ac.in/id/eprint/16629 |
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