Ananda, S. and Jagadeesha, M. B. and Rai, K. M. Lokanatha and Made Gowda, N. M. (1999) Kinetics of the ruthenium(III) catalyzed oxidation of amides by sodium N-bromotoluenesulfonamide in hydrochloric acid solution. Synthesis and Reactivity In Inorganic and Metal-Organic Chemistry, 29 (1). pp. 1-21. ISSN 0094-5714
Full text not available from this repository. (Request a copy)Abstract
The kinetics of Ru(III) catalyzed oxidations of urea, methylurea and ethylurea by sodium N-bromo-p-toluenesulfonamide, also known as bromamine-T (BAT), in HCl solution has been studied at 30 degrees C. The reaction rate shows a first-order dependence each on BAT], amide] and Ru(III)I and fractional-order on H+]. Additions of halide ions and the reaction product of BAT (p-toluenesulfonamide) and the variation of ionic strength and dielectric constant of the medium do not have any significant effect on the reaction rate. Activation parameters have been evaluated. A Taft linear free energy relationship is observed for the reaction, with rho*= -0.64 and -2.95 and delta = -0.25, indicating that electron donating groups enhance the rate. An isokinetic relationship is observed with beta = 391 K indicating that enthalpy factors control the rate. The existence of the relationship has been supported by the Exner criterion. The protonation constant of monobromamine-T calculated from a plot of 1/k' versus 1/H+] is 29.15. Mechanisms consistent with the observed kinetic data have been proposed.
| Item Type: | Article |
|---|---|
| Subjects: | C Chemical Science > Chemistry |
| Divisions: | Department of > Chemistry |
| Depositing User: | Vasantha uom |
| Date Deposited: | 22 Jan 2020 11:40 |
| Last Modified: | 20 Jan 2023 07:54 |
| URI: | http://eprints.uni-mysore.ac.in/id/eprint/11179 |
Actions (login required)
 |
View Item |
