Kinetics of the ruthenium(III) catalyzed oxidation of amides by sodium N-bromotoluenesulfonamide in hydrochloric acid solution

Ananda, S. and Jagadeesha, M.B. and Rai, K.M.L. and Gowda, N.M.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

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Kinetics of the Kuthenium III Catalyzed Oxidatjon of Amides by Sodium N Bromotoluenesulfonamide in Hydrochloric Acid Solution.pdf
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Official URL: https://doi.org/10.1080/00945719909349431

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: lpa venkatesh user
Date Deposited: 12 Jun 2021 07:15
Last Modified: 12 Jun 2021 07:15
URI: http://eprints.uni-mysore.ac.in/id/eprint/16857

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