Oxidation of some catecholamines by sodium N-chloro-p-toluenesulfonamide in acid medium: A kinetic and mechanistic approach

• Authors: Puttaswamy , R. Jagadeesh , Nirmala Vaz
• Languages of publication: EN

Abstracts

EN

The kinetics of the oxidation of five catecholamines viz., dopamine (A), L-dopa (B), methyldopa (C), epinephrine (D) and norepinephrine (E) by sodium N-chloro-p-toluenesulfonamide or chloramine-T (CAT) in presence of HClO4 was studied at 30±0.1 °C. The five reactions followed identical kinetics with a first-order dependence on [CAT]o, fractional-order in [substrate]o, and inverse fractional-order in [H+]. Under comparable experimental conditions, the rate of oxidation of catecholamines increases in the order D>E>A>B>C. The variation of ionic strength of the medium and the addition of p-toluenesulfonamide or halide ions had no significant effect on the reaction rate. The rate increased with decreasing dielectric constant of the medium. The solvent isotope effect was studied using D2O. A Michaelis-Menten type mechanism has been suggested to explain the results. Equilibrium and decomposition constants for CAT-catecholamine complexes have been evaluated. CH3C6H4SO2NHCl of the oxidant has been postulated as the reactive oxidizing species and oxidation products were identified. An isokinetic relationship is observed with β=361 K, indicating that enthalpy factors control the reaction rate. The mechanism proposed and the derived rate law are consistent with the observed kinetics.

Keywords

EN

Catecholamines; oxidation kinetics; chloramine-T; acid medium

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2005
• Volume: 3
• Issue: 2
• Pages: 326-346

Dates

published

1 - 6 - 2005

online

1 - 6 - 2005

Contributors

author

Puttaswamy

• Department of Post-Graduate Studies in Chemistry, Central College, Bangalore University, 560 001, Bangalore, India

author

R. Jagadeesh

• Department of Post-Graduate Studies in Chemistry, Central College, Bangalore University, 560 001, Bangalore, India

author

Nirmala Vaz

• Department of Post-Graduate Studies in Chemistry, Central College, Bangalore University, 560 001, Bangalore, India

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Identifiers

DOI

10.2478/BF02476000