Oxyhalogen–Sulfur Chemistry: Kinetics and Mechanism of Oxidation of Tiopronin by Acidified Bromate and Aqueous Bromine
Wilbes Mbiya A , Risikat Adigun A , Thai Tran A , Yadana Htwe A and Reuben H. Simoyi A B C
+ Author Affiliations
- Author Affiliations
A Department of Chemistry, Portland State University, PO Box 751, Portland, OR 97207-0751, USA.
B School of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus, Durban 4014, South Africa.
C Corresponding author. Email: rsimoyi@pdx.edu
Australian Journal of Chemistry 68(2) 262-272 https://doi.org/10.1071/CH14126
Submitted: 15 March 2014 Accepted: 25 April 2014 Published: 21 July 2014
Abstract
N-2-(Mercaptopropionyl)glycine (MPG) is a free-radical scavenger, a detoxicating synthetic aminothiol which also acts as an antioxidant with a wide range of clinical applications. The oxidation of MPG by aqueous bromine and acidified bromate has been studied by spectrophotometric techniques. The stoichiometry for the reaction of acidic bromate with MPG is 1 : 1, HS(CH3)CH(=O)N(H)CH2COOH + BrO3– → HO3S(CH3)CH(=O)N(H)CH2COOH + Br–, with reaction occurring only at the thiol centre. The involvement of thiyl radicals in the oxidation of MPG competes with a non-radical pathway involving two-electron oxidations of the sulfur centre. A bimolecular rate constant of 5.68 (±0.94) × 103 M–1 s–1 for the direct reaction of MPG with bromine was determined. Electrospray ionization spectral data show that MPG is oxidized through its sulfinic acid, by-passing the unstable sulfenic acid. A simplified reaction network consisting of 19 reactions was simulated and it gave a very good fit to the experimental data.
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