Oxyhalogen–sulfur chemistry — Kinetics and mechanism of the bromate oxidation of cysteamine

Abstract

The kinetics and mechanism of the oxidation of the biologically important molecule, cysteamine, by acidic bromate and molecular bromine have been studied. In excess acidic bromate conditions, cysteamine is oxidized to N-brominated derivatives, and in excess cysteamine the oxidation product is taurine according to the following stoichiometry: BrO3–+ H2NCH2CH2SH → H2NCH2CH2SO3H + Br–. There is quantitative formation of taurine before N-bromination commences. Excess aqueous bromine oxidizes cysteamine to give dibromotaurine: 5Br2+ H2NCH2CH2SH + 3H2O → Br2NCH2CH2SO3H + 8Br–+ 8H+, while excess cysteamine conditions gave monobromotaurine. The oxidation of cysteamine by aqueous bromine is effectively diffusion-controlled all the way to the formation of monobromotaurine. Further formation of dibromotaurine is dependent on acid concentrations, with highly acidic conditions inhibiting further reaction towards formation of dibromotaurine. The formation of the N-brominated derivatives of taurine is reversible, with taurine regenerated in the presence of a reducing agent such as iodide. This feature makes it possible for taurine to moderate hypobromous acid toxicity in the physiological environment.Key words: cysteamine, hypobromous acid, toxicities, antioxidant.