Reductive dehalogenation and formation of sulfonated quinones in the aqueous reactions between various chloro-1,4-benzoquinones and sulfur(IV)

Abstract

In this paper, the kinetic study of the reaction between substituted 1,4-benzoquinones (RBQs) and Na2SO3 (S(IV)) is presented in aqueous solutions at different pH values and reagent concentrations. The stoichiometry of the reaction is 1:2 RBQs:S(IV) and one equivalent of chloride ion was also detected as a product when using mono- (2-CBQ) or dichloro-benzoquinones (2,5-DCBQ; 2,6-DCBQ) as reactants. This shows that reductive dehalogenation occurs instead of simple reduction to the corresponding substituted 1,4-hydroquinones (RBQHs) and quinone bisulfites are formed, analogously to the addition of bisulfite ion to carbonyl compounds. Various sulfonated quinones have been identified as products by electrospray mass spectrometry. Kinetic traces at different wavelengths were obtained by the stopped-flow technique with spectrophotometric detection, a kinetic fitting program (ZiTa) was used to fit a multi-step model to the data. A detailed mathematical evaluation of the reaction scheme was carried out under non-pseudo-first order conditions showing that our model can be fitted with a double exponential function even when none of the reagents are in large excess.