Chlorination of Phenols Revisited: Unexpected Formation of α,β-Unsaturated C4-Dicarbonyl Ring Cleavage Products

Despite decades of research on the fate of phenolic compounds when water is disinfected with hypochlorous acid (HOCl), there is still considerable uncertainty regarding the formation mechanisms and identity of ring cleavage products, especially at higher chlorine doses. This study focuses on the formation of electrophilic ring cleavage products—a class of compounds that poses potential health risks at relatively low concentrations—from the reactions of phenols with chlorine. By monitoring the formation of products of reactions between ring cleavage products and the model nucleophile N-α-acetyl-lysine, we identified the α,β-unsaturated dialdehyde 2-butene-1,4-dial (BDA) and its chlorinated analogue, chloro-2-butene-1,4-dial (Cl-BDA), after the chlorination of phenol, para- and ortho-substituted chlorophenols (2-Cl, 4-Cl, 2,4-diCl-, 2,6-diCl, and 2,4,6-triCl-phenol), and 3,5-di-Cl-catechol. Maximum yields of BDA were observed when chlorine was present in large excess (HOCl/phenol ratios of 30:1 to 50:1), with yields ranging from 18% for phenol to 46% for 3,5-diCl-catechol. BDA and Cl-BDA formation was also observed during the chlorination of brominated phenols. For methyl-substituted phenols, the presence of methyl substituents in both positions ortho to the hydroxy group inhibited BDA and Cl-BDA formation, but the chlorination of cresols and 2,3-dimethylphenol yielded methyl- and dimethyl-BDA species. This study provides new insights into the formation of reactive and toxic electrophiles during chlorine disinfection. It also provides evidence for the importance of phenoxy radicals produced by one-electron transfer reactions initiated by chlorine in the production of dicarbonyl ring cleavage products.