Halogen substitution reactions of halobenzenes during water disinfection

Abstract

Although being successfully applied all over the world for more than 100 years water disinfection by means of chlorination possesses certain drawbacks, first of all formation of hazardous disinfection by-products (DBP). Aromatic halogenated DBPs significantly contribute to the total organic halogen and developmental toxicity of chlorinated water. The present study deals with investigation of possible substitution of one halogen for another in aromatic substrates in conditions of aqueous chlorination/bromination. The reaction showed high yields especially in case of substrates with proper position of an activating group in the aromatic ring. Thus, ipso-substitution of iodine by chlorine is the main process of aqueous chlorination of para-iodoanisole. Oxidation of the eliminating I⁺ ions into non-reactive IO₃^- species facilitates the substitution. Oxidation of eliminating Br⁺ is not so easy while being highly reactive it attacks initial substrates forming polybrominated products. Substitution of iodine and bromine by chlorine may also involve migration of electrophilic species inside the aromatic ring resulting in larger number of isomeric DBPs. Substitution of chlorine by bromine in aromatic substrates during aqueous bromination is not so pronounced as substitution of bromine by chlorine in aqueous chlorination due to higher electronegativity of chlorine atom. However, formation of some chlorine-free polybrominated products proves possibility of that process.

Keywords: Aqueous bromination; Aqueous chlorination; Disinfection by-products; Electrophilic aromatic substitution; Gas chromatography/high resolution mass spectrometry.