Photochemistry and environment IV- Photochemical behaviour of monochlorophenols in dilute aqueous solution

The photochemical behaviour of chlorophenols is different to that of non-halogenated phenols. In the former, the first step is a C-Cl bond scission, which is not influenced by oxygen. Chlorine is converted into hydrochloric acid. For monochlorophenols, the position of the chlorine on the ring strongly influences the transformation. In the molecular form, 2-chlorophenol is converted into pyrocatechol. In the anionic form however, it is reduced in a cyclopentadienic acid which dimerizes according to a Diels-Alder reaction. The irradiation of 3-chlorophenol leads to resorcinol whatever the pH. This would appear to suggest a photohydrolysis mechanism. With 4-chlorophenol, the photochemical conversion is not so specific. Hydroquinone is formed (mainly in aerated solution), along with polyphenolic oligomers. A radical mechanism is proposed.