Aqueous chlorination of resorcinol

An investigation of the aqueous chlorination (NaOCl) of resorcinol is reported. The following intermediates were detected in moderate to high yield at different pH values and varying percentages of chlorination: 2-chloro-, 4-chloro-, 2,4-dichloro-, 4,6-dichloro- and 2,4,6-trichlororesorcinol. Only trace amounts of the intermediates were detected when the chlorination was conducted in the presence of phosphate buffer. This result has significant implications since resorcinol in phosphate buffer has been used as a model compound in several recent studies on the formation of chlorinated hydrocarbons during chlorination of drinking water. Relative rates of chlorination were determined for resorcinol and several of the chlorinated resorcinols. Resorcinol was found to chlorinate only three times faster than 2,4,6-trichlororesorcinol. The structure 2,4,6-trichlororesorcinol was established as a monohydrate even after sublimation. A tetrachloro or pentachloro intermediate was not detected, suggesting that the ring-opening step of such an intermediate must be rapid.