Sulfuryl Chloride as a Reagent for Selective Chlorination of Symmetrical Ketones and Phenols

Article abstract of DOI:10.1021/jo00335a033

Cyclohexanone reacts with sulfuryl chloride in sulfur dioxide, ether, tetrahydrofuran, dioxane, and tetraglyme to give mixtures of mono- and dichlorocyclohexanones.However, when the reaction was carried out in sulfur dioxide solution containing a slight excess of methanol, only monochlorocyclohexanone was obtained in high yield.Almost as good selectivities are obtained in methylene chloride solution in the presence of methanol.A similar procedure with acetone affords monochloroacetone cleanly.While phenols do not react with sulfuryl chloride in methylene chloride even under reflux, the chlorination can be induced by the addition of various organic "bases", resulting in selective monochlorination.