Chlorination of Aliphatic Ketones in Methanol

Article abstract of DOI:10.1021/jo00325a019

The chlorination of aliphatic ketones in methanol has been examined.The product distributions in methanol differ substantially from those obtained by chlorination in carbon tetrachloride.The reaction in methanol favors addition of chlorine to the least substituted carbon α to the carbonyl group.The effect is especially pronounced if an α carbon bearing two substituents is present.The distribution of products is determined by the relative stability of the enol ethers formed from the ketone under the reaction conditions.