Reactions of Dimedone with Sulfur Chlorides

Article abstract of DOI:10.1021/jo00337a017

A comparative study of the reactions of dimedone (1), as a representative β-diketone, with various simple sulfur chlorides has revealed that the product distribution observed can best be accounted for in terms of competing mechanisms of oxygen attack or carbon attack (at C-2) in the enol form.Oxygen attack is particularly important with SCl2 and S2Cl2 and appears to involve a subsequent intramolecular transfer of Cl (or ClS) to C-2, via an intermediate such as 12.The relative electrophilicity of the reagents and the facility with which 12 can be expected to rearrange to a C-2 substituted product appear to be among the factors influencing the course of these reactions.Some of the reactions show promise as synthetic routes to potentially useful dimedone derivatives.