NUCLEOPHILIC REACTIONS OF SEMIIONIC OXYGEN. II. A NOVEL PREPARATION OF ETHYL GLYOXYLATE FROM ETHYL BROMOACETATE AND DIMETHYL SULFOXIDE. THE STOICHIOMETRY AND THE SULFUR-CONTAINING BY-PRODUCTS

The reaction of excess dimethyl sulfoxide with ethyl romoacetate produce ethyl glyoxylate, hy rogen bromide, and dimethyl sulfide. A convenient preparation of ethyl glyoxylate in yields averaging 70% was developed. The generality of the dimethyl sulfoxide oxidation was demonstrated by applying it to a variety of alpha-halogenated acids and esters. An ionic mechanism for this oxidation is suggested which involves nucleophilic displacement of the halogen by the sulfoxide oxygen. A number of earlierreported reactions of sulfoxides al o appear to depend on the nucleophilic nature of their oxygen atoms. It is suggested that other compounds containing semiionic oxygen will exhibit analogous reactions. (Author)