Reactions of Polyfluoroalkyl Fluorosulfates with Nucleophiles: An Unusual Substitution at the Sulfur-Fluorine Bond

摘要

Polyfluoroalkyl fluorosulfates RfOSO2F(Rf-CF3CH2 double bond and (CF3)2CH) react with amines and alcohols or alkoxides to yield new polyfluoroalkyl sulfamates and dialkyl sulfate esters, respectively. Unlike both perfluoroalkyl fluorosulfates and alkyl fluorosulfates, the sulfur-oxygen bond in these polyfluoroalkyl fluorosulfates remains intact in the presence of hard nucleophiles. With methanethiol, however, nucleophilic attack occurs primarily at the alpha-carbon of CF3CH2OSO2F to give methyl 2,2,2-trifluoroethyl sulfide. (Author)