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

Abstract

Polyfluoroalkyl fluorosulfates RfOSO2F [Rf = CF3CH2 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 α-carbon of CF3CH2OSO2F to give methyl 2,2,2-trifluoroethyl sulfide. © 1984, American Chemical Society. All rights reserved.