Several polyfluoroalkyl fluorosulfates, RfOS02F (Rf = CF3CH(CH3), CF3C(CH3)2, and (CF3)2CH), have been synthesized by the reaction of polyfluoro alcohols with sulfuryl fluoride or sulfuryl chloride fluoride. They reacted with nucleophilic reagents such as amines, polyfluoro alcohols, polyfluoroalkoxides and bromide ion to give sulfamates, dialkyl sulfates, and polyfluoroalkyl bromides, respectively. In the case of CF3(CH3)2C0S02F with bromide ion, the polyfluoroalkyl bromide loses hydrogen bromide to give 2-(trifluoromethyl)propene in high yield.The presence of three electrophilic centers in polyfluoroalkyl fluorosulfates and chlorosulfates,1 carbon, sulfur, and fluorine (chlorine), render the Rf0S02X (X = Cl, F) substrates of considerable interest because nucleophiles may potentially react at one or several of these centers. It is well known that perfluoroalkyl and polyfluorohaloalkyl fluorosulfates undergo facile attack by nucleophiles such as fluoride ion, ammonia, or methanol to cleave the S-0 bond to form ketones (eq l),2 amides (eq 2),3 or esters (eq 3).4
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.