On the reactions of alkylsulfonyl and perfluoroalkylsulfonyl fluorides with hydroxylamines and hydrazines

Abstract Sulfonic acid chlorides react with hydroxylamine to form predominantly N-substituted products [1]. Sulfonic acid fluorides react with hydroxylamine by formation of N-mesylhydroxylamine, hydrazinium(1+) and hydroxylammonium mesylate [2]. R f SO 2 F (R f = C 4 F 9 , C 8 F 17 ) reacting in the same way as CH 3 SO 2 F [3], the latter is considered to be a model compound for this kind of reactions. The formation of the hydrazinium salt is explained by the occurrence of O-mesylhydroxylamine as intermediate. We conclude from the yields that sulfonic acid fluorides react with hydroxylamine to form predominantly O-substituted products. In order to prepare this O-derivative the reaction between O-(trimethylsilyl)hydroxylamine and mesylfluoride was carried out. Hydrazinium mesylate could be isolated also, which indicates the formation of the instable O-derivative. The reactions of methylhydrazines and silylated hydrazines with mesylfluoride lead to mesylated products as expected.