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

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_fSO₂F (R_f = C₄F₉, C₈F₁₇) reacting in the same way as CH₃SO₂F 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.