Synthesis of Poly- and the First Perfluoroalkyl-N(SO2F)2Derivatives: Improved Methods for the Preparation of XN(SO2F)2(X = H, Cl) and Single-Crystal Diffraction Studies of HN(SO2Cl)2, HN(SO2F)2, and CF3CH2N(SO2F)2

Abstract

The preparation of HN(SO2F)2 was achieved conveniently by fluorination of HN(SO2Cl)2 with SbF3. Reactions of Hg[N(SO2F)2]2 with fluoroalkyl iodides RI (R = i-C3F7CH2CH2 and CF3CH2) gave i-C3F7CH2CH2N(SO2F)2 (1) and CF3CH2N(SO2F)2 (2). The chlorination of Hg[N(SO2F)2]2 provided a high-yield method of synthesizing the well-known ClN(SO2F)2. N-alkylation of ClN(SO2F)2 with fluorinated ethenes CF2CHal2 (CHal2 = CF2, CFCl, and CCl2) resulted in the formation of CF2ClCF2N(SO2F)2 (3), CF2ClCFClN(SO2F)2 (4a, major), CFCl2CF2N(SO2F)2 (4b, minor), and CCl3CF2N(SO2F)2 (5). The synthesis of the first perfluoroalkyl-N(SO2F)2 derivatives CF3N(SO2F)2 (6), C2F5N(SO2F)2 (7), n-C3F7N(SO2F)2 (8), and n-C4F9N(SO2F)2 (9) was accomplished with moderate-to-good yields by reacting ClN(SO2F)2 with iodoperfluoroalkanes RFI (RF = CF3, C2F5, n-C3F7, and n-C4F9). Similarly, ClN(SO2F)2 reacted with CF3CH2I to give 2. Photolysis of ClN(SO2F)2 with iodoperfluoroalkanes RFI (RF = n-C3F7, and n-C4F9) gave 8 and 9 in low yields. HN(SO2F)2 ...