The syntheses of fluorinated alkanesulfonamides and poly-(fluorinated alkanesulfonamides)
Huang Wei‐Yuan, Chang‐Ming Hu, Hengyao Lu · Acta Chimica Sinica · 1983
In order to synthesize poly-(fluorinated alkanesulfonamides) a series of model experiments were carried out: (1) reactions of fluorinated alkanesulfonyl fluorides with amines, (2) reactions of fluorinated alkanesulfonyl chloride with amines and (3) reactions of sodium salts of fluorinated alkanesulfonamides with alkyl iodides of fluorinated alkanesulfonic acid esters. Seventeen new fluorinated alkanesulfonamides were prepared in good yields, namely: RFO(CF2)2SO2NR1R2 (1a-h), R1R2NSO2RFSO2NR1R2 (2a-h) and [Cl (CF2)4O(CF2)2SO2NH(CH2)3]2 (3). Reaction of RFSO2NH2 with equivalent amount of NaOCH3 and methyl iodide was shown to give both the N-mono- and N,N-di-substituted amides. Consequently the N-monosubstituted alkanesulfonamides were chosen as monomers for syntheses of the poly-(fluorinated alkanesulfonamides) and two new polymers were synthesized. The effect of the condition of the polycondensation on M̄n of the polymers were discussed and elemental composition, 19F NMR, IR, M̄n, Tg, tensile strength, thermal and chemical stabilities of the polymers were measured. Several new perfluoroalkanesulfonyl chlorides CISO2RFSO2Cl (4a-c) and fluorinated alkanesulfonic acid esters (6a-d) were synthesized. However, reaction of CFCl2CF2O(CF2)2SO2F with AlCl3 was found to give Cl3CCF2O(CF2)2SO2F (5) instead of the expected sulfonyl chloride.