全氟和多氟烷基磺酸的研究 XI: 全氟3-氧杂戊磺酸全氟苯酯的合成及其和亲核试剂的反应

Perfluoro and polyfluorosulfonic acids XI: The synthesis and nucleophilic reactions of perfluorophenyl-3-oxaperfluoroalkanesulfonates

Pentafluorophenyl and p-chlorotetrafluorophenyl-3- oxaperfluoroalkanesulfonates XCF2CF2OCF2CF2SO3C6F4Y (1) (Y=F, p-Cl) were synthesized by the reaction of 3-oxaperfluoroalkanesulfonyl fluoride with the corresponding sodium phenoxide in good yield. 1 reacted with various nucleophilic reagents more readily than phenyl perfluoroalkanesulfonates. The reactivity of nucleophiles toward 1 is parallel to the pKa values of their corresponding acids. All nucleophiles used (except C6H5S^-) attacked sulfur of 1 giving RfSO2Nu. Treatment of 1 with CH3CO^-2 produced perfluorophenyl acetate. When equivalent amount of KF was added to the reaction mixture the yield of the acetate decreased and main product was acetyl fluoride. This showed that the reaction followed the course of intermediary mixed anhydride formed through the attack of CH3CO^-2 on sulfur of 1. But when 1 was treated with ArS^- the only reaction occurred was C-O scission of the sulfenate by the nucleophilic attack of ArS^- on the fluorinated benzene ring to give the totrasubstituted perfluorobenzene, 1, 2, 4, 5-C6F2 (SAr)4. In contrast to the nucleophilic reaction of the mono-substituted pentafluorobenzene it was shown that in all reactions with nucleophiles para or ortho di-substituted compounds such as ReSO3C6F4Nu were not found.