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本文报道溴代全氟烷和α,ω-二溴代全氟烷在亚磺化脱卤反应体系中与烯烃的反应及其与相应的碘代全氟烷的区别。合成了全氟仲溴代烷CF_3FBrOCF_2CF(CF_3)O(CF_2)_2SO_2F(7),它与烯烃反应可得到1:1的加成物。7的水解产物CF_3CFBrOCF_2CF(CF_3)O(CF_2)_2SO_3Na(11)与连二亚硫酸钠反应只得到氢化脱溴产物。多氟溴化物CF_3CBrX(13X=F;14X=Cl;15X=Br)经亚磺化脱溴可得到相应的亚磺酸钠盐CF_3BrXSO_2O_2Na(16X=F;17X=Cl;18X=Br),其中间体多氟烷自由基可用烯烃捕集,得到高产率的1:1加成产物。
This paper reports the reaction of brominated perfluoroalkanes and α, ω-dibromofluoroalkanes with olefins in the sulfonated dehalogenation reaction system and their differences from the corresponding iodinated perfluoroalkanes. The perfluoro secondary brominated hydrocarbons CF_3FBrOCF_2CF (CF_3) O (CF_2) _2SO_2F (7) were synthesized, which reacted with olefins to obtain 1: 1 adducts. Hydrolyzed product CF3CFBrOCF2CF (CF3) O (CF2) _2SO3Na (11) reacted with sodium dithionite to give only the hydrodebrominated product. The corresponding sulfinic acid sodium salt CF_3BrXSO_2O_2Na (16X = F; 17X = Cl; 18X = Br) can be obtained by sulfonating debromination of polyfluorinated bromide CF_3CBrX (13X = F; 14X = Cl; Bulk polyfluoroalkane radicals can be trapped with olefins to give high yields of 1: 1 addition products.