Organophosphorus chemistry. Part X. Reaction of dimethyl- and bis(trifluoromethyl)-phosphines with trifluoroethylene
作者:R. Fields、R. N. Haszeldine、N. F. Wood
DOI:10.1039/j39700000744
日期:——
Dimethyl- and bis(trifluoromethyl)-phosphines react smoothly with trifluoroethylene under u.v. irradiation to give good yields of 1 : 1 addition products. Bis(trifluoromethyl)phosphine gives almost exclusively 1,2,2-trifluoro-ethylbis(trifluoromethyl) phosphine, as expected on the basis of the stabilities of the two possible intermediate free radicals. Dimethylphosphine gives dimethyl-1,2,2-trifluoroethylphosphine
二甲基和双(三氟甲基)膦在紫外光照射下与三氟乙烯平稳反应,得到1:1加成产物的良好收率。根据两个可能的中间自由基的稳定性,双(三氟甲基)膦几乎只产生1,2,2-三氟-乙基双(三氟甲基)膦。基于中间自由基稳定性,二甲基膦得到二甲基-1,2,2-三氟乙基膦,以及几乎相等量的1,1,2-三氟乙基异构体。因此,对于Me 2 P,对三氟乙烯的CF 2基团的进攻比例要高于先前报道的任何自由基的进攻比例。Me 2 P,H 2 P,(CF3) 2 P与附着在磷上的基团的电子效应有关。