Perfluoroalkyl derivatives of nitrogen. Part XXVI. The preparation and rearrangement of polyfluorovinylamines and of trifluoromethyl trifluorovinyl ether
作者:R. N. Haszeldine、A. E. Tipping
DOI:10.1039/j39680000398
日期:——
trifluorovinyl ether, and pentafluoropropionyl fluoride. Pyrolysis of perfluoro-(NN-dimethylvinylamine) or of trifluoromethyl trifluorovinyl ether gives perfluoro-2-azapent-2-ene (55%) and pentafluoropropionyl fluoride (67%), respectively. The rearrangement of the vinylamine probably occurs by two mechanisms (mainly intramolecular and partly radical), since pyrolysis with a large excess of toluene gives
全氟-(1-二甲基氨基-2-甲氧基环丁烷)在600°C,低压(1-2 mm。)的流动热解条件下,接触时间约为600℃ 。1秒。给出全氟- (NN -dimethylvinylamine)(76%),全氟-2- azapent -2-烯(21%),三氟甲基三氟乙烯基醚(22%),和五氟丙酰氟(54%)。全氟-(1,2-双二甲基氨基环丁烷)的类似热解反应也产生了前两种化合物(分别为78%和17%)。双(全氟-2-甲氧基环丁基)的热解得到更复杂的产物,包括四氟乙烯,全氟环丁烯,全氟-1,3-丁二烯,三氟甲基三氟乙烯基醚和五氟丙酰氟。全氟热解-(NN-二甲基乙烯基胺)或三氟甲基三氟乙烯基醚分别得到全氟-2-氮杂戊-2-烯(55%)和五氟丙酰氟(67%)。乙烯胺的重排可能是通过两种机理发生的(主要是分子内和部分自由基的),因为用大量过量的甲苯进行热解会以较低的收率(46%)和氟仿(31%)产生重排的氮杂戊烯。乙烯基胺(CF