Radical additions to fluoroolefins. Photochemical fluoroalkylation of alkanols and alkane diols with perfluoro vinyl ethers; photo-supported O-alkylation of butane-1,4-diol with hexafluoropropene
作者:Vladimír Cîrkva、Radek Polák、Oldřich Paleta
DOI:10.1016/s0022-1139(96)03514-2
日期:1996.10
photoaddition reactions with hexafluoropropene and perfluoro (propyl vinyl) ether under atmospheric pressure, by which monofluoroalkylated and bis-fluoroalkylated products were obtained. 1,3-Diols were completely unreactive under the conditions. 2,2,2-Trifluoroethanol, tert.butyl alcohol and methyl tert.butyl ether appeared to be inert solvents for the additions while acetonitrile quenched the reactions. The
在大气压下,通过与六氟丙烯和全氟(丙基乙烯基)醚的光加成反应,将丁烷-1,4-二醇进行氟烷基化,从而获得单氟烷基化和双氟烷基化的产物。1,3-二醇在这种条件下是完全不反应的。2,2,2-三氟乙醇,叔丁醇和甲基叔丁基醚似乎是添加的惰性溶剂,而乙腈则使反应猝灭。在全氟乙烯基醚与与六氟丙烯相比具有较低区域选择性(相对于区域异构体为7%相对)的烷醇的光加成反应中,对全氟乙烯基醚的反应性进行了研究(测试)。出人意料的是,在乙腈中观察到了光支撑的碱诱导的丁烷1,,4-二醇的亲核性单双加双加成反应。