Reactions of quadricyclane with fluorinated nitrogen-containing compounds. Synthesis of 3-aza-4-perfluoroalkyl-tricyclo[4.2.1.02,5]non-3,7-dienes
作者:Viacheslav A. Petrov、Frederic Davidson、Will Marshall
DOI:10.1016/j.jfluchem.2004.09.003
日期:2004.11
7-dienes rapidly react with CF3Si(CH3)3 in the presence of CsF catalyst. The reaction results in addition of CF3Si(CH3)3 across the CN bond of the azadienes with selective formation of only one stereoisomer of exo-3-aza-3-(trimethylsilyl)-4,4-bis(perfluoroalkyl)-tricyclo[4.2.1.02,5]non-7-enes. Silyl group in this compounds can be removed either by the action of tetrabutylammonium fluoride hydrate, leading
研究了四环烷(1)与多氟化亚胺和腈的环加成反应。发现(CF 3)2 CNH和(CF 3)2 CN(2-FC 6 H 4)对1的反应性低,从而以低收率得到相应的[2 + 2 + 2]环加合物。然而,C 2 F 5 NCFCF 3与1迅速反应,以高收率得到两种同分异构的环加合物的混合物。全氟烷基腈R f CN(R f = CF 3,C 2 F 5,Ñ -C 3 ˚F 7)被发现具有令人惊奇地高的反应性,以1产生外-3-氮杂-4-(氟代烷基) -三环[4.2.1.0 2,5 ]壬-3,7-二烯在56-81%在高温下收率。在CsF催化剂存在下,Exo -3- aza-4-(全氟烷基)-三环[4.2.1.0 2,5 ]非-3,7-二烯迅速与CF 3 Si(CH 3)3反应。该反应导致在氮杂二烯的CN键上添加CF 3 Si(CH 3)3,仅选择性地形成一种exo立体异构体。-3-氮杂-3-(三甲基甲硅