作者:Alex Nickon、Pamela St. John Zurer、Bruce Hrnjez、Joseph Tino
DOI:10.1016/s0040-4020(01)91978-7
日期:1983.1
media and, in acid solution, varied with time. Rearrangement of the spirocyclic precursor to the non-fused, bicyclic skeleton (present in olefins 11 and 12) is favored kinetically; but, on prolonged treatment in acid, the fused bicyclic skeleton (present in alkenes 19 and 20) increases in amount at the expense of 11 and 12. We also examined acid-catalyzed isomerizations of olefin 19 as well as of 11
我们的目标是通过大螺环阳离子的重排探索获得双环四取代烯烃的途径。此类烯烃用作随后的光转化为半球形双环烯烃(间烷)的前体。我们合成了螺环醇13-羟基螺基-[12.11]四二十烷(14a),并在各种酸性和非酸性条件下将其脱水为包含以下成分的烯烃混合物:环十二烷基-环十二烷(11),(E)-和(Z)-1-环癸基十二碳烯(12),(E)-和(Z)-螺[12.11] tetracos-13-ene(16),(Z)-双环[11.11.0] tetracos-1(13)-ene(19),(E)和(Z)-双环[11.11.0] tetracos-1-烯(20)。烯烃的比例根据脱水介质而变化,并且在酸性溶液中随时间变化。动力学上有利于将螺环前体重排至非稠合的双环骨架(存在于烯烃11和12中);但是,在酸中进行长时间处理后,稠合的双环骨架(存在于烯烃19和20中)的数量增加,但以11和12为代价。我们还检查了