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有机化学
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有机化学 ›› 1996, Vol. 16 ›› Issue (4): 344-348. 上一篇    下一篇

研究论文

磷化氢与环烯烃反应的原位^3^1P NMR研究

夏春谷;宋焕玲;李达刚   

  1. 中国科学院兰州化学物理研究所;羰基合成与选择氧化国家重点实验室
  • 发布日期:1996-08-25

In situ ^3^1P NMR study on the reaction of cyclic olefins with phosphine

XIA CHUNGU;SONG HUANLING;LI DAGANG   

  • Published:1996-08-25

本文应用加压原位核磁共振波谱技术, 在反应温度50-70℃、反应压力1.0-2.0MPa, 氘代苯为溶剂, 偶氮二异丁腈为引发剂的条件下, 考察了磷化氢与环烯烃1, 5-环辛二烯、双环戊二烯、1, 3-环己二烯、1, 4-环己二烯及1, 5, 9-环十二三烯的反应。实验结果表明, 磷化氢与1, 5-环辛二烯反应主要生成双环膦杂环壬烷; 与其它环烯烃均不生成膦杂环化合物, 仅为一取代伯膦或二取代仲膦产物。磷化氢与环烯烃反应仍为串行机理。

关键词: 环烯烃, 磷化氢, 原位核磁, 偶氮二异丁腈, 氘代苯

Under the following reaction conditions: temperature 50-70℃, pressure 1.0-2.MPa, solvent C~6D~6, initiator AIBN, the reactions of 1,5-cyclooctadiene, dicyclopentadiene, 1, 3-cyclohexadiene, 1, 4- cyclohexadiene and 1, 5, 9-cyclododecatriene with PH~3 were studied by using the pressurized in-situ NMR technique. Experimental results indicated that the bicyclophosphanonane was formed by the addition of PH~3 to 1, 5-cyclooctadiene. On the other hand, the heterocyclic compounds containing phosphorus could not be obtained in the reaction of PH~3 with other three cyclic olefins, primary phosphines being the only products observed. The results also indicated that the reaction of PH~3 with cyclic olefins proceeded with a sequential mechanism.

Key words: PHOSPHOROUS HYDRIDE, AZOBISISOBUTYRONITRILE (AIBN), CYCLOALKENE

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