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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。
In this paper, pressurized in situ nuclear magnetic resonance spectroscopy was used to investigate the effect of phosphine in hydrogen peroxide on the conditions of reaction temperature 50 ~ 70 ℃, reaction pressure 1.0 ~ 2.0MPa, deuterated benzene as solvent and azobisisobutyronitrile as initiator. With cycloalkene 1,5-cyclooctadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene and 1,5,9-cyclododecatriene. The experimental results show that the reaction of phosphine with 1,5-cyclooctadiene leads to the formation of bicyclic phosphazenonane, and none of the other cyclic olefins produce a phosphine heterocyclic compound, which is only the mono-substituted primary phosphine or the disubstituted secondary phosphine . The reaction of phosphine with cycloolefins is still a serial mechanism.