摘要
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。
Under the following reaction conditions- temperature 50 - 70C℃ , pressure 1.0 - 2.0 MPa, solvent C6D6, initiator AIBN, the reactions of 1, 5 - cyclooctadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,4 - cyclohexadiene and 1,5,9 - cyclododecatriene with PH3 were studied by using the pressurized in - situ NMR technique. Experimental results indicated that the bicyclophosphanonane was formed by the addition of PH3 to 1,5 - cyclooctadiene. On the other hand, the heterocyclic compounds containing phosphorus could not be obtained in the-reactions of PH3 with other three cyclic olefins, primary phosphines being the only products observed. The results also indicated that the reactions of PH3 with cyclic olefins proceeded with a sequential mechanism.
出处
《有机化学》
SCIE
CAS
CSCD
北大核心
1996年第4期344-348,共5页
Chinese Journal of Organic Chemistry
