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化学学报
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化学学报 ›› 1993, Vol. 51 ›› Issue (8): 815-818. 上一篇    下一篇

研究论文

磷化氢与直链烯烃反应的原位^31PNMR研究

宋焕玲;夏春谷;李达刚   

  1. 中国科学院兰州化学物理研究所
  • 发布日期:1993-08-15

In-situ ^31P NMR study on the reactions of linear olefins with phosphine

SONG HUANLING;XIA CHUNGU;LI DAGANG   

  • Published:1993-08-15

PDF

487

被引次数

9

本文应用加压原位核磁共振技术,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,考察了磷化氢与直链烯烃1,4-戊二烯,1,7-辛二烯及1-十八烯的反应.实验结果表明,磷化氢与1,4-戊二烯可以生成6员膦杂环己烷,与1,7-辛二烯不易生成9员膦杂环壬烷,与1-十八烯主要生成伯膦产物.原位^31PNMR谱的研究也表明,磷化氢与直链烯烃反应为串行机理.

关键词: 反应机理, 核磁共振谱法, 烯烃, 膦, 加成反应, 戊二烯, 磷化氢, 辛二烯, 十八碳烯

Under the following reaction conditions: temperature 50~70癈, pressure 1.0~2.0 MPa, solvent C6D6, initiator AIBN, the reactions of 1,4-pentadiene, 1,7-octadiene and 1-decaoctene with PH3 were studied by using the pressurized in-situ NMR technique. Experimental results indicated that the six-membered phosphorinane is formed by the addition pf PH3 to 1,4-pentadiene, phosphonane can't be obtained by 1,7-octadiene, and primary phosphine is the predominant product in the reaction of PH3 with 1-decaoctene. The results obtained by in-situ 31P NMR spectra also indicated that the reactions of PH3 with linear olefins proceed with a sequential mechanism.

Key words: REACTION MECHANISM, NMR SPECTROMETRY, ALKENE, PHOSPHINE, ADDITION REACTION, PENTADIENE, PHOSPHOROUS HYDRIDE, OCTADIENE

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