高等学校化学学报

高等学校化学学报 ›› 1995, Vol. 16 ›› Issue (3): 395.

• 论文 • 上一篇    下一篇

烷氧基磷烷的合成及假旋转

刘纶祖, 李国炜, 张翱, 曾兴忠, 付岚冰   

  1. 南开大学元素有机化学研究所, 天津 300071
  • 收稿日期:1994-03-14 修回日期:1994-10-05 出版日期:1995-03-24 发布日期:1995-03-24
  • 通讯作者: 刘纶祖,男,55岁,教授.
  • 作者简介:刘纶祖,男,55岁,教授.
  • 基金资助:

    国家自然科学基金

Preparation and Pseudorotation of Alkoxyphosphoranes

LIU Lun-Zu, LI Guo-Wei, ZHANG Ao, ZENG Xing-Zhong, FU Lan-Bing   

  1. Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071
  • Received:1994-03-14 Revised:1994-10-05 Online:1995-03-24 Published:1995-03-24

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摘要： 氢膦烷2与苯基次磺酸酯3反应,制得几种带有取代基的螺双环烷氧基磷烷4.变温31PNMR谱监测,观察到化合物4的假旋转,并计算出了假旋转的活化自由能。

关键词: 烷氧基磷烷, 假旋转, 五配位磷, 苯基次磺酸酯, 氢膦烷

Abstract: Reaction of hydridophosphoranes 2 with benzensulfenic esters 3 provides a series of substituted spirobicyclic alkoxyphosphoranes 4.The pseudorotation process of compound 4 was observed by the variable temperature 31PNMR spectra. The free energy of activation for this process was calculated. Coalescence for 4a,4boccurred at 130℃ ,4cand 4dat 140℃.The △G≠ for 4a,4b,4c,4dare 81.8,81.8,85.8,84. 99kJ/mol,respectively.The results have indicated that pseudorotation process is subject to steric infltiences.

Key words: Alkoxyphosphoranes, Pseudorotation, Pentacoordinated phosphorus, Benzene sulfenic esters, Hydridophosphoranes

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