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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (14): 1318-1322. 上一篇    下一篇

研究论文

大取代茂锆配合物合成及分子内消除反应研究

许胜，黄吉玲*   

  1. (华东理工大学应用化学研究所 上海 200237)
  • 投稿日期:2004-11-24 修回日期:2005-03-29 发布日期:2010-12-10
  • 通讯作者: 黄吉玲

Syntheses of Bulkily Substituted Zirconocene Dichloride Complexes and Study on Their Intramolecular Elimination Reaction

XU Sheng, HUANG Ji-Ling*   

  1. (Institute of Applied Chemistry, East China University of Science and Technology, Shanghai 200237)
  • Received:2004-11-24 Revised:2005-03-29 Published:2010-12-10
  • Contact: HUANG Ji-Ling

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1085

被引次数

24 | 7

通过6,6-二烷基富烯与2-MeOArLi进行加成反应, 得到含芳氧取代的环戊二烯基锂盐, 再与取代茂三氯化锆反应, 合成了不对称大位阻取代茂锆配合物RCpCpoZrCl2 [Cpo＝2-MeOArCR1R2Cp, R1, R2＝CH3, C2H5, (CH2)5, etc.], 所得的配合物均通过1H NMR, IR, MS和EA鉴定. 在此过程中发现该类配合物能进行分子内消除反应, 脱去苯甲醚得到烯基取代的二氯二茂锆配合物, 该反应为未见文献报道的新反应, 对该反应进行了研究.

关键词: 合成, 二氯二茂锆, 分子内消除

The bulkily substituted zirconocene dichloride complexes of the type RCpCpoZrCl2 [Cpo＝2-MeOArCR1R2Cp, R1, R2＝CH3, C2H5, (CH2)5, etc.] have been synthesized by the reaction of 6, 6-dialkylfulvene with 2-MeOArLi followed by treatment with RCpZrCl3•DME (R＝H, Me, i-Pr), and all the complexes were characterised by 1H NMR, IR, MS and elemental analysis. A new type of intramolecular elimination reaction was found and anisole was eliminated from the complexes with formation of alkenyl-substituted zirconocene.

Key words: syntheses, zirconocene dichloride, intramolecular elimination