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化学学报
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化学学报 ›› 1988, Vol. 46 ›› Issue (7): 711-714. 上一篇    下一篇

研究论文

过渡金属催化烯烃异构化的研究 VI: Cp2TiCl2/i-C3H7MgBr催化4-乙烯基环己烯异构化的研究

吕家琪;钱延龙;何宝乙;聂崇实;张才华   

  1. 中国科学院上海有机化学研究所
  • 发布日期:1988-07-15

Studies on olefin isomerization catalyzed by transition metals VI: Isomerization of 4-Vinylcyclohexene catalyzed by Cp2TiCl2/i-C3H7MgBr

LU JIAQI;QIAN YANLONG;HE BAOYI;NIE CHONGSHI;ZHANG CAIHUA   

  • Published:1988-07-15

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研究了用二茂钛氯化物和异丁基溴化镁格氏试剂催化的4-乙烯基环己烯的异构化,这一体系具有良好的催化活性和高选择性, 4-乙烯基环己烯在50℃时反应2小时能定量地异构化成3-乙叉环己烯而在15℃时, 主要异构化产品是4-乙叉环己烯、异构化产物被分离了, 并用质子磁共振, 质谱和红外光谱测定, 讨论了反应机理.

关键词: 催化, 反应机理, 氯化物, 环戊二烯 P, 烯烃, 异丁基, 溴代烃, 金属茂络合物, 钛络合物, 过渡金属络合物

The isomerization of 4-vinylcyclohexene catalyzed by Cp2TiCl2/Me2CHMgBr was studied. The system was found to have excellent catalytic activity and high selectivity. Thus, 4-vinylcyclohexene can be isomerized quant. into 3-ethylidenecyclohexene at 50 癈 in 2 h, and at 15 癈 for 2 h the main isomerization product was 4-ethylidenecyclohexene with 88% selectivity and 97% conversion. All the isomerization products were isolated and characterized by 1H NMR, MS and IR. The catalytic mechanism was discussed.

Key words: CATALYSIS, REACTION MECHANISM, CHLORIDE, CYCLOPENTADIENE P, ALKENE, ISOBUTYL GROUP, BROMOHYDROCARBON, METALLOCENES, TITANIUM COMPLEX, TRANSITION METAL COMPLEX

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