高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (8): 1553.doi: 10.7503/cjcu20150221

• 物理化学 • 上一篇    下一篇

有机胺功能化离子液体中离子型铑(Ⅲ)配合物催化的1-辛烯两相氢甲酰化反应

石丁夫, 谭忱, 王鹏, 李永琪, 陈胜洁, 刘晔()   

  1. 华东师范大学化学与分子工程学院, 上海市绿色化学与化工过程绿色化重点实验室, 上海200062
  • 收稿日期:2015-03-23 出版日期:2015-08-10 发布日期:2015-06-30
  • 作者简介:联系人简介: 刘 晔, 女, 博士, 教授, 主要从事绿色均相催化研究. E-mail:yliu@chem.ecnu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 21273077, 21076083)资助

Biphasic Hydroformylation of 1-Octene Catalyzed by Ionic Rh(Ⅲ)-complex in the Presence of Tertiary Amine Functionalized Ionic Liquid

SHI Dingfu, TAN Chen, WANG Peng, LI Yongqi, CHEN Shengjie, LIU Ye*()   

  1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry & Molecular Engineering, East China Normal University, Shanghai 200062, China
  • Received:2015-03-23 Online:2015-08-10 Published:2015-06-30
  • Contact: LIU Ye E-mail:yliu@chem.ecnu.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(Nos.21273077, 21076083)

摘要:

考察了离子型+3价铑配合物1a和2a作为催化剂前体在1-辛烯氢甲酰化反应中的催化行为. 实验结果表明, 在无助剂存在下, 配合物1a和2a表现出较差的催化性能, 而廉价低毒的有机叔胺助剂如三乙胺或N-甲基哌啶可以显著提升配合物1a和2a的催化性能, 可获得800 h-1以上的转化频率(TOF). 当以哌啶功能化离子液体[PEmim]BF4兼作助剂和溶剂时, 不仅可以促进配合物1a和2a对氢甲酰化反应的活性和选择性, 还可实现“离子液体-有机”两相氢甲酰化反应, 使得锁定在[PEmim]BF4离子液体相中的配合物1a(或2a)催化剂得以简单两相分离和回收循环使用, 但在5次循环使用过程中锁定在[PEmim]BF4中的催化剂存在向有机相流失和失活的问题, 导致产物壬醛的收率逐渐下降.

关键词: 铑配合物, 功能化离子液体, 氢甲酰化, 1-辛烯, 叔胺

Abstract:

The ionic Rh(Ⅲ)-complexes 1a and 2a exhibited poor catalytic performance for hydroformylation of 1-octene without the presence of any auxiliary additive. The involvement of cheap and low-toxic tertiary amines such as Et3N or N-methylpiperidine could dramatically boost the catalytic performance of compounds 1a and 2a up to turnover frequency(TOF) of 800 h-1. When piperidinyl-functionalized ionic liquid of [PEmim]BF4 was dually used as the additive and the solvent, not only the positive roles of N-methylpiperidine in spurring up the activity of compounds 1a and 2a were embodied, but also the easy recovery and recycling of compounds 1a(or 2a)in [PEmim]BF4 were fulfilled in biphasic hydroformylation. The TOFs of compounds 1a and 2a in [PEmim]BF4 were gradually decreased in the course of the recycling uses due to the leaching and deactivation of the catalysts.

Key words: Rh-complex, Functionalized ionic liquid, Hydroformylation, 1-Octene, Tertiary amine

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