高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (3): 524-530.doi: 10.7503/cjcu20130664

• 有机化学 • 上一篇    下一篇

桥连双(酮亚胺)和双(二酮亚胺)及其铝配合物的合成与催化活性

黄庆东1,2, 李春兰2, 张宇2, 崔立山1, 朱百春3, 义建军3, 刘林4, 郝海军4()   

  1. 1. 中国石油大学(北京)理学院材料科学与工程系, 北京102249
    2. 中国石油天然气股份有限公司华北化工销售分公司, 北京100009
    3. 中国石油天然气股份有限公司石油化工研究院合成树脂重点实验室, 北京 100195
    4. 北京化工大学理学院有机化学系, 北京 100029
  • 收稿日期:2013-07-16 出版日期:2014-03-10 发布日期:2019-08-01
  • 作者简介:联系人简介: 郝海军, 男, 博士, 副教授, 主要从事金属有机化学与催化研究. E-mail: hjhao@mail.buct.edu.cn
  • 基金资助:
    中国石油天然气集团公司科技项目(批准号: 09-YK-05-19)资助

Synthesis and Catalytic Activity of Aluminum Complexes Supported by Bis(β-ketimine) and Bis(β-diketimine) Ligands

HUANG Qingdong1,2, LI Chunlan2, ZHANG Yu2, CUI Lishan1, ZHU Baichun3, YI Jianjun3, LIU Lin4, HAO Haijun4,*()   

  1. 1. Department of Materials Science and Engineering, College of Science, China University of Petroleum(Beijing), Beijing 102249, China
    2. Petrochina North China Chemicals Marketing Company, Beijing 100009, China
    3. Key Laboratory of Synthetic Resin, Petrochemical Research Institute, PetroChina Company Limited, Beijing 100195, China
    4. Department of Organic Chemistry, College of Science, Beijing University of Chemical Technology, Beijing 100029, China
  • Received:2013-07-16 Online:2014-03-10 Published:2019-08-01
  • Contact: HAO Haijun E-mail:hjhao@mail.buct.edu.cn
  • Supported by:
    † Supported by the Science and Technology Project of Petrochina Company Limited(No.09-YK-05-19).

摘要:

通过桥连双β-二酮类化合物与取代苯胺反应, 合成了5个新的桥连双(β-单酮亚胺)化合物(1~5)和2个新的桥连双(β-二酮亚胺)化合物(6,7), 它们与三甲基铝反应, 得到了相应的3个双(β-酮亚胺基)二铝配合物(8~10)和2个双(β-二酮亚胺基)二铝配合物(11,12). 采用核磁共振、 红外光谱和质谱等对这些化合物进行了表征, 通过X射线单晶衍射分析证实了铝配合物的结构, 并考察了这些铝配合物在ε-己内酯开环聚合反应中的催化活性.

关键词: 桥连双(β-酮亚胺), 桥连双(β-二酮亚胺), 铝, 晶体结构, 催化活性

Abstract:

Owing to its special physical and chemical properties as well as good coordination activity with transition metals, β-diketone-derived β-ketimines and β-diketimines have been extensively studied in recent years. In this work, five new bridged bis(β-ketimine)(1—5) and bis(β-diketimine) ligands(6,7) were synthesized by the condensation reaction of 3,3'-(1,4-phenylene)bis(2,4-pentanedione) with various anilines. Treatment of these ligands with AlMe3 afforded five new aluminum complexes(8—12). All these compounds were characterized via elemental analysis, 1H NMR, 13C NMR, ESI-MS and IR spectroscopy. Structures of two aluminium complexes were determined by the X-ray single-crystal diffraction analysis. The bridged β-ketimine acted as a chelating N, O-bidentate ligand to the aluminium atom. Each aluminum atom showed a distorted tetrahedral coordination geometry. These aluminum complexes exhibited effective catalytic activity in the ring-opening polymerization of ε-caprolactone.

Key words: Bridged bis(β-ketimine), Bridged bis(β-diketimine), Aluminum, Crystal structure, Catalytic activity

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