有机化学 ›› 2017, Vol. 37 ›› Issue (9): 2275-2286.DOI: 10.6023/cjoc201703021 上一篇    下一篇

综述与进展

草酸酯加氢制乙二醇钌金属均相催化体系的研究进展

张亦伟, 陈艺林, 方霄龙, 袁友珠, 朱红平   

  1. 厦门大学化学化工学院 固体表面物理化学国家重点实验室 醇醚酯清洁生产国家工程实验室 厦门 361005
  • 收稿日期:2017-03-10 修回日期:2017-05-02 出版日期:2017-09-25 发布日期:2017-05-17
  • 通讯作者: 袁友珠, 朱红平 E-mail:yzyuan@xmu.edu.cn;hpzhu@xmu.edu.cn
  • 基金资助:

    国家自然科学基金(Nos.21473142,91545115,21473145)和教育部创新团队(Nos.IRT_14R31,J1310024)资助项目.

Advances for the Ruthenium Complexes-Based Homogeneous Catalytic Hydrogenation of Oxalates to Ethylene Glycol

Zhang Yiwei, Chen Yilin, Fang Xiaolong, Yuan Youzhu, Zhu Hongping   

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005
  • Received:2017-03-10 Revised:2017-05-02 Online:2017-09-25 Published:2017-05-17
  • Contact: 10.6023/cjoc201703021 E-mail:yzyuan@xmu.edu.cn;hpzhu@xmu.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21473142, 91545115, 21473145) and the Innovative Research Team of China (Nos. IRT_14R31, J1310024).

草酸酯加氢是重要的有机化学反应,在工业制乙二醇生产中有着重要的应用.对钌金属配合物均相催化反应的研究进行了综述.以催化反应体系为焦点,探讨了多种因素如温度、氢气压力、催化剂浓度、反应时间、添加剂等对底物转化率以及产物选择性的影响,并讨论了催化反应机理,其中金属-配体协同促进的H2分子异裂,进而完成对底物分子中酯基依次加氢的反应机理是探讨的重点,这为新型催化剂的设计和应用提供参考.

关键词: 草酸酯加氢, 钌金属均相催化体系, 乙二醇, 反应条件, 催化机理

Hydrogenation of oxalates is one of the important organic reactions, which has an ultimate use for the industrial production of ethylene glycol. The studies on the ruthenium complexes-based homogeneous catalytic reaction systems are herein summarized. With the focus on the catalytic reaction systems, the important factors with significant influences on the oxalate transformation efficiency as well as the product selectivity are discussed, including temperature, H2 pressure, catalyst concentration, reaction duration, additives, and so on. The catalytic reaction mechanisms are also discussed in detail, where the mechanism for the H2-heterolysis promoted under the metal-ligand cooperation for the oxalate hydrogenation to ethylene glycol is enhanced. This study would be useful for designing the new catalyst applicable in industry.

Key words: hydrogenation of oxalate, ruthenium complexes-based homogeneous catalytic system, ethylene glycol, reaction conditions, catalytic mechanism