Chin. J. Org. Chem. ›› 2019, Vol. 39 ›› Issue (6): 1720-1726.DOI: 10.6023/cjoc201901018 Previous Articles     Next Articles

Special Issue: 金属有机化学

Articles

交联壳聚糖微球负载铜水相催化Ullmann反应

吕小妹a,b, 阮建成a, 陈新志a, 钱超a   

  1. a 浙江省化工高效制造技术重点实验室 浙江大学化学工程与生物工程学院 杭州 310027;
    b 新加坡南洋理工大学化学与生物医学工程学院 新加坡 637459
  • 收稿日期:2019-01-14 修回日期:2019-03-25 出版日期:2019-06-25 发布日期:2019-04-11
  • 通讯作者: 钱超 E-mail:qianchao@zju.edu.cn
  • 基金资助:

    国家自然科学基金(No.21476194)、国家重点研发计划(No.2016YFB0301800)资助项目.

Cross-Linked Chitosan Bead Supported Copper Complex in Water as a Green and Efficient Catalytic Protocol for Ullmann Reaction

Lü Xiaomeia,b, Ruan Jianchenga, Chen Xinzhia, Qian Chaoa   

  1. a Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027;
    b School of Chemical and Biomedical Engineering, College of Engineering, Nanyang Technological University, 62 Nanyang Drive, Singapore 637459, Singapore
  • Received:2019-01-14 Revised:2019-03-25 Online:2019-06-25 Published:2019-04-11
  • Contact: 10.6023/cjoc201901018 E-mail:qianchao@zju.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21476194), and the National Key Research and Development Program of China (No. 2016YFB0301800).

A green, efficient, and recyclable catalytic protocol for Ullmann C-N reaction in water was developed. The catalyst Chi-Gly@CuI was prepared by the cross-linking reaction of chitosan bead with glyoxal and subsequently anchored with copper salt. Chi-Gly@CuI bead of 0.3 mm in mean diameter possesses porous micro-structure demonstrated by scanning electron microscope (SEM). The structure of Chi-Gly@CuI was characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG), X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectrometry (ICP-AES), and X-ray photoelectron spectroscopy (XPS). This catalytic protocol for Ullmann reaction in water exhibited high applicability, from which the corresponding coupling products were afforded in good to excellent yields. Chi-Gly@CuI could be easily separated from products by simple filtration almost without weight loss. Most notably, after 10 times of recycling, its catalytic activity and chemical stability were still maintained.

Key words: cross-linked chitosan bead, Ullmann reaction, copper, heterogenous catalysis, in water