有机化学 ›› 2015, Vol. 35 ›› Issue (8): 1792-1796.DOI: 10.6023/cjoc201501005 上一篇    下一篇

研究简报

新型1,10-菲咯啉衍生物的设计与合成

金海明a, 邹亮a, 陈南雨a, 孙圆圆a, 罗书平a, Junge Henrikb, Beller Matthiasb   

  1. a 浙江工业大学化学工程学院 绿色化学合成技术国家重点实验室培育基地 杭州 310014;
    b 罗斯托克大学莱布尼茨催化研究所 罗斯托克 18059 德国
  • 收稿日期:2015-01-05 修回日期:2015-03-20 出版日期:2015-08-25 发布日期:2015-04-10
  • 通讯作者: 罗书平 E-mail:luoshuping@zjut.edu.cn
  • 基金资助:

    国家自然科学基金(Nos. 21361130021, 21376222)资助项目.

Design and Synthesis of Novel 1,10-Phenanthroline Derivatives

Jin Haiminga, Zou Lianga, Chen Nanyua, Sun Yuanyuana, Luo Shupinga, Henrik Jungeb, Matthias Bellerb   

  1. a State Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014;
    b Leibniz Institute for Catalysis at the University of Rostock LIKAT, Rostock 18059, Germany
  • Received:2015-01-05 Revised:2015-03-20 Online:2015-08-25 Published:2015-04-10
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21361130021, 21376222).

以功能化氮配体为导向, 设计合成了一类新型1,10-菲咯啉衍生物1a~1d. 以1-溴代芳基-3-氯-丙酮(2)和邻苯二胺(3)为原料, 一锅法混酸催化合成4,7-二溴代芳基-1,10-菲咯啉(4), 收率可达64%. 以有机锂试剂为卤锂交换试剂和亲核试剂, 以CO2为淬灭剂, 对溴代菲咯啉中间体进行定向结构修饰, 合成了2,9-二烷基-4,7-二(羧芳基)-1,10-菲咯啉衍生物, 收率可达59%, 为获得2,9-烷基化的羧酸功能化的菲咯啉提供了一条反应简洁、操作方便的合成路线.

关键词: 1,10-菲咯啉衍生物, 邻苯二胺, 一锅法, 羧酸

To access functionalized nitrogen ligands, a series of novel 1,10-phenanthroline derivatives 1a~1d were designed and synthesized. Starting from 1-bromoaryl-3-chloroacetone (2) and o-phenylenediamine (3), 4,7-dibromoaryl-1,10-phenanthroline (4) were obtained in up to 64% yield by using a straightforward one-pot method catalyzed by mixed acids. Next, halogen lithium exchange reactions were performed to give 4. Finally, quenching of the reaction mixture with CO2 gave the desired 2,9-dialkyl-4,7-bis(carboxy-aryl)-1,10-phenanthroline derivatives 1 in up to 59% yield. This work provides a simple and convenient route to synthesize new 2,9-alkylated carboxylic acid-functionalized phenanthrolines.

Key words: 1,10-phenanthroline derivatives, o-phenylenediamine, one pot, carboxylic acid