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.
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.