系列三联吡啶衍生物的合成及在催化氧化中的应用  

Synthesis of a Series of Terpyridine Derivatives and Their Application in Catalytic Oxidation Reactions

作　　者：范伟伟 刘建奇 李攀攀 詹红菊[1] 熊航行[1] FAN Wei-wei;LIU Jian-qi;LI Pan-pan;ZHAN Hong-ju;XIONG Hang-xing(College of Chemical Engineering and Pharmacy,Jingchu University of Technology,Jingmen 448000,China)

机构地区：[1]荆楚理工学院化工与药学院,湖北荆门448000

出　　处：《化学试剂》2022年第1期142-146,共5页Chemical Reagents

基　　金：湖北省优秀中青年科技创新团队计划项目(T2020023);荆门市重点科技计划项目(2020ZDYF002);荆楚理工学院科技计划项目(T202101)。

摘　　要：采用一步法合成了5种三联吡啶的衍生物:4′-(吡啶-4-基)-2,2′∶6′,2″-三联吡啶(L1)、4′-苯基-2,2′∶6′,2″-三联吡啶(L2)、4′-(3,5-二氯吡啶-4-基)-2,2′∶6′,2″-三联吡啶(L3)、4′-(3,5-二溴吡啶-4-基)-2,2′∶6′,2″-三联吡啶(L4)、4′-(4-(吡啶-4-基)苯基)-2,2′∶6′,2″-三联吡啶(L5),其中L3和L4为尚未见报道的新颖化合物。以制备的多吡啶化合物为配体,和MnCl_(2)·4H_(2)O共同催化苄基醇的氧化反应,研究发现5种多吡啶配体均具备良好的性能,配体分子结构中的4′-吡啶取代基对提高催化活性有重要作用。最后选用性能最优的4′-(4-(吡啶-4-基)苯基)-2,2′∶6′,2″-三联吡啶为配体,与MnCl_(2)·4H_(2)O共同催化叔丁基过氧化氢氧化苄基醇和苄基烷烃,5种典型底物的转化率均在95%以上,产率在90%以上。该催化氧化方法有望应用于芳香酮类化合物及相关药物中间体的绿色、高效合成。Five terpyridinederivatives,4′-(pyridin-4-yl)-2,2′∶6′,2″-terpyridine(L1),4′-phenyl-2,2′∶6′,2″-terpyridine(L2),4′-(3,5-dichloropyridin-4-yl)-2,2′∶6′,2″-terpyridine(L3),4′-(3,5-dibromopyridin-4-yl)-2,2′∶6′,2″-terpyridine(L4)and 4′-(4-(pyridin-4-yl)phenyl)-2,2′∶6′,2″-terpyridine(L5),were synthesized by one-step method.Among them,the novel compounds L3 and L4 have not yet been reported.Then these polypyridine compounds were used as the ligand to catalyze the oxidation of benzyl alcohol with MnCl_(2)·4H_(2)O.It was found that all the five polypyridine ligands had good properties.The 4′-pyridine substituent in the molecular structure of the ligands played an important role in improving the catalytic activity.Finally,4′-(4-(pyridine-4-yl)phenyl)-2,2′∶6′,2″-tribipyridine was selected as the best ligand to catalyze the oxidation of benzyl alcohols and benzyl alkanes with MnCl_(2)·4H_(2)O.The conversion rates of five typical substrates were all above 95%and the yields were all above 90%.This catalytic oxidation method is expected to be applied to the green and efficient synthesis of aromatic ketones and related drug intermediates.

关 键 词：多吡啶化合物 催化 氧化反应 叔丁基过氧化氢 芳香酮 

分 类 号：TQ032[化学工程]