熔融反应合成2,2′-联吡啶桥联二(4,4′-联吡啶)类哑铃型化合物  

Fusion Reaction for Synthesis of Dumbbell-shape Compounds Containing Two Units of 4,4′-Bipyridine Bridged by 2,2′-Bipyridine

作　　者：贺干武[1,2] 张青丽[1] 许新华[1] 邱仁华[1] 李言杰[1] 张胜天[1] 刘凤伟[1] 

机构地区：[1]湖南大学化学化工学院,长沙410082 [2]邵阳学院化学系 邵阳

出　　处：《应用化学》2007年第1期8-11,共4页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金资助课题(20372020)

摘　　要：研究阻塞基的乙氧乙醇磺酸酯(1a～1c)与4,4′-联吡啶在熔融条件下反应合成单取代4．4′-联吡啶衍生物(28～2c)。结果显示,在熔融条件下30 min完成反应。投料比对产物有很大的影响。当投料比为1:1时,主要产物为双取代4,4′-联吡啶产物,增加4,4′-联吡啶的用量,单取代产物增加。当投料比为1:10时,单取代产物占绝对优势,分离后的收率达90％。中间体(2a～2c)与4,4′-二(溴甲基)-2,2′-联吡啶按1:1摩尔比混合,按照上述相同的方法进行反应,得到2,2′-联吡啶桥联二(4,4′-联吡啶)类哑铃型化合物(38～3c),收率分别为化合物3a为81％,3b为87％,3c为79％。In the synthesis of N-substituted derivatives of 4,4＇-bipyridine（2a - 2c） v/a the fusion reaction of tosylate with 4,4＇-bipyridine, it was found that the reaction was completed within 30 min, but the molar ratio of the tosylate to 4,4＇-bipyridine had significantly influence on the yields of N-substituted derivatives of 4,4＇- bipyridine. If the ratio was 1 ： 1, N, N＇-disubstituted derivatives of 4,4＇-bipyridine was major products. Increasing the ratio of tosylate to 4,4＇-bipyridine, the yields of （2a -2c） were increased. When the ratio was 1：10, it generated the N-substituted derivatives of 4,4＇-bipyridine（2a -2c） in about 90% yields. By reacting intermediates （2a - 2c ） （0. 6 mmol ） with 4,4＇-di （ bromomethyl ） -2,2 ＇-bipyridine （ 0. 3 mmol） according to the same method as above, the dumbbell-shape compounds containing two units of 4,4＇-bipyridine bridged by 2,2＇-bipyridine（3a -3c） were obtained in 79% - 87%.

关 键 词：无溶剂反应 联吡啶 固相熔融 哑铃型化合物 

分 类 号：O614[理学—无机化学]