2，2′-联吡啶参与的分子梭合成与^1H NMR研究  

Synthesis of Molecular Shuttle Containing the Unit of 2,2'-Bipyridine and Study of Its 1H NMR

作　　者：卢锐亮[1] 周冰[1] 许新华[1] 张青丽[1] 李言杰[1] 方敬坤[1] 

机构地区：[1]湖南大学化学化工学院,长沙410082

出　　处：《有机化学》2005年第3期299-303,共5页Chinese Journal of Organic Chemistry

基　　金：湖南大学人才基金;大型精密仪器开放基金资助项目.

摘　　要：2-{2-[4-苯基-二(4-特丁基苯基)甲基]苯氧基}乙氧乙醇磺酸酯(1)与4,4'-联吡啶在乙腈中回流36h,随后通过阴离子交换得到N-{2-{2-[4-苯基-二(4-特丁基苯基)甲基]苯氧基}乙氧乙基}-4,4'-联吡啶六氟磷酸盐(3),产率为93.4%.3与4,4'-二(溴甲基)-2,2'-联吡啶在乙腈中、70℃下反应72h,生成哑铃型化合物5,产率为45%.5与冠醚BPP34C10在55℃下搅拌5d,得到分子梭6和7,产率分别为42.3%和27.3%.HNMR数据表明,富电子冠醚BPP34C10与哑铃型组分上1贫电子4,4'-联吡啶的非键作用使4,4'-联吡啶上氢的化学位移向高场有较大移动.The reaction of the tosylate 1 of 2-{2-{4-[1-phenyl-1,1'-bis(4-tert-butylphenyl)methyl]- phenoxy}ethoxy}ethanol with 4,4'-bipyridine in CH3CN under refluxing for 36 h afforded N-{2-{2-{4- [1-phenyl-1,1-bis(4-tert-butylphenyl)methyl]phenoxy}ethoxy}ethyl}-4,4'-bipyridinium tosylate (2), and 2 exchanged anion with NH4PF6 to give hexafluoro-phosphate 3 in 93.4%. The compound reacted with 4,4'-di(bromomethyl)-2,2'-bipyridine to give the dumbbell-shaped compound 5 in 45% yield. The molecular shuttles 6 and 7 were synthesized by the self assembly of the dumbbell-shaped compound 5 and bispara- phenylene-34-crown-10. The H NMR data indicated that noncovalent interaction between the bipyridinium 1 and crown ether provoked a considerable high-field shift.

关 键 词：2 2′-联吡啶 冠醚 NMR 分子 乙腈 甲基 高场 产率 苯基 合成 

分 类 号：O626[理学—有机化学]