“黑洞型”缺电子联吡啶环蕃的合成  

Synthesis of "Black Hole" 4,4'-Bipyridinium Cyclophane

作　　者：席海涛[1] 孙小强[2] 魏海林[2] 孟启[2] 潘毅[1] 胡宏纹[1] 

机构地区：[1]南京大学化学化工学院,南京210093 [2]江苏工业学院精细石油化工重点实验室,常州213164

出　　处：《有机化学》2007年第12期1547-1551,共5页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.20272019);江苏省高校研究生创新计划(2006)资助项目

摘　　要：利用2,3,5,6-四氟-1,4-苯二甲酸为原料,经过酯化、还原及溴代,合成1,4-二溴甲基-2,3,5,6-四氟苯.以其为原料在低温下利用模板效应合成高度缺电子的"黑洞型"缺电子联吡啶环蕃化合物,经过连续液液萃取及离子交换得到"黑洞型"缺电子联吡啶环蕃单体.产品经1HNMR,13CNMR,MS表征.利用变温核磁共振技术研究"黑洞型"缺电子联吡啶环蕃与经典的双环(百草枯-对苯撑)型缺电子联吡啶环蕃在溶液中的变化.The 4,4＇-bipyridinium-based cyclophane cyclo（paraquat-2,3,5,6-tetrafluoro-p-phenyleneparaquat） was prepared by the template-directed synthesis in a 21% yield, of which the starting material 1,4-bis（bromomethyl）-2,3,5,6-tetrafluorobenzene was prepared by the esterification of 2,3,5,6-tetrafluoro-p- phthalic acid with methanol, reduction with LiA1H4 to give 1,4-bis（hydroxymethyl）-2,3,5,6-tetrafluorobenzene, and then bromination with toluene and 48% HBr. The free cyclophane was characterized by MS, ^1H NMR and ^13C NMR spectra. The influence of fluorine on the cyclophane in solution was studied by dynamic ^1H NMR spectroscopy.

关 键 词：2 3 5 6-四氟-1 4-苯二甲酸 1 4-二溴甲基-2 3 5 6-四氟苯 模板效应 黑洞型 环蕃 变温核磁共振 

分 类 号：O626[理学—有机化学]