2-(对羟基苯氧基)乙基取代的Cyclen的合成和结构研究  

Synthesis and Their Construction Studies of Substituted Cyclen Compounds Containing 2-(p-Hydroxyphenoxy)ethyl

作　　者：张秀芹[1] 席海涛[1] 孟启[1] 姜艳[1] 孙小强[1] 胡宏纹[2] 

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

出　　处：《有机化学》2008年第3期484-488,共5页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.20272019)资助项目

摘　　要：在酸性条件下(pH=2～3),1,4,7,10-四氮杂环十二烷(Cyclen)和氯甲酸苄酯反应,得到高选择性1,7-二保护Cyclen衍生物1,7-二(苄氧基羰基)-1,4,7,10-四氮杂环十二烷(4),然后在二异丙基乙胺作用下和化合物1-苄氧基-4-(2-溴乙氧基)苯(2)一锅法有效合成了中间体1,7-二(2-对苄氧基苯氧基)乙基-4,10-二(苄氧基羰基)-1,4,7,10-四氮杂环十二烷(5)和4-(2-对苄氧基苯氧基)乙基-1,7-二(苄氧基羰基)-1,4,7,10-四氮杂环十二烷(6),在乙醇溶液中经Pd/C催化氢解得到两种新型的用取代苯酚基修饰的Cyclen衍生物1,7-二(2-对羟基苯氧基)乙基-1,4,7,10-四氮杂环十二烷(7)和1-(2-对羟基苯氧基)乙基-1,4,7,10-四氮杂环十二烷(8),其结构经1HNMR,IR和MS确证.用单晶X射线衍射法测定了化合物7的晶体结构,晶体属单斜晶系,C2/c空间群,晶胞参数a=2.4145(6)nm,b=1.6012(4)nm,c=1.6632(4)nm,α=γ=90°,β=120.360(3)°,V=5.5486(6)nm3,Z=8,Dc=1.146g/cm3,F(000)=2056,μ=0.082mm-1,R=0.0853,wR=0.2331[I>2σ(I)].A simple and efficient method has been reported by following a close pH control between 2 and 3 during slow addition of benzyl chloroformate to give the symmetrically 1,7-diprotected 1,4,7,10-tetraazacyclododecane （cyclen） derivative 1,7-bis（benzyloxycarbonyl）-cyclen （4）. The benzyloxycarbonyl derivative 4 reacted with 1-[4-（2-bromoethoxy）phenoxy]methyl benzene （2） by one-pot reaction in the presence of diisopropylethylamine to aftord intermediates 1,7-bis[2-（4-benzyloxyphenoxy）ethyl]-4,10-bis（benzyloxyphenoxy）-1,4,7,10-tetraazacyclododencane （5） and 4-[2-（4-benzyloxyphenoxy）ethyl]-1,7-bis（benzyloxycarbonyl）-1,4,7,10-tetraazacyclododecane （6）. Catalytic hydrogenation of 5 and 6 in ethanol cleaved the benzyloxycarbonyl and benzyl groups to give two novel pendant-armed phenol-containing cyclen derivafives 1,7-bis[2-（4-hydroxyphenoxy）ethyl]-1,4,7,10-tetraazacyclododecane （7） and 1-[2-（4-hydroxyphenoxy）ethyl]-1,4,7,10-tetraazacyclododecane （8） in high yields. The structures of the new macrocyclic compounds were characterized by 1H NMR, IR and MS spectra. The crystal structure of compound 7 was determined by X-ray single crystal diffraction method, which belongs to a monoclinic system with space group C2/c, a = 2.4145（6） nm, b= 1.6012（4） nm, c= 1.6632（4） nm, α=γ=90°,β=120.360（3）°V=5.5486（6）nm^3,Z=8,Dc=1.146g/cm^3,F（000）=2056,μ=0.082mm^-1,R=0.0853,wR=0.2331[1〉2σ（I）].

关 键 词：1 4 7 10-四氮杂环十二烷 氯甲酸苄酯 晶体结构 

分 类 号：O626[理学—有机化学]