有机化学 ›› 2008, Vol. 28 ›› Issue (03): 484-488. 上一篇    下一篇

研究简报

2-(对羟基苯氧基)乙基取代的Cyclen的合成和结构研究

张秀芹a,席海涛a,孟启a,姜艳a,孙小强*,a,胡宏纹b   

  1. (a江苏工业学院精细石油化工重点实验室 常州 213164)
    (b南京大学化学系 南京 210093)
  • 收稿日期:2007-05-10 修回日期:2007-08-06 发布日期:2008-03-18
  • 通讯作者: 孙小强

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

ZHANG Xiu-Qina,XI Hai-Taoa,MENG Qia,JIANG Yana
SUN Xiao-Qiang*,a,HU Hong-Wenb   

  1. (a Key Laboratory of Fine Petrochemical Engineering, Jiangsu Polytechnic University, Changzhou 213164)
    (b Department of Chemstry, Nanjing University, Nanjing 210093)
  • Received:2007-05-10 Revised:2007-08-06 Published:2008-03-18
  • Contact: SUN Xiao-Qiang

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1H NMR, 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, αγ=90°, β=120.360(3)°, V=5.5486(6) nm3, Z=8, Dc=1.146 g/cm3, F(000)=2056, μ=0.082 mm-1, R=0.0853, wR=0.2331 [I>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

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-tetraaza- cyclododecane (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(benzyloxy- phenoxy)-1,4,7,10-tetraazacyclododencane (5) and 4-[2-(4-benzyloxyphenoxy)ethyl]-1,7-bis(benzyloxy- car-bonyl)-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 phe-nol-containing cyclen derivatives 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, αγ=90°, β=120.360(3)°, V=5.5486(6) nm3, Z=8, Dc=1.146 g/cm3, F(000)=2056, μ=0.082 mm-1, R=0.0853, and wR=0.2331 [I>2σ (I)].

Key words: benzyl chloroformate, crystal structure, 1,4,7,10-tetraazacyclododecane