2-(对羟基苯氧基)乙基取代的Cyclen的合成和结构研究

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, α＝γ＝90°, β＝120.360(3)°, V＝5.5486(6) nm³, Z＝8, D_c＝1.146 g/cm³, F(000)＝2056, μ＝0.082 mm^－1, R＝0.0853, wR＝0.2331 I＞2σ(I)].

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

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-bis2-(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-bis2-(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) nm³, Z＝8, D_c＝1.146 g/cm³, F(000)＝2056, μ＝0.082 mm^－1, R＝0.0853, and wR＝0.2331 I＞2σ (I)].