设计实验:选择性保护1,4,7,10-四氮杂环十二烷的仲胺  

Design Experiment:Selective Protection of the Amino Groups of 1,4,7,10-Tetraazacyclododecane

作　　者：张琴芳[1] 王爱群 任小雨 张红素[1] 余孝其[2] ZHANG Qinfang;WANG Aiqun;REN Xiaoyu;ZHANG Hongsu;YU Xiaoqi(Basic Chemistry Experiment Teaching Center,Sichua University,Chengdu 610064,China;College of Chemistry,Sichua University,Chengdu 610064,China)

机构地区：[1]四川大学化学基础实验教学中心,成都610064 [2]四川大学化学学院,成都610064

出　　处：《实验室研究与探索》2020年第1期241-244,共4页Research and Exploration In Laboratory

基　　金：四川大学实验室及设备管理处实验技术立项(20170033);新世纪高等教育教学改革工程(第八期)研究项目(SCU8165)。

摘　　要：氨基官能团存在于很多有生理活性的化合物中,氨基的保护策略选择对合成化学工作者非常重要。基于1,4,7,10-四氮杂环十二烷(Cyclen)的化合物应用广泛,为了合成基于Cyclen的具有不同结构和功能的产品,就需要系统的合成化学,尤其是对其仲胺的选择性保护。该设计实验以Cyclen为原料,分别采用(Boc)2O和Boc-OSu为胺基保护试剂,制备1,4,7-3 Boc-Cyclen和1,7-2 Boc-Cyclen;采用上一步合成的1,4,7-3 Boc-Cyclen为原料,Fmoc-Cl为保护试剂,制备1,4,7-3 Boc-10-Fmoc-Cyclen,再用CF3COOH脱掉Boc保护基制备Fmoc-Cyclen,以此得到单保护、对位二保护和三保护的Cyclen。结合1H NMR、13C NMR和HR-MS的鉴定结果,目标化合物结构正确。Amino functional groups are present in many physiologically active compounds,and the choice of amino protection strategy is important to synthetic chemists.Compounds based on 1,4,7,10-tetraazacyclododecane(Cyclen)are widely used.In order to synthesize Cyclen-based products with different structures and functions,systematic synthetic chemistry is required,especially selective protection of secondary amines.This design experiment uses Cyclen as raw material,and uses(Boc)2O and Boc-OSu as amino protecting reagents respectively to prepare 1,4,7-3 Boc-Cyclen and 1,7-2 Boc-Cyclen;Next,the 1,4,7-3 Boc-Cyclen synthesized in the previous step was used as a raw material,Fmoc-Cl was used as a protective reagent to prepare 1,4,7-3 Boc-10-Fmoc-Cyclen,and then the Boc protecting group was removed by CF3COOH to prepare Fmoc-Cyclen.In this way,single protected,para-double protected and triple protected Cyclen are obtained.Combining the results of 1H NMR,13C NMR and HR-MS,the structures of the target compounds are correct.

关 键 词：设计实验 1 4 7 10-四氮杂环十二烷 选择性保护仲胺 

分 类 号：O633[理学—高分子化学]