化学学报 ›› 2004, Vol. 62 ›› Issue (5): 514-517. 上一篇    下一篇

研究论文

新型臂式氮杂冠醚的合成及其多价螯合的热力学特征

张强, 李莉, 刘育   

  1. 南开大学化学系, 元素有机化学国家重点实验室, 天津, 300071
  • 投稿日期:2003-07-07 修回日期:2003-11-08 发布日期:2014-02-18
  • 通讯作者: 刘育,E-mail:yuliu@public.tpt.tj.cn;Tel:022-23503625;Fax:022-23504853 E-mail:yuliu@public.tpt.tj.cn
  • 基金资助:
    国家自然科学基金(Nos.90306009,20372038),教育部博士点基金(Oo.20010055001)资助项目.

Synthesis of Novel Armed-tetraazacrown Ethers and Their Thermodynamic Characteristics of Multivalency Chelation

ZHANG Qiang, LI Li, LIU Yu   

  1. Department of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071
  • Received:2003-07-07 Revised:2003-11-08 Published:2014-02-18

通过采用微波方法提高了1,10-二氧-4,7,13,16-四氮杂18-冠-6 (L1)的合成产率.以该化合物作为母体与溴乙酸乙酯反应合成了两种新型的臂式冠醚L2和L3.采用等温滴定量热法测定了这三种氮杂冠醚与Ca(Ⅱ)键合的热力学参数,量热滴定拟合结果表明,除母体氮杂冠醚外,臂式氮杂冠醚L2和L3均能与Ca(Ⅱ)形成1:1的稳定配合物,其稳定性主要来自于多价螯合的焓贡献.

关键词: 臂式氮杂冠醚, 合成, 等温滴定量热法, Ca(Ⅱ)配合物, 多价螯合

The azacrown ether, 1,10-dioxa-4,7,13,16-tetraaza-18-crown-6 (L1) was synthesized by improved microwave-method, and its two armed-derivatives (L2 and L3) were firstly prepared by introducing the bromoethyl acetate. The thermodynamic parameters of the complexation of the three azacrowns and Ca(Ⅱ) were determined by isothermal titration calorimetry (ITC) at 25℃ in Tris/HCl buffer solution (pH 8.0). The results showed that, except for the parent azacrown (L1), the two armed-derivatives both form the stable 1:1 stoichiometric complexes with Ca(Ⅱ), which is mainly contributed by the enthalpy changes arising from the multivalency chelation between the arms of azacrown ethers and Ca(Ⅱ).

Key words: armed-azacrown ether, synthesis, isothermal titration calorimetry, calcium(Ⅱ)complex, multivalency chelation