高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (3): 490-497.doi: 10.7503/cjcu20190317

• 有机化学 • 上一篇    下一篇

含噁二唑大环冠醚的合成、 结构及金属离子识别性能

田霞1,杨福群1,袁伟1,赵雷1,姚雷1,甄小丽1,韩建荣1,*,刘守信2,*   

  1. 1. 河北科技大学理学院
    2. 河北省药用分子化学重点实验室, 石家庄 050018
  • 收稿日期:2019-05-31 出版日期:2020-02-26 发布日期:2019-12-10
  • 通讯作者: 韩建荣,刘守信
  • 作者简介:韩建荣, 女, 博士, 教授, 主要从事超分子化学研究. E-mail: han_jianrong@126.com|刘守信, 男, 博士, 教授, 主要从事药物合成研究. E-mail: chlsx@263.net
  • 基金资助:
    国家自然科学基金资助(No.21272052)

Synthesis, Structure and Recognition Properties of Macrocyclic Crown Ethers with Oxadiazole

TIAN Xia1,YANG Fuqun1,YUAN Wei1,ZHAO Lei1,YAO Lei1,ZHEN Xiaoli1,HAN Jianrong1,*,LIU Shouxin2,*   

  1. 1. College of Science, Hebei University of Science & Technology
    2. State Key Laboratory Breeding Base-Hebei Province Key Laboratory of Molecular Chemistry for Drug, Hebei University of Science & Technology, Shijiazhuang 050018, China
  • Received:2019-05-31 Online:2020-02-26 Published:2019-12-10
  • Contact: Jianrong HAN,Shouxin LIU
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.21272052)

摘要:

合成了含有1,3,4-噁二唑基团的大环冠醚: 2,3,11,12-二苯并-4,7,10,16-四氧-14,15-二氮杂双环[11.2.1]-十六烷-13,15-二烯(2)、 2,3,14,15-二苯并-4,7,10,13,19-五氧-17,18-二氮杂双环[14.2.1]-十九烷-16,18-二烯(3)和2,3,17,18-二苯并-4,7,10,13,16,22-六氧-20,21-二氮杂双环[17.2.1]-二十二烷-19,21-二烯(4), 并培养得到其单晶; 通过核磁共振波谱、 高分辨质谱及X射线单晶衍射对其结构进行了表征. 结果表明, 冠醚2属正交晶系, Pna21空间群; 冠醚3属于单斜晶系, C2/c空间群; 冠醚4属正交晶系, Pbca空间群. 在3个主体化合物中均存在分子间氢键和π-π相互作用将分子连接成三维空间结构. 采用荧光光谱测定了开链冠醚2,5-二[2-(2-甲氧乙氧基)苯基]-1,3,4-噁二唑(1)和不同环空腔大小的噁二唑冠醚(2~4)对金属离子Li +, Na +, K +, Rb +, Mg 2+和Ca 2+的键合行为. 研究结果表明, 开链冠醚1和冠醚4对碱土金属Mg 2+和Ca 2+表现出荧光猝灭行为, 且对Ca 2+表现出良好的键合能力和选择性; 而冠醚2对Na +和K +表现出良好的键合能力, 但其Na +/K +的选择性较差.

关键词: 1,3,4-噁二唑, 冠醚, 阳离子识别, 晶体结构, 荧光光谱

Abstract:

A series of macrocyclic crown ethers containing oxadiazole groups were synthesized and their single crystals were obtained. Their structures were characterized by nuclear magnetic resonance(NMR), high resolution electrospray ionization mass spectroscopy(HRESI-MS) and X-ray single crystal diffraction. The single crystal X-ray diffraction revealed that 2,3,11,12-dibenzo-4,7,10,16-tetraoxa-14,15-diazabicyclo[11.2.1]-hexadecane-13,15-diene(2) belonged to orthorhombic crystal system with space group Pna21, 2,3,14,15-dibenzo-4,7,10,13,19- pentaoxa-17,18-diazabicyclo[14.2.1]-nonadecane-16,18-diene(3) belongs to monoclinic crystal system with space group C2/c and 2,3,17,18-dibenzo-4,7,10,13,16,22-hexaoxa-20,21-diazabicyclo[17.2.1]-docosadecane-19,21-diene(4) belonged to orthorhombic crystal system with space group Pbca. Three crown ethers were all connected to form a three-dimensional supramolecular structure by C—H…O or C—H…N hydrogen bond intramolecular and π-π stacking. The bonding behaviors of 2,5-bis[2-(2-methoxyethoxy)phenyl]-1,3,4-oxadiazole(1) and crown ethers 2—4 with different sizes to metal ions Li +, Na +, K +, Rb +, Mg 2+ and Ca 2+ was determined by fluorescence spectroscopy. The results showed that open-chain crown ether 1 and macrocyclic crown ether 4 exhibited fluorescence quenching behavior and good bon-ding ability and selectivity on alkaline earth metal Ca 2+. While crown ether 2 showed good bonding ability to Na + and K +and poor Na +/K + selectivity.

Key words: 1,3,4-Dioxazole, Crown ether, Cationic recognition, Crystal structure, Fluorescence spectroscopy

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