【作者】 李会旭；

【导师】 张文勤；

【作者基本信息】 天津大学 ， 有机化学， 2007， 硕士

【摘要】 冠醚是一类人工合成的受体,人们经过几十年的研究,仍然方兴未艾。如何设计对单一金属离子具有高选择性的冠醚,一直是人们所面临的具有挑战性的课题。本论文第一部分以2-甲基苯并噁唑、邻苯二酚、氯乙醇、苯胺和三甘醇为初始原料设计合成了5种冠醚——2,3,11,12-二苯并-1,4,7,10,13,16-六氧杂环十八碳-2,11-二烯,二(4’-甲酰基)-2,3,11,12-二苯并-1,4,7,10,13,16-六氧杂环十八碳-2,11-二烯,二{4’-[2-(2-苯并噁唑基)乙烯基]}-2,3,11,12-二苯并-1,4,7,10,13,16-六氧杂环十八碳-2,11-二烯,7,16-二苯-1,4,10,13-四氧杂-7,16-六氧杂环十八烷,N,N’-二(4’-甲酰苯基)-7,16-二苯-1,4,10,13-四氧杂-7,16-二氮杂环十八烷。其中二{4’-[2-(2-苯并噁唑基)乙烯基]}-2,3,11,12-二苯并-1,4,7,10,13,16-六氧杂环十八碳-2,11-二烯是未经文献报道的新化合物。我们在冠醚的苯环上接上了带有杂原子的较大的共轭体系,目的是改变母体冠醚的光物理性能,通过研究其结合阳离子后光谱的变化规律进一步研究新型冠醚化合物对碱金属和碱土金属离子的配位及识别性能。我们预期它们在构筑冠醚-金属配位聚合物时,将会产生π-π堆积、阳离子-π相互作用等超分子构筑力,从而组装成为结构新颖的超分子物种。本文通过熔点测定、核磁共振氢谱分析表征了化合物的结构。用荧光光谱的方法初步研究了新型冠醚化合物对碱金属和碱土金属离子的配位及识别性能。本论文第二部分以高哌嗪、4-羟基苯甲酸和6-羟基-2-萘甲酸为原料合成了一种高哌嗪不对称双酰胺类抗氧剂,这个化合物以前没有文献报道过,并通过核磁共振氢谱表征了化合物的结构。更多还原

【Abstract】 Crown ether is a kind of man-made receptor, and its study is still of ongoing interest for more than thirty years. It is a challengible task for researchers to design more highly selective crown ether for single metal ions. In the first part of this thesis, Five crown ethers were synthesized by using 2-methylbenzo[d]oxazole, pyrocatechol, 2-chloroethanol, aniline and triethylene glycol. They are 2,3,11,12-dibenzo-1,4,7,10, 13,16-hexaoxacyclooctadeca-2,11-diene, bis(4’-formyl)-2,3,11,12-dibenzo-1,4,7,10,13, 16-hexaoxacyclooctadeca-2,11-diene, bis{4’-[2-(2-benzooxazolyl)ethenyl]}-2,3,11,12 -dibenzo-1,4,7,10,13,16-hexaoxacyclooctadeca-2,11-diene, 7,16-diphenyl-1,4,10,13- tetraoxa-7,16-diaza-cyclooctadecane, N,N’-bis(4-formyl)-7,16-diphenyl-1,4,10,13- tetraoxa-7,16-diaza-cyclooctadecane. Bis{4’-[2-(2-benzooxazolyl)ethenyl]}-2,3,11,12 -dibenzo-1,4,7,10,13,16-hexaoxacyclooctadeca-2,11-diene is new. In order to improve the electronic spectra properties of the crown ether, efficient conjugatingπ-πgroup is connected with the benzene ring. The recognization ability with alkali metals and alkali earth metals was investigated via the spectra changing after the above metal cations are combined. It was expected that novel non-covalent forces in crystal such asπ-πstacking, cation-πinteractions and so on would aid the formation of supramolecular aggregation when those crown ethers coordinate with metal cations. These compounds were determined by melting point and 1H-NMR. Through fluorescence spectrum method, we primarily study on the linkage and selectivity of novel armed crown ethers-metal.In the second part, asymmetric diamide of homopiperazine was synthesized by using homopiperazine, 4-hydroxybenzoic acid and 6-hydroxynaph-thalene-2- carboxylic acid, this compound is new. Its structure was determined by 1H-NMR.更多还原