DESIGH AND SYNTHESIS OF POLYETHER COMPOUNDS WITH THEIR CONTROLLED THREE-DIMENSIONAL STRUCTURES

用核磁共振波谱法研究了一种合成羧酸类离子载体（1）的碱金属盐的溶液构型。这些盐在晶体中的构象类似于已报道的网球缝的分子结构。化合物2中1的两个苯环被两个萘环取代。用X射线晶体学分析钾盐的分子结构与钾盐的分子结构相似。但由2形成的空穴尺寸略大于1，这可能是由于萘环的空间效应。钾盐2在溶液中的构象与晶体中的构象相似，合成了钾盐1的间位和对位取代异构体（3和4），并研究了它们的离子传输能力。虽然4的迁移能力较差，但间位异构体3迁移了相当数量的碱金属离子。发现3的离子选择性低于1和2。1H-NMR谱表明，3的碱金属盐的构象与1和2的相应盐相似，由比1链长更短的羧酸类离子载体合成了内酯.内酯对碱金属离子的萃取效率远低于冠醚。

Solution confomations of alkali metal salts of a synthetic carboxylic ionophore (1) were investigated by NMR spectroscopy. These salts adopt conformations similar to molecular structures in the crystal like the seam of a tennis ball which has been already reported.Compound 2 in which the two benzene rings of 1 are replaced with two naphtalene rings was synthesized. Molecular structure of the potassium salt analyzed by X-ray crystallography was similar to that of potassium salt. but the cavity size made of 2 was slightly larger than that of 1 probably because of steric effect of the naphthalene rings. The conformation of potassium salt 2 in solution resembled that in the crystal.The m- and p-subsutituted isomers (3 and 4) of 1 were synthesized and their ion transport ability was studied. While the transport ability of 4 was poor, the m-isomer 3 transported a considerable amount of alakli metal ions. The ion selectivity by 3 was found to be lower than those by 1 and 2. It was revealed by ^1H-NMR spectroscopy that the conformations of alkali metal salts of 3 were similar to the corresponding salts of 1 and 2.Lactones were synthesized from carboxylic ionophores with shorter chain lengh than that of 1. Extraction efficiency of alkali metal ions by the lactones was much lower than that by crown ethers.