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

用核磁共振光谱法研究了合成的羧基离子载体(1)的碱金属盐的溶液构象。这些盐的构象类似于晶体中的分子结构，就像已经报道过的网球的接缝。合成了1的两个苯环被两个萘环取代的化合物2。x射线晶体学分析的钾盐分子结构与钾盐相似。但2的空腔尺寸略大于1的空腔尺寸，这可能是由于萘环的空间效应所致。钾盐2在溶液中的构象与晶体中的构象相似。合成了1的m-和p-取代异构体（3和4），并研究了它们的离子传输能力。4的输运能力较差，而m-异构体3输运了相当数量的碱金属离子。发现3的离子选择性比1和2的离子选择性低。经^1H-NMR谱分析发现，碱金属盐3的构象与相应的盐1和盐2相似。以链长小于1的羧基离子载体为原料合成内酯。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.