Development of Calixarene Derivatives Having Molecular Recognition Ability and Catalytic Ability

对杯芳烃衍生物的合成及其性质进行了研究，以期开发出具有高分子识别能力和高催化能力的材料。所得结果总结如下1。以p- h -杯[4]芳烃为起始原料，合成了杯[4]醌和杯[4]对苯二酚，并对其构象性质进行了研究。对苯并杂杯[4]和[6]芳烃对Ag^+、Hg^+和Hg^<2+>等重金属离子具有较强的捕获能力。它们也表现出变色的性质。对叔丁基杯[6]芳烃衍生物在6个酚氧上含有3,6,9-三氧六烷基，具有较高的捕获K^+离子的能力。利用这一能力，开发了新的酯化反应和二氯苯生成反应。上述杯芳烃衍生物在烯烃、炔烃和伯醇的kmno_4氧化制羧酸和仲醇氧化制酮等反应中起催化剂作用。上述杯芳烃衍生物还表现出包含二烯-碘配合物的能力。此外，杯芳烃衍生物在ti配合物催化分离二烯与NaBH_4.6氢化反应中的反应活性和选择性均有所提高。建立了对叔丁基杯[6]芳烃的工艺生产方法。

The synthesis and properties of calixarene derivatives have been studied with the intention of developing materials having a high molecular recognition ability and a high catalytic ability. The results obtained are summarized below.1. Calix[4]quinone and calix[4]hydroquinone were synthesized starting with p-H-calix[4]arene, and their conformational properties were elucidated.2. p-Phenylazocalix[4]and[6]arenes exhibited the high ability of capturing heavy metal ions such as Ag^+, Hg^+, and Hg^<2+>. They also exhibited a chromotropic property.3. The p-t-butylcalix[6]arene derivative bearing 3,6,9-trioxadecyl group at six phenolic oxygens showed the high ability of capturing K^+ion. By utilizing this ability, new esterification reaction and dichlorocarbene generation reaction were developed.4. The above calixarene derivative served as catalysts for the KMnO_4oxidation of alkenes, alkynes, and primary alcohols to yield carboxylic acids and also for the oxidation of secondary alcohols to ketones.5. The above calixarene derivatives also exhibited the ability of including diene-iodine complexes.Moreover, the calixarene derivative enhanced the reactivity and selectivity in the Ti-complex catalyzed hydroboration of isolated dienes with NaBH_4.6. The method for technical production of p-t-butylcalix[6]arene was established.