含芳香Isoxazoline取代的Calix[4]pyrroles與偶氮Calix[4]pyrrole之合成研究

Abstract

對於陰離子的辨識及結合研究，是近年來主客化學中逐漸發展的領域。 其中，calix[4]pyrrole因其合成的簡易更是受到重視。 而本論文分為三部份，分別敘述對於calix[4]pyrrole衍生化的研究。 第一部份，我們利用單取代的hydroximoyl chloride 59a-b與 allyl-calix[4]pyrrole 56進行1,3-偶極環化加成反應， 成功的合成出含isoxazoline官能基的calix[4]pyrrole 衍生物62a-b， 而我們也發現化合物62b對於氯離子有不錯的結合作用。 第二部份，我們亦利用雙取代的hydroximoyl chloride 61a-b與allyl-calix[4]pyrrole 56進行1,3-偶極環化加成反應， 希望能得到含雙isoxazoline官能基的calix[4]pyrrole雙聚物63a-b。 出乎意料之外，我們並未得到預期的雙聚物63a-b，反而是得到一邊進行1,3-偶極環化加成反應，而另一邊進行pyrrole環的親電子取代反應的產物64。 第三部份是敘述將calix[4]pyrrole衍生為具偶氮發色團之化合物65，並對其與鹵素陰離子間的結合做了初步的研究，發現化合物65僅對氟離子有顯著的作用，但詳細的情形有待未來進一步的探討。

The chemistry of recognition and binding of anions is a developing area of host-guest chemistry. Among them, the easy-to-make anion-binding agent, calix[4]pyrrole, specially receives lots of attention. In this thesis, we report three synthetic routes for modification of calix[4]pyrroles. First, we successfully synthesized the calix[4]pyrrole derivatives 62a-b which contain different isoxazoline function groups through 1,3-dipolar cycloaddition reactions of hydroximoyl chloride 59a-b with allyl-calix[4]pyrrole 56. Preliminary results from mass spectroscopy show that calix[4]pyrrole 62b could bind the chloride anion. Secondly, we tried to synthesize bis-calix[4]pyrrole bearing a biisoxazoline spacer by using bishydroximoyl chloride 61a-b and allylcalix[4]pyrrole 56. Surprisingly, we did not get the desired bis-calix[4]pyrrole 63a-b, but obtained an unexpected macromolecule 64. Compound 64 is a product of a 1,3-dipolar cycloaddition on the one side and an electrophilic substitution of pyrrole ring on the other side. The final part of this thesis describes the synthetic route for the calix[4]pyrrole derivative 65 containg azophenol chromophore. By UV-Vis spectroscopy technique, we had a rough understanding about the anion-binding behaviors of 65. In all of the tested halogen anions (F‾, Cl‾, Br‾ and I‾), only the fluoride anion shows the remarkable changes in the UV-Vis spectra of 65 in chloroform. And we are continuing to investigate the physical and binding properties of this modified calix[4]pyrrole.