偶氮Calix[4]arenes與含芳香Isoxazoline取代的Calix[4]arenes之合成研究

Abstract

在超分子化學領域裡calix[4]arenes一直被慣用為主體分子，而本論文主要分為四部份，分別敘述關於calix[4]arenes上下緣做不同修飾之合成研究。首先，合成出含發色基團之calix[4]arenes衍生物56-57，其下緣為三個酯基是用來鉗合金屬，上緣為單取代偶氮基團是為發色團。 第二部份敘述關於含螢光基團之calix[4]arenes衍生物62-64，其合成方法是取下緣含不同數目丙烯基取代之calix[4]arenes為起始物和具有不同螢光基團取代之hydroximoyl chloride衍生物，進行1,3-偶極環化加成反應以得到下緣具有螢光基團的isoxazolinomethyl- calix[4]arenes。 第三部份敘述關於calix[4]arenes上緣或下緣分子內架橋之合成研究，我們利用雙偶極化合物與丙烯基進行1,3-偶極環化加成反應。合成方法為取雙親偶極化合物(25,27-diallyloxy-26,28-dihydroxycalix[4] -arene 5，5,17-diallyl-25,26,27,28-tetrahydroxycalix[4]arene 54)和雙偶極化合物(tetrephthaldinitrile oxide，isophthaldinitrile oxide)反應，主要得到1:1環化加成產物(65-66)。 最後我們嘗試合成calix[4]arenes上緣或下緣分子間架橋之合成研究。合成設計為取上緣或下緣單取代丙烯基之calix[4]arenes為起始物和雙偶極化合物( tetrephthaldinitrile oxide)，進行1,3-偶極環化加成反應，預期得到含兩個calix[4]arenes巨分子衍生物(67及69)。很意外地，我們並未得到calix[4]arenes上緣分子間架橋之化合物67，反而是得到calix[4]arenes上緣分子內架橋之化合物68。

Calix[4]arenes have been extensively used as hosts in supramolecular chemistry. This thesis reports four synthetic routes for the modification of calix[4]arenes on upper or lower rims to provide new hosts for inclusion complex studies. The first part of this thesis is focussed on the synthesis of chromogenic calix[4]arenes 56-57 , where the lower rim of calix[4]arene was modified with triester group for metal binding and the upper rim was attached with a azophenol chromophore. The second part of this thesis describes the synthesis of fluorogenic calix[4]arenes 62 and 64. Starting with various substituted allyl groups on the lower rim of calix[4]arenes, isoxazolinomethylcalix[4]arenes with different fluorecent groups were synthesized through 1,3-dipolar cycloaddition reaction. The third part of the thesis is focused on the synthesis of calix[4]- arenes with intramolecular bridge at their upper-rim or lower-rim. Our synthetic strategy for novel compounds 65-66 is based on the double 1,3- dipolar cycloaddition reactions between bifunctional dipoles and bifunctional dipolarophiles. In the reactions of divinyl dipolarophiles (25,27-diallyloxy-26,28-dihydroxycalix[4]arene 53 and 5,17-diallyl-25, 26,27,28-tetrahydroxycalix[4]arene 54) with bifunctional dipoles (tetrephthaldinitrile oxide, isophthaldinitrile oxide), the 1:1 double cycloadducts (65-66) were obtained as major products. Finally we tried to synthesize calix[4]arenes with intermolecular bridge at the upper-rim or lower-rim. The 1,3-dipolar cycloaddition reaction of mono allyl group on the upper rim or lower rim of calix[4]- arenes with bifunctional dipoles (tetrephthaldinitrile oxide), would expect to give macromolecules (67 and 69) which consists of two calix[4]arenes. Unexpectedly, we obtained a macromolecule 68 with intramolecular bridge at the upper-rim.