| 摘要: | calixarene，為一種酚與甲醛的環狀聚合物，因其分子內具有杯型中空之結構，故可以嵌合一些小型的有機分子或金屬離子，而形成"主-客化合物"，其特性可推廣應用於微量金屬檢測、離子分離及酵素模擬的研究；本論文主要目的為探討一系列1-乙基-3-苯甲醯基酯化calix[4]arenes之苯甲醯基轉位的研究。
三級丁基酚和甲醛在鹼性的催化下，可聚合成黃綠色的聚合物，我們稱此種化合物為前驅物。此前驅物可在二苯醚的迴流下，被轉換為p-tert-butylcalix[4]arene；此環狀聚合物的對位三級丁基可利用三氯化鋁進行反向的 Friedel-Crafts 反應，進行減除而得到對位無取代之 calix[4]arene(6)。
根據本實驗室在過去的研究中發現，calix[4]arene與過量的不同鹵化烷類及甲醇鈉在乙腈中迴流，可一步合成出一系列單烷基醚化之 calix[4]arenes (25-29)；這些單烷基醚化之calix[4]arenes進行不同種類的單苯甲酸酯化時，可分別得到一系列的1-單烷基醚化-3-苯甲醯基酯化calix[4]arenes (30-34)、(35-39)、(40-44)。
因此，本論文最終的目的便是對化合物 (30、35、40)在K2CO3的鹼性條件下，探討其下緣苯甲酸酯基之轉移反應的動力學研究，並分離及利用1H-NMR、13C-NMR和COSY來鑑定出轉移後的產物。
Calixarenes, which are cyclic oligomers of p-substituted phenols and formaldehyde, are able to include small organic molecules or metal ions within molecular cavities to form the “host-guest complexes”. This phenomenon has been proposed in the research area of micro-analysis detection devices, ion separation, and enzyme-mimic studies. The main purpose of this thesis is to study the benzoyl-migration behavior in 1-ethoxy-3-benzoyloxycalix[4]arenes systems.
In the present of a base, p-tert-butylphenol and formaldehyde were polymerized to form a yellowish precursor. By refluxing of this precursor in diphenyl ether yielded the p-tert-butylcalix[4]arene. The p-tert-butyl groups were then removed by AlCl3-catalyzed that will follow a reverse Friedel-Crafts reaction to give a para calix[4]arene(6).
In our earlier studies on the series of calix[4]arene, we have noticed that in the present of sodium methoxide as the reacting base. The monoalkylated calix[4]arenes can be prepared by refluxing of calix[4]arene with different kind of alkyl halides in acetonitrile yielded monoalkylate claix[4]arenes as the main products (25-29).
Esterification of those monoalkylated calix[4]arenes (25-29) with an excess of benzoyl chloride in pyridine produced the corresponding 1-alkoxy-3-benzoyloxycalix[4]arenes (30-34)、(35-39)、(40-44) . There- fore, the final purpose of this studies is those products under basic condit- ion to study its kinetic transformation of benzoyl and then after separation, by using 1H-NMR,13C-NMR and COSY to identify those products. |
