1-烷基醚化-3-甲氧基苯甲酸酯化之calix[4]arenes分子內苯甲酸酯基轉移的動力研究

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Title:	1-烷基醚化-3-甲氧基苯甲酸酯化之calix[4]arenes分子內苯甲酸酯基轉移的動力研究 The Study of the Benzoyl-migration Behavior in 1-alkoxy-3-(p-methoxybenzoyl)oxycalix[4]arenes
Authors:	黃鼎評 Huang, Ding-Ping
Contributors:	化學系應用化學碩士班
Keywords:	動力研究苯甲酸酯基轉移 calix[4]arenes
Date:	2013-06
Issue Date:	2014-09-30 18:20:37 (UTC+8)
Abstract:	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的結構，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離子分離、微量金屬檢測及酵素模擬的研究。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之苯甲醯基及1-苯甲基-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，可聚合成黃綠色的前驅物。此前驅物在二苯醚的迴流下，可被轉換為p-tert-butylcalix[4]arene；環狀聚合產物上的對位三級丁基，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)。根據本實驗室過去的研究中發現，calix[4]arene與適量的甲醇鈉及鹵化烷類在乙腈中迴流，可一步合成出一系列單烷基醚化之calix[4]arenes (27-31)；這些單烷基醚化之calix[4]arenes再與不同種類的單苯甲酸醯氯進行酯化時，可分別得到一系列的1-單烷基醚化-3-苯甲酸酯化calix[4]arenes(32-35)。而這一類1-單烷基醚化-3-苯甲酸基酯化calix[4]arenes(32-35)，可在鹼性條件下，被轉換成1-單烷基醚化-2-苯甲酸基酯化calix[4]arenes(36-39)。因此，本論文最終的目的便是在K2CO3的鹼性條件下，探討對化合物32-35之下緣苯甲酸酯基的轉移反應的動力學研究，並利用1H-NMR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 and 1-benzyloxy-3-benzoyloxy- calix[4]arenesystems. In the present of a base, p-tert-butylphenol and formaldehyde were polymerized to form a yellowish precursor. Refluxing the precursor in diphenyl ether yielded the p-tert-butylcalix[4]arene. The p-tert-butyl groups were then removed via AlCl3-catalyzed reverse Friedel-Crafts reaction to give the calix[4]arene (6). In our earlier studies, we have noticed that in the present of sodium methoxide,the the calix[4]arene can be converted to monoalkyloxycalix[4]arenes (27-31) by refluxing with different kind of alkyl halides in acetonitrile. Esterification of the monoalkylated calix[4]arenes (27-31) with excess of benzoyl chloride or p-substituted benzoyl chlorides in pyridine produced the corresponding 1-alkoxy-3-benzoyloxycalix[4]arenes (32-35). The 1-alkoxy-3-benzoyloxycalix[4]arenes (32-35) were then conrected to 1-alkoxy-3-benzoyloxycalix[4]arenes(36-39) under basic condition. The kinetic property of the benzoyl-migration was investigated, and the benzoyl-migrated products were isolated and characterized by 1H-NMR
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