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，進而形成"主-客化合物"，這一個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。
在早期文獻中，calix[4]arene 下緣單取代、1,3-對位雙取代、三取代和四取代醚化衍生物，都曾被報導過，但1,2-鄰位雙醚化的化合物，直至數年前才被本實驗室經由多步合成法製備出。在製備的過程中發現，1-單烷基醚化-3-苯甲酸酯化calix[4]arenes 在鹼中進行第二醚化反應時，苯甲酸酯基會轉移至相鄰的苯酚上，因此本實驗室便開始探討1-單烷基醚化-3-苯甲酸酯化calix[4]arenes 轉位的研究，而本論文則專注於1-單苯甲基醚化-3-苯甲酸酯化calix[4]arene轉位的研究。
對位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。而此一環狀聚合產物的對位三級丁基，可利用反向的 Friedel-Crafts 反應進行減除，得到對位無取代之calix[4]arene。
根據本實驗室過去研究的發現，calix[4]arene 與適量的甲醇鈉及苯甲基溴在乙腈中迴流，可一步合成出單苯甲基醚化之 calix[4]arene；如將單苯甲基醚化之 calix[4]arene 與 benzoyl chloride 或對位取代的 benzoyl chlorides 進行酯化反應時，可得到1-苯甲基醚化-3-苯甲酸酯化calix[4]arene 或其相對酯化產物。而這一類1-苯甲基醚化-3-苯甲酸酯化calix[4]arene，可在 K2CO3 與乙腈迴流的條件下，被轉換成1-苯甲基醚化-2-苯甲酸酯化的 calix[4]arene。
本論文除了將分離及鑑定出在 K2CO3 的條件下， 1-苯甲基醚化-3-苯甲酸酯化calix[4]arene的轉移產物外，另將同時利用1H-NMR來檢測1-苯甲基醚化-3-苯甲酸酯化 calix[4]arene 分子中苯甲酸醯基的轉移。
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”.
In the literature, four different kinds of calix[4]arene ether derivatives (monoalkoxy-, 1,3-dialkoxy-, trialkoxy-, and tetra- alkoxycalix[4]arenes) had been reported. To achieve the preparation of last set of calix[4]arene ether derivative (1,2-dialkoxycalix[4]arenes), a multi-step synthesis route was developed by this laboratory. An unexpecting benzoyl-migration phenomenon was observed during the preparation of 1,2-dialkoxycalix[4]arene, and the investigation of benzoyl-migration was performed in this thesis.
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.
The calix[4]arene monobenzyl ether was prepared by refluxing calix[4]arene with sodium methoxide and benzyl bromide in acetonitrile, and the esterification of the benzyl ether product with p-nitrobenzoyl chloride yielded the 1-benzoyloxy-3-(p-nitrobenzoyl)oxycalix[4]arene. 1-benzoyloxy-3-(p-nitrobenzoyl)oxycalix[4]arene was then converted to 1-benzoyloxy-2-(p-nitrobenzoyl)oxycalix[4]arene under basic condition.
Purification and characterization of 1-benzoyloxy-2-(p-nitrobenzoyl) oxy-calix[4]arene will be reported in this thesis. The 1H-NMR spectroscopy will also be applied to study the benzoyl-migration.
