| 摘要: | Calixarenes，為一種酚和甲醛的環狀聚合物，因為其具有分子內中空，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”，而這一種特性應可推廣應用於微量檢驗，離子分離及酵素模擬的研究；而本論文主要的目的首先是合成出一系列 1,3-雙烷基醚化的 calix[4]arenes，接著利用 ClO2 的氧化能力，來製備出一系列 1,3-雙烷基醚化的 calix[4]diquinones；本論文進一步的進行雙乙基醚化之氧化的動力學研究，並期望藉由雙乙基醚化之calix[4]arenes 進行苯甲酸單一酯化，再進行氧化的實驗，最終水解；藉由此最終產物與1-3 diethoxycalix[4]diquinones的差異進行比較。
p-tert-Butylphenol 和甲醛在鹼催化下可聚合成黃綠色之聚合前驅物 26，此一聚合前驅物於二苯醚 (diphenyl ether) 中迴流可被轉換成 p-tert-butylcalix[4]arene (1)；而此環狀聚合物上的對位三級丁基可再利用三氯化鋁 (AlCl3) 作為催化劑，以反向的 Friedel-Crafts 反應移除，而得到對位無取代之 calix[4]arene (6)。
依據文獻報導，calix[4]arene 和多量的鹵化烷類及 K2CO3 在 CH3CN 中迴流，可得到高產率的 1,3-雙烷基醚化之 calix[4]arenes；而本論文則採用了碘化乙烷 (iodoethane)，碘化正丙烷 (1-iodopropane)，碘化正丁烷 (1-iodobutane)，溴化甲苯 (benzyl bromide)，和溴化丙烯 (allyl bromide) 等五種鹵化烷類，來製備出相
對應的 25,27-diethoxy-26,28-dihydroxycalix[4]arene (27)、25,27-di-
propoxy-26,28-dihydroxycalix[4]arene (28)、25,27-dibutoxy-26,28-di-
hydroxycalix[4]arene (29)、25,27-dibenzyloxy-26,28-dihydroxycalix[4]-
arene (30) 及 25,27-diallyloxy-26,28-dihydroxycalix[4]arene (31)。
本實驗室曾成功的利用 ClO2 將雙烷基醚化的 calix[4]arenes 氧化成為相對應的 calix[4]quinones，本論文亦利用相同的 ClO2 氧化特性，來對雙烷基醚化之 calix[4]arenes 進行氧化。其中發現乙基醚的官能團能經由亞甲基之單鍵向環內作翻轉，而得到syn-25,27-diethoxy-26,28-calix[4]diquinone (32) 和anti-25,27-diethoxy-
26,28-calix[4]diquinone (33) 之外，其餘的氧化反應均只能得到其相對應之 25,27-dipropoxy-26,28-calix[4]diquinone (34)、25,27-dibutoxy-
26,28-calix[4]diquinone (35)、25,27-dibenzyloxy-26,28-calix[4]di-
quinone (36) 及 25,27-diallyloxy-26,28-calix[4]diquinone (37)。
因此本論文將探討雙乙基醚化之calix[4]diquinones的動力學研究，利用1HNMR的光譜測量來計算syn組態與anti組態的百分比，並利用動力學一級反應的公式 (a0/xe)ln(xe/xe-x)=k1t 計算出在CDCl3與C5D5N的 K1值.
Calixarenes, which are cyclic oligomers of p-substituted phenols and formaldehyde, are able to include small organic molecules or metal ions within the molecular cavities to form ‘‘ host-guest ’’ complexes. These phenomena have been proposed in the applications of micro-analysis, ion separation, and enzyme-mimic studies. The main purpose of this thesis is to synthsis 1,3-diethoxycalix[4]diquinones and study its kinetic。
p-tert-Butylphenol and formaldehyde was polymerized, in the presence of a base, to form an yellowish precursor 26. Refluxing of this precursor in diphenyl ether yielded the p-tert-butylcalix[4]arene (1). The p-tert-butyl groups were then removed with AlCl3 by reverse Friedel-Crafts reaction to give the parent calix[4]arene (6).
Literature reported that calix[4]arene was dialkylated by refluxing with alkyl halides and potassium carbonate in acetonitrile for 4 hours. Five alkyl halides (iodoethane, 1-iodopropane, 1-iodobutane, benzyl bromide, and allyl bromide) were selected in this thesis, and the corresponding syn-1,3-dialkoxycalix[4]arenes 27, 28, 29, 30 and 31 were prepared.
The chlorine dioxide oxidation was performed on these 1,3-dialkylated calix[4]arenes, and except for the case of diethoxy-
calix[4]arene, which afforded syn- and anti- stereoisomers of diethoxy-
calix[4]diquinones 32 and 33, the other dialkoxycalix[4]arenes yielded the corresponding calix[4]diquinones 34, 35, 36 and 37.
The main purpose of this thesis is to study the kinetic of 1,3-diethoxycalix[4]diquinones and use 1H-NMR to calculate proportion of syn-32 and anti-33，and used first order of kinetic formula to calculate
K1。
All of the products were characterized by 1H-NMR, 13C-NMR, COSY, FAB-MS, and EA. |
