The synthesis of 5,17,25,26,27,28-Hexahysroxycalix[4]arene

• Main Authors: Yang, ker-ming, 顏克明
• Other Authors: Lin Lee-Gin
• Format: Others
• Language: zh-TW
• Published: 1998
• Online Access: http://ndltd.ncl.edu.tw/handle/35758918768123222977

碩士 === 中國文化大學 === 應用化學研究所 === 86 === Calixarenes, 為一種酚和甲醛的環狀聚合物, 因為其含有分子內中空, 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", 此 一特性可應用於酵素模擬的研究。本論文主要的目的在合成出部份對位含 有羥基的 calix[4]arene, 並期望進一步的發展出另一種對 calixarenes 對位進行官能基化之合成途徑。 p-tert-Butylphenol 和聚甲醛在鹼催化 下可聚合成黃綠色之聚合前驅物, 而此一前驅物於二苯醚中迴流便被轉換 成 p-tert-butylcalix[4]arene; 此環狀聚合物上的對位三級丁基可利用 三氯化鋁 (AlCl3) 以反向的 Friedel-Crafts 反應移除, 而得到對位無 取代的 calix[4]arene。將 calix[4]arene 和 benzoyl chloride 在不 同的反應條件下, 可分別得到 tribenzoate 24, syn-1,3-dibenzoates 25, 和 anti-1,3-dibenzoates 26; 然後利用ClO2 將化合物 24, 25 氧 化成相對應之 calix[4]quinones 27 和 28 的苯甲酸酯類衍生物; 接著 利用乙二醇及 p-TsOH 將化合物 27 和 28 轉換成部份保護之 calix[4 ]quinone ethylene ketals 30 和 31 苯甲酸酯類衍生物; 化合物 30 和 31 在鹼的催化下, 可進行苯甲酸酯基的水解, 而得到部份酮基被保護之 calix[4]quinone-ethylene ketals 33 和 34。 化合物 33 可先進行 NaBH4 還原再加以酸水解 ketal 或先酸水解 ketal 再以 NaBH4 還原, 而得到對位單羥基之 p-monohydroxycalix[4]arene (37); 而化合物 34 僅能以酸水解 ketal 再以 NaBH4 還原的方式, 而得到對位雙羥基之 p- dihydroxy-calix[4]arene (39)。 本論文各步驟之產物的合成及其 1H- NMR 和 FAB-MS 之光譜鑑定均有詳細的說明。 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 the "host-guest complexes"。 This phenomenor complexation has been proposed in the enzyme-mimic studies。 The main purpose of this thesis is to study the synthesis of p-hydroxy-calix[4]arenes, and subsequently, to develop a new synthetic method for p- substituted calixarenes。Condensation of p-tert-butylphenol with formaldehyde under basic conditions afforded yellowish precursor, and the precursor were then converted to p-tert- butylcalix[4]arene by refluxing in diphenyl ether。 The tert- butyl group of p-tert-butylcalix[4]arene was removed via reverse Friedel-Crafts reaction to yield the parent calix[4]arene in moderate yield。 Treatment of calix[4]arene with benzoyl chloride under different conditions produced tribenzoate 24, syn-1,3- dibenzoate 25, or anti-1,3-dibenzoate 26。 These benzoates 24 and 25 were easily oxidized with ClO2 and gave the corresponding calix[4]quinones 27 and 28。 The "upper rim" carbonyl moieties were protected with ethylene glycol and produced the partial protected calix[4]quinone-ethylene ketal benzoates 30 and 31, the benzoate moieties were then cleavage under basic conditions to yield the partial protected calix[4 ]quinone-ethylene ketals 33 and 34。NaBH4 reduction following with acidic hydrolysis of ketal or vice versa would convert the calix[4]monoquinone monoethylene ketal 35 into p-mono- hydroxycalix[4]arene (37) 。 Whereas, p-dihydroxycalix-[4]arene (39) prepared by acidic hydrolysis and following with NaBH4 reduction。 All products which prepred in this thesis were characterized by 1H-NMR and FAB-MS, and the synthetic procedure were also discussed in detail。