| Summary: | 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。
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