Title: 含芳基 Isoxazoline 取代的Calix[4]arenes
Synthesis of Aryl-Isoxazoline substituted Calix[4]arenes
Authors: 張來昌
Lai Chong Zhang
Wen Sheng Chung
Keywords: 雜環化合物;螢光;isoxazoline;calix[4]arene
Issue Date: 2000
Abstract: 利用上緣或下緣不同數目丙烯基取代calix[4]arenes為起始物和具有不同螢光基團取代 hydroximoyl chloride 衍生物進行 1,3 偶極環化加成反應以得到在上緣或是下緣具有螢光基團的 isoxazolinocalix[4]arenes。 在這一系列的反應中,除了化合物 24b 能得到雙取代的產物外,其餘皆因為立體障礙的因素而只能得到單取代的化合物。 Monoisoxazolinomethylcalix[4]arene 與金屬離子錯合物的紫外/可見光光譜分析,我們發現化合物 22b、23b 對多種金屬離子具有萃取的效果;而化合物22b 在鉗合銫離子或鉻離子後螢光強度大幅增加,化合物 23b 則在鉗合鉀離子後螢光強度衰減。 最後我們嘗試利用照光反應進行 isoxazoline 的開環,不同於使用 Raney-Ni 在開環後得到 β-hydroxyketone,照光反應之後會得到α-imine ketone,官能基的轉換可由紅外線光譜的比較而得知。然而,利用照光反應進行 isoxazolinocalix[4]arene 的開環反應的最佳化條件尚未完成,這是今後必須努力的方向。
Based on the variously substituted allyl groups on the upper rim or lower rim of calix[4]arenes, isoxazolinocalix[4]arenes with different fluorecent groups have been synthesized by the 1,3-dipolar cycloaddition. Only compound 24b is di-isoxazoline substituted whereas others are mono-substituted because of the steric barrier for di-substitution. By the UV-vis spectra analysis , we found that these calix[4]arene derivatives are able to chelate metal ions. The fluorecence of 22b is enhanced after chelating with Cr3+ and Cs+ ions, whereas the fluorecence of 23b decreased after chelating with K+ ion. Finally we tried to explore the ring-opening of isoxazoline reaction by irra- diation. The isoxazoline is believed to have been transformed into α-imine ketone from the evidences provided by IR and Mass spectra data, however, further work is needed to optimize the reaction yield.
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