臺灣博碩士論文加值系統

第一部分，我們合成出上緣具有推電子甲氧基之偶氮芳杯34 及
36。由紫外-可見光吸收光譜初步篩選實驗可得知，下緣修飾有單一
氧乙腈基團之偶氮芳杯34 及 36 在乙腈中皆對於Cr3+ 有很好的選
擇性；而引入醚酯基之34 則顯著的提升了對Ca2+ 的辨識能力。由
NOE、Job Plot 及氫核磁共振光譜滴定等實驗，可推測34 主要藉由
下緣兩個偶氮酚上的羥基，與氧乙腈基團協助對Ca2+ 離子進行一比
一之錯合，而醚酯基也輔助了錯合。並且， 34 與 Ca2+ 離子錯合後
會導致構形產生變化，由原本flattened cone 趨向於cone 構形。由
Benesi-Hildebrand plots 可求得34?杭a2+、34?杭r3+ 和 36?杭r3+ 錯合常數分別為3.7 ?e 104、2.1 ?e 104 及 8.1 ?e 104。
第二部分，我們合成出偶氮酚對位具有拉電子之硝基的偶氮芳杯
38 以及 41。金屬篩選實驗可得知38 在較高極性質子性溶劑系統，
例如CH3CN/CH3OH (v/v = 19:1) 的溶劑系統中，仍然有能力對金屬
進行錯合。而41 則沒有此能力。由氫核磁共振光譜滴定實驗可推
測，偶氮芳杯38 除了下緣兩個偶氮酚上的羥基幫助之外，主要由氧
乙腈基團對Ca2+ 進行錯合，並由醚酯基輔助；對於Ba2+ 則藉由醚
酯基進行錯合，而氧乙腈基團也有所輔助。38?杭a2+、38?朋a2+、41?杭a2+和 41?朋a2+ 之錯合常數分別為7.3 ?e 104、2.9 ?e 104、1.7 ?e 105 及 3.9 ?e103。
第三部分研究，則藉由偶極環化加成反應於芳杯下緣引入C5-單
取代四唑，合成出44。我們有效的提升偶氮芳杯在較高極性質子性，
例如含有甲醇或是水之溶劑系統中，對金屬之篩選能力，並增加芳杯
應用於離子篩選或生化及藥物領域上的潛力。

First of all, 4-(4-methoxyphenyl)azo-coupled calix[4]arenes 34 and 36 were synthesized. UV-vis screening of calix[4]arenes 34 (with ester and oxyacetonitrile) and 36 (with oxypropyl and oxyacetonitrile) with 15 metal ions showed that both of them gave rise to color changes toward
Cr3+ ion, and 34 exhibited good binding ability to Ca2+. According to NOE, Job plot and NMR titration experiments, we proposed that 34 chelated Ca2+ with the helps of both oxyacetonitrile and ester groups, and it moved form flattened cone toward cone conformation upon complexation with metal ion. The Ka of 34?杭a2+, 34?杭r3+ and 36?杭r3+
calculated by Benesi-Hildebrand plots were 3.7 ?e 104, 2.1 ?e 104 and 8.1 ?e104 , respectively.
In the second part, the syntheses of calix[4]arenes with
4-(4-nitrophenyl)azo calix[4]arenes 38 and 41 were carried out. UV-vis screening showed that calix[4]arene 38 exhibited large bathochromic shifts toward Ca2+ and Ba2+ in more polar protic solvent systems, such as CH3CN/CH3OH (v/v = 19:1). Moreover, 41 was deficient in this ability.The 1H NMR titration results suggested that both azophenols and ester/or oxyacetonitrile groups are required in the chromogenic sensing with metal ions. The Ka of 38?杭a2+, 38?朋a2+ , 41?杭a2+ and 41?朋a2+ were 7.3 ?e104, 2.9 ?e 104, 1.7 ?e 105 and 3.9 ?e 103 , respectively.
In the final part, the tetrazole-modified azocalix[4]arenes 44 were synthesized using 1,3-dipolar cycloaddition. We evaluated the metal ion screening abilities of azocalix[4]arenes in more polar protic solvent systems, such as CH3OH or H2O contained solvent systems. The utilities
of calix[4]arenes in biological systems or pharmaceutical studies were improved upon tetrazole substitution.

中文摘要 i
英文摘要 iii
謝誌 v
目錄 vii
圖目錄 ix
式圖目錄 xv
表目錄 xvi
附圖目錄 xvii
化合物對照表 xix
第一章緒論 1
1.1 超分子化學1
1.1.1 超分子化學歷史1
1.1.2 超分子化學發展實例3
1.2 芳杯 6
1.2.1 芳杯簡介6
1.2.2 芳杯發展實例8
1.3 化學感測器11
1.4. 偶氮芳杯於化學感測器之應用15
1.5 四唑簡介 22
第二章研究動機 27
第三章結果與討論29
3.1 含酯基與乙腈基團之偶氮芳杯34 對離子辨
識的研究 29
3.1.1 偶氮芳杯 34 之合成 29
3.1.2 含丙基與乙腈基團偶氮芳杯36 之合成 31
3.1.3 偶氮芳杯 34 與 36 對金屬離子篩選能力之
研究 33
3.1.4 偶氮芳杯 34 對金屬離子錯和能力之研究 36
3.1.5 偶氮芳杯 36 對金屬離子錯和能力之研究 40
3.1.6 偶氮芳杯 34 對金屬離子錯和模式之研究 42
3.1.7 偶氮芳杯 36 對金屬離子錯和模式之研究 49
3.2 含酯基與乙腈基團之偶氮芳杯38 對離子辨識之研究 52
3.2.1 偶氮芳杯 38 與 41 之合成 52
3.2.2 偶氮芳杯 38 與 41 對金屬離子篩選能力之研究 54
3.2.3 偶氮芳杯 38 對金屬離子錯和能力之研究 58
3.2.4 偶氮芳杯 41 對金屬離子錯和能力之研究 61
3.2.5 變換溶劑系統對偶氮芳杯篩選金屬離子能力影響之研究 63
3.2.6 偶氮芳杯 38 對金屬離子錯和模式之研究 69
3.3 含酯基與四唑基團之偶氮芳杯44 對離子辨識之研究 76
3.3.1 偶氮芳杯 44 與45 之合成 76
3.3.2 偶氮芳杯 44 與 45 對金屬離子篩選能力之研究 78
3.3.3 偶氮芳杯 44 對金屬離子錯和能力與模式之研究 82
3.3.4 偶氮芳杯 45 對金屬離子錯和能力之研究 89
第四章結論 90
第五章相關研究與未來工作 92
5.1 雙芳杯之合成研究 92
5.2 芳杯分子結合色胺酸衍生物之研究 96
第六章實驗部分 102
第七章參考文獻 124
第八章附錄 132
簡歷 162

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