臺灣博碩士論文加值系統

本研究主要分為四個研究主題，分別探討上緣偶氮苯或下緣beta-胺基-alpha,beta-不飽和酮基取代的芳杯對於金屬離子的錯合能力。
在第一章中，我們合成出一系列以丙烯基與偶氮苯修飾上緣的芳杯
43、44、45a-b 和 46a-b，探討偶氮苯與丙烯基在芳杯上緣空間上的排列，
對於錯合 Hg2+ 能力的影響。結果顯示偶氮芳杯與 Hg2+ 錯合能力大小為
Ka (42a) > Ka (42b) > Ka (43) > Ka (44) > Ka (45a) > Ka (45b) > Ka (46a) > Ka
(46b)。此結果說明了對位甲氧基取代的偶氮苯與丙烯基在芳杯上緣的排列
方式，採對位雙取代的空間排列對 Hg2+ 的錯合能力較強 (如芳杯42a)。此
外，我們亦利用共振拉曼光譜的實驗，證實偶氮芳杯 43 與 Hg2+ 離子錯
合時，形成了醌?{苯腙的結構。在第二章，我們合成能同時錯合陽離子與陰離子的雙螯合接受器芳杯
74。利用 Mo(CO)6 對下緣 isoxazole 取代芳杯 73 進行開環反應即可得
beta-胺基-alpha,beta-不飽和酮基團取代芳杯 74。利用紫外可見光與螢光光譜探討芳
杯 73 和 74 對金屬離子的錯合能力。芳杯 73 和 74 為對 Cu2+ 有高選擇
性的化學感測器。當加入 Cu2+ 離子時，芳杯 73 的螢光會被淬熄，而芳杯
74 則為螢光增強。從 EPR 的實驗證明， Cu2+ 離子與芳杯 73 和 74 錯
合時，會與苯酚或beta-胺基-alpha,beta-不飽和酮基團發生氧化還原反應，而形成
Cu+ 離子。當芳杯 74 與 Cu+ 錯合後，可協助錯合 F?{ 和CH3COO?{ 離子，
而造成螢光增強效應。在第三章，我們合成芳杯 92b，其下緣取代為beta-胺基-alpha,beta-不飽和酮
和醯胺基團。初步金屬離子篩選結果顯示，芳杯 92b 對 Cu2+、Hg2+ 和
Pb2+ 離子有辨識效果，其中以 Cu2+ 所造成的螢光增強效應最明顯。芳杯
92b 可同時辨識兩當量的 Cu2+，其可能錯合位置推測為 (1) 雙邊的beta-胺基-alpha,beta-不飽和酮基團和 (2) 下緣苯酚與醯胺基間的互相協助。其錯合常數
為 2.02 x 109 M-2。且從 EPR 實驗得知，Cu2+ 會被芳杯 92b 還原成 Cu+。
控制化合物 93 和 96b 對 Cu2+ 的錯合研究亦支持 92b 與 Cu2+ 的可能
iii
錯合模式
在第四章，我們合成了1,3-alternate 構形芳杯 104，分別在下緣修飾beta-胺基-alpha,beta-不飽和酮基和蒽基取代的三唑基團。初步的研究結果顯示，Li+、
Na+ 和 K+ 錯合在beta-胺基-alpha,beta-不飽和酮基位置，而 Pb2+、Cu2+、Hg2+ 和
Cr3+ 等離子不但影響了吸收度的變化，也造成的螢光的淬熄，推測應是beta-胺基-alpha,beta-不飽和酮基和三唑基團兩部分皆有錯合現象。未來，將進行金屬
離子間的競爭效應。並合成控制化合物 109 及 110 比較其與金屬離子間
的錯合效應

In this thesis, we investigated the binding abilities of calix[4]arenes substituted with upper-rim azophenyl groups or lower-rimbeta-amino-alpha,beta-unsaturated ketones toward metal ions.
In chapter 1, we described the synthesis of a series of upper-rim p-allyl- and p-phenylazo substituted calix[4]arenes 43, 44, 45a-b and 46a-b. We expected that these ligands might show some specific stereoselectivity toward Hg2+ ion. The results showed that the binding abilities of calix[4]arenes toward Hg2+ followed the order: Ka (42a) > Ka (42b) > Ka (43) > Ka (44) > Ka (45a) > Ka (45b) > Ka (46a) > Ka (46b). It implied that the two p-methoxyphenylazo and the two p-allyl groups prefered to bind Hg2+ in a distal orientation (such as 42a). Furthermore, the resonance Raman spectrum of 43·Hg2+ supported the formation of quinone-hydrazone tautomer.
v
In chapter 2, we reported a new ditopic calix[4]arene receptor 74 for the
simultaneous complexation of anionic and cationic species. The host molecule
73 was synthesized first, followed by Mo(CO)6 mediated ring–opening reaction
which gave the target receptor calix[4]arene 74. The binding properties of
ligands 73 and 74 in acetonitrile toward metal ions were investigated by UV?{vis
and fluorescence spectroscopies. The results showed that both ligands 73 and
74 were highly selective to recognize Cu2+ ion. Upon titration with Cu2+, the
fluorescence of 73 was severely quenched, whereas, 74 showed a strong
fluorescence enhancement. According to EPR experiments, the Cu2+ was
reduced to Cu+ by the free phenolic?{OH or beta-amino-alpha,beta-unsaturated keton,
during the complexation of 73 and 74 with Cu2+. Ditopic behaviour was
observed for the complex 74·Cu+ which showed further enhancement on its
fluorescence intensity upon complexation with anions such as acetate or
fluoride.
In chapter 3, we synthesized a Cu2+ induced fluorescence turn-on sensor,
calix[4]arene 92b, which contains amide groups linkedbeta-amino-alpha,beta-unsaturated ketone units with naphthalene pendant as the fluorophore. Calix[4]arene 92b
can recognize Cu2+, Hg2+ and Pb2+, in which Cu2+ induced a remarkable
fluorescence enhancement. The binding ratio between 92b and Cu2+ was 1:2,
and the two possible binding sites for Cu2+ in 92b were conjectured to be: (1) at
vi
the low-rim phenolic-OH and amide groups, and (2) at the
beta-amino-alpha,beta-unsaturated ketones. The association constant (Ka) of the 1:2
complex 92b·2Cu+ was calculated to be 2.02 × 109 M-2. Futhermore,
according to EPR experiments, the Cu2+ was reduced to Cu+ by the free
phenolic?{OH and beta-amino-alpha,beta-unsaturated ketone, during the complexation of
92b with Cu2+. The binding studies of control compounds 93 and 96b toward
Cu2+ also supported the proposed binding mode of 92b with Cu2+.
In chapter 4, we report the synthesis of a chemosensor based on
1,3-alternate calix[4]arene 104 containing two different cationic binding sites,
constructed by anthrylmethyl-triazole and β-amino-α,β-unsaturated ketone
groups. Preliminary studies of UV-vis and fluorescence measurements on 104
toward metal ions showed that Li+, Na+ and K+ might be bound with
β-amino-α,β-unsaturated ketone, whereas Pb2+, Cu2+, Hg2+ and Cr3+ might be
bound with triazole and/or β-amino-α,β-unsaturated ketone. In the future, we
will also investigate the allosteric effect of 104 for metal ions by UV-vis,
fluorescence, and 1H NMR spectroscopy. The control compounds 109 and 110
will be synthesized for comparison.

中文摘要................................................................................................................ i
Abstract................................................................................................................. iv
謝誌....................................................................................................................viii
目錄...................................................................................................................... ix
圖目錄................................................................................................................xiv
Chart 目錄........................................................................................................ xxv
式圖目錄........................................................................................................xxviii
表目錄..............................................................................................................xxix
式目錄............................................................................................................... xxx
附圖目錄..........................................................................................................xxxi
化合物對照表................................................................................................xxxix
第一章上緣丙烯基與對位甲氧基偶氮苯取代芳杯之合成及其對汞離子之感測研究............................................................................................................... 1
1-1 緒論.......................................................................................................... 1
1-1-1 芳杯(Calixarene) 簡介.................................................................. 1
1-1-2 化學感測器(Chemosensor) 的設計.............................................. 4
x
1-1-3 芳杯於化學感測器的應用.............................................................. 5
1-1-4 偶氮芳杯的特性.............................................................................. 6
1-1-5 偶氮芳杯於化學感測器之應用?{?n偶氮作為發色基團的相關研究....................................................................................................................... 8
1-1-6 偶氮基團於感測器之應用?n?{?n作為金屬螯合基的相關研究....... 14
1-2 研究動機................................................................................................ 21
1-3 結果與討論............................................................................................ 21
1-3-1 偶氮芳杯43、44、45a-b和46a-b對Hg2+之錯合研究............ 24
1-3-2 偶氮芳杯43 和 45a 對 Hg2+ 氫核磁共振光譜滴定實驗...... 28
1-3-3 測試偶氮芳杯在酸性條件下的紫外可見光光譜變化................ 31
1-3-4 偶氮芳杯43加入Hg2+ 離子之拉曼光譜測量............................ 34
1-3-4-1 拉曼光譜技術(Raman spectroscopy) .................................... 34
1-3-4-2 拉曼儀器設備........................................................................... 35
1-3-4-3 偶氮芳杯之拉曼光譜實驗...................................................... 36
1-3-5 鄰位雙偶氮芳杯44對於Ag+ 離子的滴定實驗.......................... 44
1-3-6 下緣雙醚酯之偶氮芳杯47 的金屬離子錯合研究...................... 46
1-4 結論........................................................................................................53
第二章下緣 ??n-胺基-?n??z??n-不飽和酮取代芳杯之合成及其選擇性辨識Cu2+ 與協助錯合陰離子之研究........................................................................ 55
xi
2-1 緒論........................................................................................................55
2-1-1 螢光基團於芳杯上的應用與其相關機制.................................... 55
2-1-2 芳杯於變構效應(Allosteric Effect)的應用................................. 61
2-1-3 芳杯於異種雙位接收器(heteroditopic receptor) 的研究.......... 67
2-1-4 1,3-偶極環化加成反應與isoxazole之開環反應......................... 72
2-2 研究動機................................................................................................ 75
2-3 結果與討論............................................................................................ 77
2-3-1 具??{胺基?{??z??{不飽和酮基取代之芳杯74與控制化合物77之合成................................................................................................................. 77
2-3-2 芳杯73、74 與控制化合物76、77 之螢光特性.................... 78
2-3-3 芳杯73 和 74 對金屬離子的篩選實驗.................................... 79
2-3-4 芳杯73 和 74 對 Cu2+ 離子的滴定實驗................................. 80
2-3-4-1 紫外-可見光吸收光譜與螢光光譜滴定實驗......................... 80
2-3-4-2 氫核磁共振光譜滴定實驗...................................................... 84
2-3-4-3 電子順磁共振(Electron Paramagnetic Resonance) 光譜實驗................................................................................................................... 86
2-3-5 芳杯74 與 Cu2+ 離子錯合後的雙螯合研究............................. 87
2-3-6 芳杯74 與 Cu2+ 和陰離子可能錯合模式................................. 90
2-3-7 控制化合物77 與 Cu2+ 離子錯合研究以及其雙螯合研究..... 91
2-3-8 芳杯73、74 與 77 對 Cu+ 離子錯合研究.............................. 94
xii
2-3-9 芳杯79 之合成及其與Cu2+ 離子錯合研究............................. 95
2-4 結論........................................................................................................98
第三章下緣含醯胺基與 ??胺基-??z?n??{不飽和酮基取代芳杯之合成及其雙螯合特性感測研究............................................................................................. 99
3-1 研究動機................................................................................................ 99
3-2 結果與討論.......................................................................................... 101
3-2-1 目標化合物92a-c 與控制化合物93 和 96a-b 之合成....... 101
3-2-1-1 Aryl amines 87a-c 和 89 之合成......................................... 101
3-2-1-2 芳杯92a-c 與控制化合物93 和 96a-b 之合成.............. 103
3-2-2 芳杯92a 的氫譜訊號標定........................................................ 104
3-2-3 芳杯92a 的結構特性探討........................................................ 108
3-2-3-1 溶劑效應................................................................................. 109
3-2-3-2 溫度效應................................................................................. 111
3-2-4 芳杯92b 對金屬離子初步篩選實驗.........................................113
3-2-5 芳杯92b 對Cu2+、Hg2+ 和 Pb2+ 的滴定實驗........................115
3-2-5-1 芳杯92b 對 Cu2+ 的滴定實驗........................................... 115
3-2-5-2 控制化合物93 和 96a-b 對 Cu2+ 的滴定實驗 ............... 122
3-2-5-3 芳杯92b 對 Hg2+ 的滴定實驗........................................... 129
3-2-5-4 芳杯92b 對 Pb2+ 的滴定實驗 ........................................... 134
xiii
3-3 結論...................................................................................................... 139
第四章 合成具有 ??{胺基?{??z?n??{不飽和酮與三唑取代之1,3-alternate 構形芳杯及其初步金屬離子篩選結果............................................................... 142
4-1 研究動機.............................................................................................. 142
4-2 結果與討論.......................................................................................... 144
4-2-1 合成步驟...................................................................................... 144
4-2-2 芳杯104 對金屬離子的初步篩選實驗.................................... 149
第五章實驗部分........................................................................................... 153
5-1 試藥及測試方法.................................................................................. 153
5-2 實驗合成步驟及光譜資料.................................................................. 155
第六章參考文獻…………………………………………………………...184
第七章 附圖................................................................................................... 197
第八章附錄................................................................................................... 284
化合物46a、52、73和74之ORTEP圖與晶體參數................................. 284

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