臺灣博碩士論文加值系統

近年來，將芳杯衍生物運用於形成超分子凝膠之研究備受重視，因為可進行離子辨識、漏油回收等工作，但其大多為單組成凝膠。直至2007年，才出現有關芳杯衍生物之雙組成凝膠，其中，以鹵素鍵作為分子間作用力的例子極少。本篇論文利用點擊化學反應，合成出含三唑吡啶單取代芳杯衍生物33，並發現此化合物可於乙醇中形成單組成凝膠，其最低凝膠濃度為30 mM。
我們將芳杯衍生物33作為主體分子，與雙、參羧酸基或雙、參碘基取代之芳香族衍生物G1~G5，於乙醇中進行混合，發現透過不同的分子間作用力，不但形成具有奈米級試管形貌之氫鍵雙組成凝膠，更能形成具有纖維狀、層狀之鹵素鍵雙組形凝膠。除了可與芳香族分子形成雙組成凝膠外，我們將芳杯衍生物33與16種過氯酸金屬混合，發現於乙醇中可與鈣、汞、鋰、鈉離子，分別形成不同形貌之金屬誘導雙組成凝膠，依序為柱狀、細長型纖維狀、頭尖尾粗型纖維狀與含有奈米試管之柱狀。其中，更以含重金屬33-Hg2+凝膠可達到大幅降低芳杯衍生物33之最低凝膠濃度，由濃度為30 mM降至6 mM，且此凝膠透過ICP-MS分析得知，可有效除去乙醇中高達99.6%之汞離子。
另外，針對本實驗室合成出的螢光膠體化合物27，我們計畫將此化合物之上緣修飾較長的碳鏈，透過碳鏈長短來控制其球體形貌之凝膠直徑大小。在合成過程中，發現化合物44之純化是有困難的，雖然可在混合物中，取得化合物44之單晶，但發現此單晶化合物的1H NMR光譜依然如反應之產物複雜。我們取此44進行後續下緣之丙炔醚化及雙1,3-偶極環化加成反應，在以薄膜色層分析追蹤時，發現其產物皆為混合物，因此，未來仍須找出純化之條件。

In recent years, calix[4]arene derivatives have been extensively studied in supramolecular gel formation. Although they can be used in ions recognition and oil spill recovery, they usually form one component gels. Two component gel formation of calix[4]arene was not known until Prof. Zheng’s work published in 2007. It worth noting that there have been few reports on using halogen bonding as intermolecular forces for gel formation. In this thesis, we used click chemistry reaction to synthesize triazolyl-pyridyl substituted calix[4]arene derivatives 33 , which was found to form a one component gel in ethanol and it minimum gelation concentration was determined to be 30 mM.
Using calix[4]arene derivatives 33 as host and dicarboxyl, tricarboxyl, diiodo, or triiodo substituted aromatic derivatives in ethanol as bridge, we found that they formed two component gel through different intermolecular interactions. The morphology of hydrogen bonding-triggered two component gel can be nanotube, fiber or rod; whereas halogen bonding-triggered two component gel can be fiber or sheet. In addition to the two component gel with aromatic derivatives, they could also form metallogels when compound 33 mixed with calcium, mercury, lithium and sodium ions in ethanol. The morphology of these metallogels were found to be rod, slender fibrous, stubby-type fibrous and nanotubes. Substantially lower the minimum gelation concentration of compound 33 can be achieved which decreased from 30 mM to 6 mM. As analyzed by ICP-MS, the two component gelation of 33 with Hg2+ can effectively remove the mercury content in ethanol by 99.6%.
In addition, we wish to modify the upper rim of 27 by substituting the t-butyl by isoaryl group so that it can control the diameter of the micro spherical gels. During the synthesis, we found that compound 44 was difficult to be purified. Although we could obtain a single crystal from the reaction, we could not understand why its 1H NMR spectrum was still complicated. We used the mixture 44 to further functionalize it to propargloxy calix[4]arene 45 and subsequent bis-1,3-dipolar cycloaddition reaction to get 49; however, we found that they are still mixtures of compounds based on TLC analysis. We need to work on the purification
procedures of compound 44 in the future.

中文摘要 I
ABSTRACT IV
目標分子結構對照表 VIII
圖目錄 XIII
式目錄 XIX
表目錄 XX
附圖目錄 XXI
1. 緒論 1
1.1 超分子化學簡介 1
1.2 芳杯簡介 1
1.2.1 芳杯的構形 3
1.2.2 芳杯之應用 4
1.3 凝膠簡介 5
1.3.1 雙組成凝膠文獻探討 10
1.3.1.1 氫鍵觸發雙組成凝膠 14
1.3.1.2 鹵素觸發雙組成凝膠 21
1.3.1.3 金屬離子誘導雙組成凝膠 25
1.3.2 芳杯凝膠文獻探討 30
2 研究動機 41
3 雙組成凝膠33之結果與討論 43
3.1 芳杯衍生物合成與結構鑑定 43
3.1.1 下緣單炔基取代芳杯化合物29之合成 44
3.1.2 4-Azidopyridine 32之合成 44
3.1.3 下緣單取代芳杯衍生物33之合成與結構鑑定 45
3.1.4 Pyridine-4-carbaldoximidoyl chloride 36之合成 48
3.1.5 下緣單取代芳杯衍生物37之合成 49
3.1.6 控制化合物40與41之合成 52
3.2 下緣單取代芳杯衍生物之性質分析 55
3.2.1 下緣單取代芳杯化合物之單組成凝膠性質測試 55
3.2.1.1 超分子凝膠分子33之SEM形貌分析 57
3.2.2 含下緣單取代芳杯化合物33之氫鍵觸發雙組成凝膠 60
3.2.2.1 氫鍵觸發雙組成凝膠之SEM分析 62
3.2.2.2 氫鍵觸發雙組成凝膠之NMR分析 65
3.2.3 含下緣單取代芳杯化合物33之鹵素鍵觸發雙組成凝膠 70
3.2.3.1 鹵素鍵觸發雙組成凝膠之SEM分析 72
3.2.3.2 鹵素鍵觸發雙組成凝膠之NMR分析 74
3.2.4 芳杯衍生物33與金屬離子之凝膠性質測試 76
3.2.4.1 雙組成有機凝膠SEM分析 78
3.2.4.2 雙組成有機凝膠之NMR分析 80
3.2.4.3 雙組成有機凝膠之ICP-MS分析 82
3.2.5 雙組成凝膠之綜合比較 86
3.2.5.1 芳杯衍生物33與控制化合物之凝膠性質 86
3.2.5.2 雙組成凝膠之SEM分析統整 87
3.2.5.3 雙組成凝膠之HRMS分析 89
3.2.5.4 雙組成凝膠之PXRD分析統整 91
3.3 結論 95
4 雙芳杯衍生物49之結果與討論 97
4.1 雙芳杯衍生物合成與結構鑑定 97
4.1.1 芳杯化合物42之合成 97
4.1.2 芳杯衍生物44之合成 98
4.1.3 下緣單炔基取代芳杯衍生物45之合成 102
4.1.4 化合物 dinitrile oxide 48之合成 103
4.1.5 下緣單橋聯雙芳杯化合物49之合成 104
4.2 結論 105
5 實驗部分 106
5.1 試藥及測試方法 106
5.2 實驗合成步驟及光譜資料 108
5.2.1 5,11,17,23-Tetra(tert-butyl)-25-propargyloxy-26,27,28- trihydroxy calix[4]arene, 30a 108
5.2.2 4-Azidopyridine, 32 108
5.2.3 5,11,17,23-Tetra(tert-butyl)-25-triazolyl-pyridyl -26,27,28- trihydroxy calix[4]arene, 33 109
5.2.4 Pyridine-4-carbaldoxime, 35 110
5.2.5 Pyridine-4-carbaldoximidoyl chloride, 36 111
5.2.6 5,11,17,23-Tetra(tert-butyl)-25- isoxazolyl -pyridyl -26,27,28- trihydroxy calix[4]arene, 37 112
5.2.7 1-tert-Butyl-4-(prop-2-ynyloxy)benzene, 39 113
5.2.8 4-P yridyl [4-tert-butylphenoxy)methyl]triazole, 40 114
5.2.9 5,11,17,23-Tetra(tert-butyl)-25,27-bis(triazolyl-pyridyl) -26,28- dihydroxy calix[4]arene, 41 115
5.2.10 25,26,27,28-Tetrahydroxycalix[4]arene, 42 116
5.2.11 5.11.17,23-Tetrakis(1,1-dimethylpropyl)-25,26.27,28-tetrahydroxycalir[4]arene, 44 117
5.2.12 5,11,17,23-Tetrakis(1,1-dimethylpropyl)-25, 26,27,28-tetra hydroxycalix[4]arene, 45 118
5.2.13 9,10-Dicarboxime-N,N-dihydroxy anthrance, 47 119
5.2.14 9,10-Dicarbonitrile oxide anthracene, 48 119
5.2.15 9,10-Bis-isoxazolyanthryl-methyl linked tetra kis(1,1-dimethyl propyl)biscalix[4]arene, 49 120
6 參考文獻 122

1. Stanley, C. E.; Clarke, N.; Anderson, K. M.; Elder, J. A.; Lenthall, J. T.; Steed, J. W. Chem. Commun. 2006, 3199-3201.
2. Oshovsky, G. V.; Reinhoudt, D. N.; Verboom, W. Angew. Chem., Int. Ed. 2007, 46, 2366-2393.
3. Stone, M. T.; Moore, J. S. J. Am. Chem. Soc. 2005, 127, 5928-5935.
4. Fabbrizzi, L.; Poggi, A. Chem. Soc. Rev. 1995, 24, 197-202.
5. Lehn, J.-M. Science 1993, 260, 1762-1763.
6. Steed, J. W.; Atwood, J. L., Supramolecular chemistry. Wiley: Chichester; New York, 2000.
7. Gutsche, C. D. Acc. Chem. Res. 1983, 16, 161-170.
8. (a) Gutsche, C. D., Calixarenes. Royal Society of Chemistry: Cambridge England, 1989; (b) Gutsche, C. D., Calixarenes revisited. Royal Society of Chemistry: Cambridge, 1998.
9. Araki, K.; Hayashida, H. Tetrahedron Lett. 2000, 41, 1209-1213.
10. Ungaro, R.; Mandolini, L., Calixarenes in action. Imperial College Press: London, 2000.
11. Hong, B. H.; Bae, S. C.; Lee, C.-W.; Jeong, S.; Kim, K. S. Science 2001, 294, 348-351.
12. Buerkle, L. E.; Rowan, S. J. Chem. Soc. Rev. 2012, 41, 6089-6102.
13. Jones, R. G.; Wilks, E. S.; Jost, J. W.; Metanomski, W. V.; Kahovec, J.; Hess, M.; Stepto, R. F. T.; Kitayama, T.; Jenkins, A. D.; Kratochvíl, P.; IUPAC (International Union of Pure and Applied Chemistry), Compendium of polymer terminology and nomenclature IUPAC recommendations 2008. New ed.; Royal Society of Chemistry,: Cambridge, 2009.
14. Sangeetha, N. M.; Maitra, U. Chem. Soc. Rev. 2005, 34, 821-836.
15. 李俊賢、孫世勝，中央研究院週報，知識天地，2008年，第1172期。
16. Hirst, A. R.; Smith, D. K. Chem. Eur. J. 2005, 11, 5496-5508.
17. Hanabusa, K.; Miki, T.; Taguchi, Y.; Koyama, T.; Shirai, H. J. Chem. Soc., Chem. Commun. 1993, 1382-1384.
18. Deacon, G. B.; Feng, T.; Nickel, S.; Skelton, B. W.; White, A. H. J. Chem. Soc., Chem. Commun. 1993, 1328-1329.
19. Lehn, J.-M.; Mascal, M.; Decian, A.; Fischer, J. J. Chem. Soc., Chem. Commun. 1990, 479-481.
20. Samanta, S. K.; Bhattacharya, S. Chem. Commun. 2013, 49, 1425-1427.
21. Chung, J. W.; An, B.-K.; Park, S. Y. Chem. Mater. 2008, 20, 6750-6755.
22. Seo, J.; Chung, J. W.; Jo, E.-H.; Park, S. Y. Chem. Commun. 2008, 2794-2796.
23. Liu, K.; Steed, J. W. Soft Matter 2013, 9, 11699-11705.
24. (a) Aakeroy, C. B.; Chopade, P. D.; Ganser, C.; Desper, J. Chem. Commun. 2011, 47, 4688-4690; (b) Metrangolo, P.; Meyer, F.; Pilati, T.; Resnati, G.; Terraneo, G. Angew. Chem., Int. Ed. 2008, 47, 6114-6127.
25. Priimagi, A.; Cavallo, G.; Metrangolo, P.; Resnati, G. Acc. Chem. Res. 2013, 46, 2686-2695.
26. Benesi, H. A.; Hildebrand, J. H. J. Am. Chem. Soc. 1949, 71, 2703-2707.
27. Hassel, O. Science 1970, 170, 497-502.
28. Meazza, L.; Foster, J. A.; Fucke, K.; Metrangolo, P.; Resnati, G.; Steed, J. W. Nat. Chem. 2013, 5, 42-47.
29. Liu, Z.-X.; Feng, Y.; Zhao, Z.-Y.; Yan, Z.-C.; He, Y.-M.; Luo, X.-J.; Liu, C.-Y.; Fan, Q.-H. Chem. Eur. J. 2014, 20, 533-541.
30. King, K. N.; McNeil, A. J. Chem. Commun. 2010, 46, 3511-3513.
31. Carter, K. K.; Rycenga, H. B.; McNeil, A. J. Langmuir 2014, 30, 3522-3527.
32. Aoki, M.; Nakashima, K.; Kawabata, H.; Tsutsui, S.; Shinkai, S. J. Chem. Soc., Perkin Trans. 2 1993, 347-354.
33. Zheng, Y.-S.; Ji, A.; Chen, X.-J.; Zhou, J.-L. Chem. Commun. 2007, 3398-3400.
34. Zhou, J.-L.; Chen, X.-J.; Zheng, Y.-S. Chem. Commun. 2007, 5200-5202.
35. (a) Tsai, C.-C.; Chang, K.-C.; Ho, I. T.; Chu, J.-H.; Cheng, Y.-T.; Shen, L.-C.; Chung, W.-S. Chem. Commun. 2013, 49, 3037-3039; (b) 蔡佳蓁，含雙異咢唑芳香取代雙芳杯衍生物之合成、性質探討與應用研究，國立交通大學，博士論文，2013年。
36. (a) Tsai, C.-C.; Cheng, Y.-T.; Shen, L.-C.; Chang, K.-C.; Ho, I. T.; Chu, J.-H.; Chung, W.-S. Org. Lett. 2013, 15, 5830-5833; (b) 鄭英材，芳香環異咢唑取代雙芳杯之合成及膠體性質探討，國立交通大學，碩士論文，2011年。
37. Senthilvelan, A.; Tsai, M.-T.; Chang, K.-C.; Chung, W.-S. Tetrahedron Lett. 2006, 47, 9077-9081.
38. Balandier, J.-Y.; Belyasmine, A.; Sallé, M. Eur. J. Org. Chem. 2008, 2008, 269-276.
39. Nakamura, M.; Kurihara, H.; Ohkubo, M.; Tsukamoto, N. Novel Isoxazolopyridone Derivatives and Use Thereof. E.P. Patent 1,408,042, April 14, 2004.
40. Schunk, S.; Reich, M.; Engels, M.; Germann, T.; Jostock, R.; Hees, S. Substituted Indole Compounds. U.S. Patent 20,100,222,324, September 02, 2010.
41. Terech, P.; Weiss, R. G. Chem. Rev. 1997, 97, 3133-3160.
42. Zheng, Y.-S.; Ran, S.-Y.; Hu, Y.-J.; Liu, X.-X. Chem. Commun. 2009, 1121-1123.
43. Zheng, Y.-S.; Huang, Z.-T. Synth. Commun. 1997, 27, 1237-1245.
44. (a) Hanhela, P.; Paul, D. Aust. J. Chem. 1989, 42, 287-299; (b) Granzhan, A.; Teulade-Fichou, M.-P. Chem. Eur. J. 2009, 15, 1314-1318.
45. (a) 王雨筠，芳杯下緣含有(1)對位羧基衍生物之蒽與三唑(2)對位雙芘-酯-三唑之化學感測器的合成及其在金屬離子辨識之研究，國立交通大學，博士論文，2011年。; (b) Ikeda, A.; Shinkai, S. Chem. Rev. 1997, 97, 1713-1734.