本研究將功能性單體1,1-di(pyridin-2-yl)-2-(4-vinylphenyl)ethan-1-ol (DPyVE)以及2,2'-(1-methoxy-2-(4-vinylphenyl)ethane-1,1-diyl)dipyridine (MVP) 與N-isopropylacrylamide (NIPAM)合成P(DPyVE-co-NIPAM)以及P(MVP-co-NIPAM) 的共聚物，分別與銅金屬及鈀金屬螯合並成功的將之用作Click反應以及Suzuki-Miyaura反應的異相催化劑。我們所合成的異相催化劑在反應完成後可以經由簡單的過濾回收並能重複用於催化反應至少五次且其反應效率並未明顯受回收次數影響。藉由ICP-AES的檢測，回收過後的催化劑其金屬含量在未回收前的99.8%以上，表示在反應中幾乎沒有金屬從催化劑上剝落。

Functional polymer of P(DPyVE-co-NIPAM) and P(MVP-co-NIPAM) were obtained from the copolymerization of N-isopropylacrylamide (NIPAM) and novel monomers of 1,1-di(pyridin-2-yl)-2-(4-vinylphenyl)ethan-1-ol (DPyVE) and 2,2'-(1-methoxy-2-(4-vinylphenyl)ethane-1,1-diyl)dipyridine (MVP). The functional polymers were coordinated to copper and palladium to form heterogeneous catalysts for click reaction and Suzuki-Miyaura reaction, respectively. The polymer-metal complexes could be recycled easily through filtrating after the reactions at least five time without significant decline in catalytic efficiency.

摘要 1
ABSTRACT 2
謝誌 3
圖次 6
表次 11
第一章 緒論 12
1.1前言 12
1.3金屬有機骨架 (METAL-ORGANIC-FRAMWORKS ,MOFS) 16
第二章 新穎功能性高分子作為異相催化劑的應用 22
2.1 PDPYMA應用於SUZUKI-MIYAURA REACTION. 22
2.2 PDPYVE-PD(OAC)2應用於SUZUKI-MIYAURA REACTION. 31
2.3 P(DPYVE-CO-NIPAM)-PD(OAC)2應用於SUZUKI-MIYAURA REACTION. 34
2.4 P(DPYVE-CO-NIPAM)-CUSO4應用於CLICK REACTION.A 38
2.5 P(MVP-CO-NIPAM)-PD(OAC)2應用於SUZUKI-MIYAURA REACTION. 40
2.6 總結 44
第三章 鄰位雙吡啶對於芐位活性的影響 46
3.1 鄰位雙吡啶對於芐位活性的影響 46
3.2 結論 54
第四章 實驗步驟及儀器鑑定 55
4.1 藥劑以及儀器 55
4.2 合成及光譜分析 59
4.2.1 Di(pyridin-2-yl)methanol (BPyOH) 的合成 66 59
4.2.2 Di(pyridin-2-yl)methyl acrylate (DPyMA) 的合成 60
4.2.3 1,1-di(pyridin-2-yl)-2-(4-vinylphenyl)ethan-1-ol (DPyVE) 的合成 62
4.2.4 2,2'-(1-methoxy-2-(4-vinylphenyl)ethane-1,1-diyl)dipyridine (MVP) 的合成 64
4.2.5 DPyMA-MX2 錯合物的合成 66
4.2.6 DPyVE-MX2 錯合物的合成 68
4.2.7 MVP-MX2 錯合物的合成 70
自由基聚合 (Free Radical Polymerization) 72
4.2.8 PolyDPyMA 的合成 73
4.2.9 PolyDPyVE 的合成 74
4.2.10 Poly(DPyVE-co-NIPAM) 的合成 75
4.2.11 PolyMVP 的合成 77
4.2.12 Poly(MVP-co-NIPAM) 的合成 78
4.2.13 PDPyMA-MX2 錯合物的合成 80
4.2.14 P(DPyVE-co-NIPAM)-MX2 錯合物的合成 82
4.2.15 P(DPyVE-co-NIPAM)-MX2 錯合物的合成 84
4.2.16 2,2'-(bromomethylene)dipyridine 的合成 86
4-2-17 4-vinylbenzyl alcohol 的合成 88
4.2.18 2-phenyl-1,1-di(pyridin-2-yl)ethan-1-ol 的合成 90
4.2.19 1,1-di(pyridin-2-yl)ethan-1-ol 的合成 92
4.2.20 diphenylmethyl benzyl ether 的合成 94
4.2.21 methyl 3-hydroxy-3,3-di(pyridin-2-yl)propanoate 的合成 96
4.2.22 2,2'-((benzyloxy)methylene)dipyridine 的合成 98
4.2.24 di(pyridin-3-yl)methanol 的合成 102
4.2.25 3,3'-((benzyloxy)methylene)dipyridine 的合成 104
4.2.26 2-((benzyloxy)methyl)pyridine 的合成 106
4.2.27 2-((benzyloxy)(phenyl)methyl)pyridine 的合成 108
4.2.28 2,2'-(methoxymethylene)dipyridine 的合成 110
4.3 晶體X-RAY 116
第五章 參考文獻 176

1. Brazel, C. S.; Peppas, N. A., Macromolecules, 1995, Start,8016
2. Chen, G.; Hoffman, A. S., Nature, 1995, Start,49
3. Galli, S.; Masciocchi, N.; Tagliabue, G.; Sironi, A.; Navarro, J. A.; Salas, J. M.; Mendez‐Liñan, L.; Domingo, M.; Perez‐Mendoza, M.; Barea, E., Chem. Eur. J., 2008, Start,9890
4. Gupta, P.; Vermani, K.; Garg, S., Drug discovery today, 2002, Start,569
5. Kwon, I. C.; Bae, Y. H.; Kim, S. W., 1991, Start
6. Lendlein, A.; Jiang, H.; Jünger, O.; Langer, R., Nature, 2005, Start,879
7. Liu, K.-W.; Li, C.-L.; Li, M.-C.; Ho, R.-M., Langmuir, 2013, Start,9016
8. Nguyen, V. Q.; Ramanujan, R., Macromol. Chem. Phys., 2010, Start,618
9. Wang, F.; Lai, Y.-H.; Han, M.-Y., Macromolecules, 2004, Start,3222
10. Welterlich, I.; Tieke, B., Macromolecules, 2011, Start,4194
11. Zheng, Y.; Li, G.; Deng, H.; Su, Y.; Liu, J.; Zhu, X., Polymer Chemistry, 2014, Start,2521
12. Zhou, S.; Chu, B., J. Phys. Chem. B, 1998, Start,1364
13. Schmaljohann, D., Advanced drug delivery reviews, 2006, Start,1655
14. Seki, T.; Kojima, J.-y.; Ichimura, K., J. Phys. Chem. B, 1999, Start,10338
15. Liu, F.; Urban, M. W., Prog. Polym. Sci., 2010, Start,3
16. Zhang, J.; Misra, R., Acta Biomaterialia, 2007, Start,838
17. Wu, D. Y.; Meure, S.; Solomon, D., Progress in Polymer Science, 2008, Start,479
18. Zhang, M.; Xu, D.; Yan, X.; Chen, J.; Dong, S.; Zheng, B.; Huang, F., Angewandte Chemie, 2012, Start,7117
19. Burnworth, M.; Tang, L.; Kumpfer, J. R.; Duncan, A. J.; Beyer, F. L.; Fiore, G. L.; Rowan, S. J.; Weder, C., Nature, 2011, Start,334
20. Chen, X.; Dam, M. A.; Ono, K.; Mal, A.; Shen, H.; Nutt, S. R.; Sheran, K.; Wudl, F., Science, 2002, Start,1698
21. Martín, R.; Rekondo, A.; Echeberria, J.; Cabañero, G.; Grande, H. J.; Odriozola, I., Chem. Commun., 2012, Start,8255
22. Rodriguez-Abreu, C.; Vilanova, N.; Solans, C.; Ujihara, M.; Imae, T.; López-Quintela, A.; Motojima, S., Nanoscale Research Letters, 2011, Start,330
23. Taguchi, A.; Schüth, F., Microporous and Mesoporous Materials, 2005, Start,1
24. Wu, Z.; Zhao, D., Chemical Communications, 2011, Start,3332
25. Trewyn, B. G.; Giri, S.; Slowing, I. I.; Lin, V. S. Y., Chemical Communications, 2007, Start,3236
26. Scott, B. J.; Wirnsberger, G.; Stucky, G. D., Chemistry of Materials, 2001, Start,3140
27. Murray, L. J.; Dinca, M.; Long, J. R., Chemical Society Reviews, 2009, Start,1294
28. Cho, S.-H.; Ma, B.; Nguyen, S. T.; Hupp, J. T.; Albrecht-Schmitt, T. E., Chemical Communications, 2006, Start,2563
29. Cavka, J. H.; Jakobsen, S.; Olsbye, U.; Guillou, N.; Lamberti, C.; Bordiga, S.; Lillerud, K. P., Journal of the American Chemical Society, 2008, Start,13850
30. Abid, H. R.; Shang, J.; Ang, H.-M.; Wang, S., International Journal of Smart and Nano Materials, 2013, Start,72
31. Manna, K.; Zhang, T.; Lin, W., Journal of the American Chemical Society, 2014, Start,6566
32. Sheraw, C.; Zhou, L.; Huang, J.; Gundlach, D.; Jackson, T.; Kane, M.; Hill, I.; Hammond, M.; Campi, J.; Greening, B., Appl. Phys. Lett, 2002, Start,1088
33. Friend, R.; Gymer, R.; Holmes, A.; Burroughes, J.; Marks, R.; Taliani, C.; Bradley, D.; Dos Santos, D.; Bredas, J.; Lögdlund, M., Nature, 1999, Start,121
34. Kraft, A.; Grimsdale, A. C.; Holmes, A. B., Angew. Chem. Int. Ed., 1998, Start,402
35. Yu, G.; Wang, J.; McElvain, J.; Heeger, A. J., Adv. Mater., 1998, Start,1431
36. Grätzel, M., Nature, 2001, Start,338
37. Huynh, W. U.; Dittmer, J. J.; Alivisatos, A. P., science, 2002, Start,2425
38. Bao, Z., Adv. Mater., 2000, Start,227
39. Yoon, J. A.; Kamada, J.; Koynov, K.; Mohin, J.; Nicolaÿ, R.; Zhang, Y.; Balazs, A. C.; Kowalewski, T.; Matyjaszewski, K., Macromolecules, 2011, Start,142
40. Yuan, Y.; Rong, M. Z.; Zhang, M., Acta Polymerica Sinica, 2008, Start,472
41. Cameron, C. G.; MacLean, B. J.; Pickup, P. G. In Electron transport in conjugated metallopolymers, Macromolecular Symposia, Wiley Online Library: 2003; pp 165.
42. Grasa, G. A.; Viciu, M. S.; Huang, J.; Zhang, C.; Trudell, M. L.; Nolan, S. P., Organometallics, 2002, Start,2866
43. Kantchev, E. A. B.; O'Brien, C. J.; Organ, M. G., Angew. Chem. Int. Ed., 2007, Start,2768
44. Miyaura, N.; Suzuki, A., Chem. Rev., 1995, Start,2457
45. Ohmura, T.; Awano, T.; Suginome, M., J. Am. Chem. Soc., 2010, Start,13191
46. Yamamoto, T.; Akai, Y.; Nagata, Y.; Suginome, M., Angew. Chem. Int. Ed., 2011, Start,8844
47. Heck, R. F., Journal of the American Chemical Society, 1963, Start,3116
48. Heck, R. F.; Nolley, J. P., The Journal of Organic Chemistry, 1972, Start,2320
49. Dieck, H. A.; Heck, R. F., Journal of the American Chemical Society, 1974, Start,1133
50. Negishi, E.-i.; Baba, S., Journal of the Chemical Society, Chemical Communications, 1976, Start,596b
51. Bell, A. T., Science, 2003, Start,1688
52. Kim, S.-W.; Kim, M.; Lee, W. Y.; Hyeon, T., J. Am. Chem. Soc., 2002, Start,7642
53. Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.; Hupp, J. T., Chem. Soc. Rev., 2009, Start,1450
54. Liu, Y.; Xuan, W.; Cui, Y., Adv. Mater., 2010, Start,4112
55. Leadbeater, N. E.; Marco, M., Chem. Rev., 2002, Start,3217
56. Harmer, M. A.; Farneth, W. E.; Sun, Q., J. Am. Chem. Soc., 1996, Start,7708
57. Zhang, J.; Yan, Y.; Chance, M. W.; Chen, J.; Hayat, J.; Ma, S.; Tang, C., Angewandte Chemie, 2013, Start,13629
58. Grasa, G. A.; Hillier, A. C.; Nolan, S. P., Org. Lett., 2001, Start,1077
59. Navarro, O.; Kelly, R. A.; Nolan, S. P., J. Am. Oil Chem. Soc., 2003, Start,16194
60. Li, J.-H.; Liu, W.-J.; Xie, Y.-X., J. Org. Chem., 2005, Start,5409
61. Kim, Y. M.; Yu, S., J. Am. Chem. Soc., 2003, Start,1696
62. Li, J.; Singh, U. G.; Schladt, T. D.; Stalick, J. K.; Scott, S. L.; Seshadri, R., Chem. Mater., 2008, Start,6567
63. Štěpnička, P.; Zábranský, M.; Císařová, I., ChemistryOpen, 2012, Start,71
64. Mai, W.; Gao, L., Synlett, 2006, Start,2553