臺灣博碩士論文加值系統

成功製備香豆素衍生物配位前驅物L1H-L8H，並將配位前驅物L1H-L8H與1.2當量的三甲基鋁反應後可合成鋁錯合物48-55，所有化合物皆可經由核磁共振光譜與元素分析鑑定，其中鋁錯合物49、51、52成功得到晶體並以X-ray單晶繞射儀進行結構分析。
所有鋁錯合物催化劑在外加醇類的條件下對環酯類皆具有活性，以同核去耦合核磁共振氫光譜可發現，鋁錯合物48-55可合成出具atactic微結構的聚乳酸，動力學研究顯示鋁錯合物48在開環聚合反應中為一級反應。

The coumarin-derived ligand precursors L1H-L8H have been prepared. Reactions of L1H-L8H with 1.2 equiv. of AlMe3 afford aluminum complexes 48-55. All compounds were characterized by NMR spectroscopy and elemental analysis. Molecular structures of 49, 51, and 52 were determined by X-ray crystallography. The catalytic activities of these complexes towards the ring-opening polymerization of cyclic esters in the presence of alcohols were also examined. Based on the homonuclear decoupled 1H NMR spectra, the atactic polylactides (Pm values ranged from 0.44 to 0.57) were produced using 48-55 as catalysts. Kenetics studies showed that the polymerization reaction is first-order for the complex 48.

第一章 緒論 1
1-1 生物可分解之高分子聚合物 1
1-2 開環聚合反應 4
1-2-1 開環聚合反應分類 4
1-2-2 金屬參與催化反應之機制探討 4
1-2-3 早期金屬催化劑應用與缺點 6
1-3 催化劑設計 8
1-3-1 催化劑設計基礎概念 8
1-3-2 配位基選擇與聚合物選擇性之關聯性 9
1-4 聚乳酸的立體化學 11
1-5 開環聚合反應的鋁金屬催化劑 12
1-5-1 Imino phenolate 形式輔助配位基 12
1-5-2 Ketimine 形式輔助配位基 18
1-6 研究方向 23

第二章 實驗部份 25
2-1 一般操作 25
2-2 溶劑處理 26
2-3 藥品處理 27
2-4 鑑定儀器 28
2-4-1 核磁共振儀( NMR ) 28
2-4-2 元素分析儀 ( EA ) 28
2-4-3 X-ray 單晶繞射儀 ( X-ray diffractometer ) 28
2-4-4 凝膠滲透層析儀 ( GPC ) 29
2-5 養晶方式 30
2-5-1 單一溶劑 30
2-5-2 兩種溶劑 30
2-6 香豆素衍生物配位基前驅物合成及鑑定 31
2-6-1起始物 3-acetyl-4-hydroxycoumarin 31
2-6-2香豆素衍生物配位基前驅物L1H 32
2-6-3香豆素衍生物配位基前驅物L2H 33
2-6-4香豆素衍生物配位基前驅物L3H 34
2-6-5香豆素衍生物配位基前驅物L4H 35
2-6-6 香豆素衍生物配位基前驅物L5H 36
2-6-7 香豆素衍生物配位基前驅物L6H 37
2-6-8 香豆素衍生物配位基前驅物L7H 38
2-6-9 香豆素衍生物配位基前驅物L8H 39
2-7 香豆素衍生物配位基錯合物合成及鑑定 40
2-7-1 鋁金屬錯合物48 40
2-7-2 鋁金屬錯合物49 41
2-7-3 鋁金屬錯合物50 42
2-7-4 鋁金屬錯合物51 43
2-7-5 鋁金屬錯合物52 44
2-7-6 鋁金屬錯合物53 45
2-7-7 鋁金屬錯合物54 46
2-7-8 鋁金屬錯合物55 47
2-8開環聚合催化反應 48
2-8-1外加醇類進行環己內酯之開環聚合反應步驟 48
2-8-2 外加醇類進行乳酸交酯之開環聚合反應步驟 48
2-9 環己內酯開環聚合反應之動力學實驗 49
2-9-1 固定苯甲醇濃度之動力學實驗 49
2-9-2 固定鋁錯合物濃度之動力學實驗 49

第三章 結果與討論 50
3-1 香豆素衍生物配位基前驅物L1H-L8H之合成 50
3-2 香豆素衍生物鋁錯合物48-55之合成與鑑定 51
3-3 晶體架構與探討 52
3-3-1 配位基 L5H 之晶體架構與探討 52
3-3-2 鋁錯合物49 之晶體架構與探討 53
3-3-3 鋁錯合物51之晶體架構與探討 54
3-3-4 鋁錯合物52之晶體架構與探討 55
3-4 環己內酯開環聚合反應 57
3-4-1 催化系統設計 57
3-4-2 鋁錯合物48-55進行開環聚合反應之催化劑優選 57
3-4-3 鋁錯合物48對環己內酯進行開環聚合反應 58
3-4-4 聚環己內酯的尾端鑑定 60
3-4-5動力學探討 61
3-4-6 開環聚合反應之機制探討 65
3-5 乳酸交酯開環聚合反應 67
3-5-1 催化系統設計 67
3-5-2 鋁錯合物48-55對左旋乳酸交酯進行開環聚合反應 67
3-5-3 聚乳酸的尾端鑑定 68

3-5-4 鋁錯合物48-55對外消旋乳酸交酯進行開環聚合反應 69
第四章 結論 71
參考文獻 72
附錄 76

1. (a) R. A. Gross, B. Kalra. Science, 2002, 297, 803-807. (b) A.P. Gupta, V. Kumar. Eur. Polym. J., 2007, 43, 4053-4074. (c) M. J.-L. Tschan, E. Brulé,
P. Haquette, C. M. Thomas. Polym. Chem., 2012, 3, 836-851.

2. (a) A.C. Albertsson, I. K.Varma. Biomacromolecules, 2003, 4, 1466-1486. (b) H. Tian, Z. Tang, X. Zhuang, X. Chen, X. Jing. Prog. Polym. Sci., 2012, 37, 237-280. (c) R. E. Drumright, P. R. Gruber, D. E. Henton. Adv. Mater., 2000, 23, 1841-1846.

3. (a) K. E. Uhrich, S. M. Cannizzaro, R. S. Langer, K. M. Shakesheff. Chem. Rev., 1999, 99, 3181-3198.(b) J. K. Oh, D. I. Leea, J. M. Park. Prog. Polym. Sci., 2009, 34, 1261-1282.

4. (a) M. C. Rocca, G. Carr, A. B. Lambert, D. J. MacQuarrie, J. H. Clark, S. A. Solvay, US patent 2003/6531615 B2, 2003.(b) M. Minami, S. Kozaki, US patent 2003/0023026 A1, 2003.

5. O. D.Cabaret, B. M.Vaca, D. Bourissou. Chem. Rev., 2004, 104, 6147-6176.

6. (a) S. Matsumura , K. Mabuchi, K. Toshima. Macromol. Rapid Commun., 1997, 18,477-482; (b) A. Kumar, R. A. Gross. Biomacromolecules, 2000, 1, 133-138.

7. (a) N. E. Kamber, W. Jeong, R. M. Waymouth, R. C. Pratt, B. G. G. Lohmeijer,
J. L. Hedrick. Chem. Rev., 2007, 107, 5813-5840. (b) N. E. Kamber, W. Jeong, S. Gonzalez, J. L. Hedrick, R. M. Waymouth. Macromolecules, 2009, 42, 1634-1639.

8. (a) A. P. Dove, Chem. Commun., 2008, 6446-6470. (b) G. W. Coates, J. Chem. Soc., Dalton Trans., 2002, 467-475. (c) K. Nakano, N. Kosaka, T. Hiyama, K. Nozaki. Dalton Trans., 2003, 4039-4050. (d) J. Wu, T.L. Yu, C.T. Chen, C. C. Lin. Coord. Chem. Rev., 2006, 250, 602-626. (e) C.A. Wheaton, P. G. Hayes, B. J. Ireland. Dalton Trans., 2009, 4832-4846.

9. (a) H. R. Kricheldorf, M. Berl, N. Scharnagl. Macromolecules, 1988, 21, 286-293. (b) Ph. Dubois, C. Jacobs, R. Jéréme, Ph. Teyssié. Macromolecules, 1991, 24, 2266-2270. (c) R. H. Platel, L. M. Hodgson, C. K. Williams. Polymer Reviews, 2008, 48, 11- 63.

10. C. M. Silvernail, L. J. Yao, L. M. R. H ill, M. A. Hillmyer, W. B. Tolman. Inorg.Chem., 2007, 46, 6565-6574.

11. (a) A. Kowalski, A. Duda, S. Penczek. Macromolecules, 1998, 31, 2114-2122.
(b) A.Kowalski, J. Libiszowski, A.Duda, S. Penczek. Macromolecules, 2000, 33, 1964-1971.

12. (a) M. H. Chisholm, J. C. Gallucci, K. T. Quisenberry, Z. Zhou. Inorg. Chem., 2008, 47, 2613-2624. (b) P. Piromjitpong, P. Ratanapanee, W. Thumrongpatanaraks,
P. Kongsaeree ,K. Phomphrai. Dalton Trans., 2012, 41, 12704-12710.

13.(a) N. Spassky , M. Wisniewski, C. Pluta, A. L. Borgne. Macromol. Chem. Phys., 1996, 197, 2627-2637. (b) Z. Zhong, P. J. Dijkstra, J. Feijen. Angew. Chem., 2002, 114,4692-4695. (c) N. Nomura, R. Ishii, Y. Yamamoto, T. Kondo. Chem. Eur. J., 2007, 13, 4433 – 4451.(d) M. Wisniewski, A. L. Borgne, N. Spassky. Macromol. Chem. Phys., 1997, 198, 1227-1238. (e) N. Nomura, R. Ishii, M. Akakura, K.Aoi.
J. Amer. Chem. Soc.,2002, 124, 5938-5939.

14.(a) C. M. Thomas. Chem. Soc. Rev., 2010, 39, 165–173. (b) M. J. Stanford, A. P. Dove. Chem. Soc. Rev., 2010, 39, 486–494.

15.(a) H. Y. Chen, H.Y. Tang, C. C. Lin. Macromolecules, 2006, 39, 3745-3752. (b) N. M. Rezayee, K. A. Gerling, A. L. Rheingold, J. M. Fritsch. Dalton Trans., 2013, 42, 5573–5586.

16.(a) W. C. Hung, C. C. Lin. Inorg. Chem. 2009, 48, 728-734. (b) W. Yi, H. Ma. Dalton Trans., 2014, 42, 5200–5210.

17.(a) D. J. Darensbourg, W. Choi, C. P. Richers. Macromolecules, 2007, 40, 3521-3523. (b) D. J. Darensbourg, W. Choi, O. Karroonnirun, N. Bhuvanesh. Macromolecules, 2008, 41, 3493-3502.

18.(a) J. Liu, N. Iwasa, K. Nomura. Dalton Trans., 2008, 3978–3988. (b) N.Iwasa, M. Fujiki , K. Nomura. J. Mol. Catal. A: Chem.,2008, 292, 67-75. (c) N. Iwasa, S. Katao, J. Liu, M. Fujiki, Y. Furukawa, K. Nomura. Organometallics, 2009, 28, 2179–2187.

19. D. Pappalardo, L. Annunziata, C. Pellecchia. Macromolecules, 2009, 42, 6056–6062.
20. W. Zhang, Y. Wang, W.H. Sun, L. Wang, C. Redshaw. Dalton Trans., 2012, 41, 11587–11596.

21. R. C. Yu, C. H. Hung, J. H. Huang, H. Y. Lee, J. T. Chen. Inorg. Chem., 2002, 41, 6450-6455.

22. C. T. Altaf, H. Wang, M. Keram, Y. Yang, H. Ma. Polyhedron, 2014, 81, 11–20.

23. W. A. Ma, Z. X. Wang. Dalton Trans., 2011, 40, 1778–1786.

24. H. J. Chuang , Y.C. Su, B.T. Ko, C.C. Lin. Inorg. Chem. Commun.,2012, 18, 38–42.

25. Y. Liu, W.S. Dong, J.Y. Liu, Y.S. Li. Dalton Trans., 2014, 43, 2244–2251.

26. X. Zhou, X. B. Wang, T. Wang, L.Y. Kong. Bioorg. Med. Chem. 2008, 16, 8011–8021.

27.(a) K. Hara, T. Sato, R. Katoh, A. Furube, Y. Ohga, A. Shinpo, S. Suga, K. Sayama, H. Sugihara, H. Arakawa. J. Phys. Chem. B., 2003, 107, 597-606. (b) K. Hara, K. Sayama, Y. Ohga, A. Shinpo, S. Suga, H. Arakawa. Chem. Commun., 2001, 569–570.

28. K.M. Zhang , W. Dou , P.X. Li , R.Shen , J. X. Ru, W. Liu, Y. M. Cui, C. Y. Chen, W. S. Liu, D. C. Bai. Biosens. Bioelectron.,2015, 64, 542–546.

29.(a) M. Huang, S.S. Xie, N. Jiang, J.S. Lan, L.Y. Kong, X. B. Wang. Bioorg. Med. Chem. Lett., 2015, 25 ,508–513. (b) K. V. Sashidhara, A. Kumar, M. Kumar, J. Sarkar, S. Sinha. Bioorg. Med. Chem. Lett., 2010, 20, 7205–7211.(c) S. Z. Ferreira, H. C. Carneiro, H. A. Lara, R. B. Alves, J. M. Resende, H. M. Oliveira, L. M. Silva, D. A. Santos, R. P. Freitas. ACS Med. Chem. Lett., 2015, 6, 271−275.

30. C.T.Chen, M.C. Wang, T.L. Huang. Molecules, 2015, 20, 5313-5328.

31.(a) S. Sukdolak, S. Solujić, N.Manojlović, N.Vuković, Lj. Krstić. J. Heterocyclic Chem., 2004, 41, 593-596.(b) N. Hamdi, C.d. Fischmeister, M. C. Puerta, P. Valerga. Med. Chem. Res., 2011, 20, 522–530. (c) D. R. Ilić, V. V. Jevtić, G. P. Radić, K. Arsikin , B. Ristić, L. H.Trajković, N.Vuković, S. Sukdolak, O. Klisurić, V. Trajković, S. R. Trifunović. Eur. J. Med. Chem.,2014, 74,502-508.

32.(a) P.A. Cameron, V. C. Gibson, C. Redshaw, J. A. Segal, A. J. P. White, D. J. Williams. J. Chem. Soc., Dalton Trans., 2002, 415–422.(b) M. Normand, V. Dorcet, E. Kirillov, J.F. Carpentier. Organometallics, 2013, 32, 1694−1709.

33.(a) C. Zhang, Z.X. Wang. J. Organomet. Chem.,2008, 693, 3151–3158.(b) M. Bouyahyi, T. Roisnel, J.F. Carpentier. Organometallics, 2012, 31, 1458−1466.

34.(a) C.T. Chen, C.A. Huang, B.H. Huang. Dalton Trans., 2003, 3799-3803.
(b) C.T. Chen, C.A. Huang, B.H. Huang. Macromolecules 2004, 37, 7968-7973.

35. S. Gong, H. Ma. Dalton Trans., 2008, 3345–3357.

36. M. Lamberti, I. D’Auria, M. Mazzeo, S. Milione, V. Bertolasi, D.Pappalardo. Organometallics, 2012, 31, 5551−5560.

37. K. Matsubara, C. Terata, H. Sekine, K. Yamatani, T. Harada, K. Eda, M. Dan, Y. Koga, M. Yasuniwa. J. Polym. Sci., Part A: Polym. Chem., 2012, 50, 957–966.

38.(a) H.Y. Chen, H.Y. Tang, C.C. Lin. Macromolecules 2006, 39, 3745-3752.
(b) C. Zhang, Z. X. Wang. Appl. Organometal. Chem., 2009, 23, 9–18.
(c) P. I. Binda, E. E. Delbridge. Dalton Trans., 2007, 4685–4692.

39. M. T. Gamer, P. W. Roesky, I. Palard, M. L. Hellaye, S. M. Guillaume. Organometallics 2007, 26, 651-657.