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Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/14190
標題: 吡唑苯酚基鋁錯合物之合成、鑑定及其對環酯類開環聚合反應之應用
Aluminum Complexes Containing Pyrazolyl-phenolate Ligands: Synthesis, Characterization and Application in Ring-Opening Polymerization of Cyclic Esters
作者: 張祐誠
Chang, Yu-Cheng
關鍵字: 鋁金屬;ring-opening polymerization;吡唑;Aluminum;Pyrazole
出版社: 化學系所
引用: 1.Polylactic Acid: Synthesis, Properties and Applications, L. Avérous, 2008, 433. 2.(a) http://www.ppck.com/about/learnpla.html (b) http://www.tairchu.com.tw/ 3.(a) M. C. Rocca, G. Carr, A. B. Lambert, D. J. MacQuarrie, J. H. Clark and S. A. Solvay, US patent 2003/6531615 B2, 2003. (b) M. Minami and S. Kozaki, US patent 2003/0023026 A1, 2003. 4.(a) A. Kumar and R. A. Gross, Biomacromolecules., 2000, 1, 133. ; (b) F. C. Loeker, C. J. Duxbury, R. Kumar, W. Gao, R. A. Gross and S. M. Howdle, Macromolecules., 2004, 37, 2450. ; (c) S. Matsumura, K. Mabuchi, and K. Toshima, Macromol. Rapid Commun., 1997, 18, 477. 5. O. D. Cabaret, B. M. Vaca and D. Bourissou, Chem. Rev., 2004, 104, 6147. 6.A. P. Dove, H. Li, R. C. Pratt, B. G. G. Lohmeijer, D. A. Culkin, R. M. Waymouth and J. L. Hedrick, Chem. Commun., 2006, 2881. 7.(a) B. J. O’Keefe, M. A. Hillmyer and W. B. Tolman, J. Chem. Soc. Dalton Trans., 2001, 2215. ; (b) G. W. Coates, J. Chem. Soc., Dalton Trans., 2002, 467. ; (c) K. Nakano, N. Kosaka, T. Hiyama and K. Nozaki, Dalton Trans., 2003, 4039. ; (d) J. Wu, T.-L. Yu, C.-T. Chen and C.-C. Lin, Coord. Chem. Rev., 2006, 250, 602. ; (e) C. A. Wheaton, P. G. Hayes and B. J. Ireland, Dalton Trans., 2009, 4832. 8.Dittrich, W.; Schulz, R. C. Angew. Makromol. Chem. 1971, 15, 109 9.Kricheldorf, H. R.; Berl, M.; Scharnagl, N. Macromolecules 1988, 21,286. 10.Dubois, P.; Jacobs, C.; Jérôme, R.; Teyssié, P. Macromolecules 1991, 24,2266. 11.C. M. Silvernail, L. J. Yao, L. M. R. Hill, M. A. Hillmyer and W. B. Tolman, Inorg. Chem., 2007, 46, 6565. 12.A. Kowalski, J. Libiszowski, A. Duda and S. Penczek, Macromolecules, 2000, 33, 1964. 13.A. Kowalski, A. Duda and S. Penczek, Macromolecules, 1998, 31, 2114. 14.M. H. Chisholm, J. C. Gallucci and C. Krempner, Polyhedron, 2007, 26, 4436. 15.B.-T. Ko and C.-C. Lin, Macromolecules, 1999, 32, 8296. 16.B. M. Chamberlain, M. Cheng, D. M. Moore, T. M. Ovitt, E. B. Lobkovsky and G. W. Coates, J. Am. Chem. Soc., 2001, 123, 3229. 17.N. Nomura. R. Ishii, Y. Yamamoto, T. Kondo, Chem. Eur. J., 2007, 13, 4433. 18.C. K. Williams, L. E. Breyfogle, S. K. Choi, W. Nam, V. G. Young, Jr., M. A. Hillmyer and W. B. Tolman, J. Am. Chem. Soc., 2003, 125, 11350.. 19.J. Liu, N. Iwasa, K. Nomura, Dalton Trans., 2008, 3978. 20.M. H. Chisholm, N. W. Eilerts, J. C. Huffman, S. S. Iyer, M. Pacold and K. Phomphrai, J. Am. Chem. Soc., 2000, 122, 11845. 21.S. Milione, F. Grisi, R. Centore and A. Tuzi, Organometallics., 2006, 25, 266. 22.K.-F. Peng and C.-T. Chen, Dalton Trans., 2009, 9800. 23.Z. Zheng, G. Zhao, R. Fablet, M. Bouyahyi, C. M. Thomas, T. Roisnel, O. Casagrande Jr and J.-F. Carpentier, New J. Chem., 2008, 32, 2279. 24.T.-L. Huang, C.-T. Chen,J. Organomet. Chem. , 2013,725, 15. 25.P.-Y. Michellys, J. Med. Chem., 2003, 46, 4087. 26.J. H. Espenson, Z. Zhu and T. H. Zauche, J. Org. Chem. 1999, 64, 1191. 27.C. D. Carmichael and M. D. Fryzuk, Dalton Trans., 2008, 800. 28.G. Fukata, T. Itoh and M. Tashiro, Heterocycles, 1982, 19, 1487. 29.J. C. Antilla, J. M. Baskin, T. E. Barder and S. L. Buchwald, J. Org. Chem., 2004, 69, 5578. 30.A.M.François, L.Azor, A.L.Schmitt, A.Coquel, L.Brelot,R.Welter, S.B.Laponnaz, S. Dagorne,J. Organomet. Chem., 2012,696, 4248. 31.C.-T. Chen, C.-A. Huang, B.-H. Huang, Dalton Trans., 2003, 3799. 32.C. K. Williams, L. E. Breyfogle, S. K. Choi, W. Nam, V. G. Young, Jr., M. A. Hillmyer and W. B. Tolman, J. Am. Chem. Soc., 2003, 125,11350. 33.M. H. Chisholm, N. W. Eilerts, J. C. Huffman, S. S. Iyer, M. Pacold and K. Phomphrai, J. Am. Chem. Soc., 2000, 122, 11845. 34.Z. Tang, V. C. Gibson, Eur. Polym. J., 2007, 43, 150. 35.Antonio Otero, Juan Fernández-Baeza, Luis F. Sánchez- Barba, Juan Tejeda, Manuel Honrado, Andrés Garcés, Agustín Lara-Sánchez, and Ana M. Rodríguez, Organometallics, 2012, 31, 4191–4202 36.2011年高雄醫學大學醫藥暨應用化學系研究所方欣柔碩士論文
摘要: 
本論文利用具不同立體障礙修飾的溴苯酚與吡唑，經由銅催化之碳-氮偶合反應可得一系列的吡唑苯酚配位基前驅物L1H-L6H，[L1H = HOPhHPzH; L2H = HOPhMePzH; L3H = HOPhtBuPzH; L4H = HOPhHPzMe; L5H = HOPhMePzMe; L6H = HOPhtBuPzMe]。以1.0當量的吡唑苯酚配位基前驅物L1H-L6H與1.2當量的三甲基鋁試劑反應，可以成功合成鋁錯合物36-41。其中鋁錯合物41與苯甲醇進一步反應，可以合成帶烷氧基的鋁錯合物47。合成之鋁錯合物，皆以核磁共振光譜以及元素分析數據進行鑑定，並經由 X-ray 單晶繞射儀之數據鑑定鋁錯合物36與47的分子結構。於外加苯甲醇的條件下，將鋁錯合物36-41對於環己內酯及左旋乳酸交酯進行開環聚合反應，皆具有良好的催化活性以及狹窄的 PDI 數值，且鋁錯合物38具有Living以及Immortal的性質。以鋁錯合物47進行動力學研究，得知單體及催化劑濃度對反應速率之影響皆為一級反應。催化合成之高分子聚合物，可經由核磁共振氫光譜以及基質輔助雷射脫附游離飛行時間質譜儀進行鑑定。

A series of pyrazolyl-phenolate ligand precursors L1H-L6H, [L1H = HOPhHPzH; L2H = HOPhMePzH; L3H = HOPhtBuPzH; L4H = HOPhHPzMe; L5H = HOPhMePzMe; L6H = HOPhtBuPzMe] was synthesized via copper- catalyzed N-arylation in good yields. The reactions of L1H-L6H with 1.2 equivalent of AlMe3 yielded aluminum alkyl complexes 36-41. Furthermore, reaction of aluminum alkyl complex 41 with benzyl alcohol afforded aluminum benzyl alkoxide complex 47. All these compounds were characterized by NMR spectroscopy and elemental analysis. The molecular structures of complexes 36 and 47 were determined by single-crystal X-ray diffraction techniques. Complexes 36-41 demonstrated catalytic activities towards the ring-opening polymerization of e-caprolactone and L-lactide in the presence of BnOH with narrow PDIs. Complex 38 exhibited both “ living ” and “ immortal ” characters. Nevertheless, the kinetics using complex 47 as an initiator was also studied, and the experimental results revealed that the rate of reaction was first-order dependence on monomer and catalyst concentration. End group analysis of the polymer was characterized by 1H NMR spectrum and MALDI-TOF mass spectrum .
URI: http://hdl.handle.net/11455/14190
其他識別: U0005-1706201317113000
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