簡易檢索 / 詳目顯示

回結果列表
研究生： 雪布
Balagopal Shainamma Shaibu
論文名稱： PtII and RuII Catalyzed Regio-Controlled Synthesis of Ethylene-Bridged para-Phenylene Oligomers, Their Photophysical and Redox properties & Gold Catalyzed / Metal free Organic Transformations
指導教授： 劉瑞雄
口試委員: 劉瑞雄
沙晉康
蔡易州
侯敦仁
孫仲銘
學位類別： 博士
Doctor
系所名稱： 理學院 - 化學系
Department of Chemistry
論文出版年： 2012
畢業學年度： 100
語文別： 英文
論文頁數： 457
中文關鍵詞： 金 、催化 、OLED 、發光材料 、炔類
相關次數： 點閱：2  下載：0 
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報

    • The synthesis of para- phenylene oligomers encapped with diphenylamine and studies of their photophysical and electronic properties are mentioned in this dissertation. Gold catalyzed [2+2+2] cycloaddition of ynamides and cross coupling of tow carbene generated from different sources to form dienes are detailed in this dissertation. A novel multicomponent reaction involving benzyne, an N-oxide and an alkyne is also described in this dissertation. For sake of convenience and better understanding, the thesis is divided into four chapters.

    In the first chapter a regiocontrolled synthesis of ethylene bridged para phenylene oligomers encapped with two aryl amines with varied spacer lengths is explained. We also presented and explained the variations of the photophysical and electronic properties of this set of para phenylene oligomers in particular their HOMO-LUMO energy levels, UV absorptions, and fluorescent emissions and quantum yields.

    The second chapter deals with a novel gold catalyzed [2+2+2] cycloaddion reaction of aryl amides with enol ethers. Particularly notable is the cycloaddition has no precedent in an intramolecular version. This reaction proved to be an efficient way for the synthesis of cyclohexenes.

    The third chapter describes the synthesis of dienes via gold catalyzed crosscoupling of carbenes arising from two different sources, a vinylcarbene fragment resulting from a propargylic ester rearrangement and a diazoalkane carbene.

    The fourth chapter presents a metal free novel muticomponent reaction involving benzyne, Pyridene N-oxide and an alkyne.

    本篇論文可分為四個章節，第一章節為合成一系列線形多苯環化合物且於分子之頭尾兩端接上二苯胺分子，並進一步測量以及探討其特殊的光物理以及電化學性質。第二以及第三章節主要利用金金屬錯合物催化 ynamides 分子進行[2+2+2] 環化加成反應以及利用碳烯分子進行交叉耦合反應合成一系列二烯類化合物。最後第四章節利用苯炔化合物、氧化胺以及炔分子進行多化合物組成反應合成一系列苯基吡啶化合物。

    第一章節我們利用了不同的金屬錯合物催化具有高度位向選擇性之環化反應，將線型對苯化合物以乙烯分子橋接起來，並於兩端引入了二苯胺分子合成了一系列不同長度的線形多苯環分子。經由測量其HOMO、LUMO、UV吸收光譜、 螢光放射光譜 以及量子產率，實驗中發現此系列分子具有特殊的光物理以及電化學性質。

    第二章節中我們開發了新型的金金屬錯合物催化芳酰胺分子以及烯醚化合物進行[2+2+2] 環化加成反應，值得注意的是此類新型反應並沒有觀察到任何分子內反應發生，可以利用於合成一系列的環己烷化合物。

    第三章節我們發展了利用炔酯類分子進行重排反應以及重氮烷基碳烯產生乙烯基碳烯再經由金金屬錯合物催化交叉耦合反應。

    最後一個章節我們利用了苯炔化合物、氧化胺以及炔分子進行多化合物組成反應合成一系列苯基吡啶化合物。

    Contents Page ACKNOWLEDGEMENTS iii ABSTRACT v LIST OF SCHEMES viii LIST OF TABLES ix LIST OF FIGURES xii LIST OF PUBLICATIONS xiv ABBREVIATIONS xv CHAPTER 1: PtII and RuII catalyzed regio-controlled synthesis of ethylene-bridged para-phenylene oligomers, studies on their photophysical and redox properties Introduction 2 Results and Discussion 11 Conclusion 22 Experimental Procedures 22 Spectral Data of key compounds 36 References 51 CHAPTER 2: Efficient synthesis of cyclohexenes via gold catalyzed [2+2+2] cycloaddition Introduction 56 Results and Discussion 70 Conclusion 77 Experimental Procedures 77 Spectral Data of key compounds 80 References 91 CHAPTER 3: Gold-Catalyzed synthesis of functionalized dienes via cross-coupling of two carbenes Introduction 99 Results and Discussion 112 Conclusion 118 Experimental Procedures 118 Spectral Data of key compounds 120 References 138 CHAPTER 4: Synthesis of Pyridinyl Phenoxy-acrylates Through a Three-Component Reaction of Arynes with Pyridine n-oxides and Alkynes Introduction 144 Results and Discussion 156 Conclusion 165 Experimental Procedures 165 Spectral Data of key compounds 167 References 186 1H & 13C NMR SPECTRA 190

    References
    1. (a) Grimsdale, A. C.; Chan, K. L.; Martin, R. E.; Jokisz, P. G.; Holmes, A. B. Chem. Rev. 2009, 109, 897. (b) Kraft, A.; Grimsdale, A. C.; Holmes, A. B. Angew. Chem. Int. Ed. 1998, 37, 402. (c) Müller, C. D.; Falcou, A.; Reckefuss, N.; Rojahn, M.; Wiederhirn, V.; Rudati, P.; Frohne, H.; Nuyken, O.; Becker, H.; Meerholz, K. Nature 2003, 421, 829. (d) Mitschke, U.; Bauerle, P. J. Mater. Chem. 2000, 10, 1471. (e) Braun, D.; Heeger, A. J. Appl. Phys. Lett. 1991, 58, 1982. (f) Burroughes, J. H.; Bradley, D. D. C.; Brown, A. R.; Marks, R. N.; Mackay, K.; Friend, R. H.; Burns, P. L.; Holmes, A. B. Nature 1990, 347, 539.
    2. (a) Dimitrakopoulos, C. D.; Malefant, P. R. L. Adv. Mater. 2002, 14, 99. (b) Bao, Z.; Lovinger, A. J.; Brown, J. J. Am. Chem. Soc. 1998, 120, 207.(c) Horowitz, G.; Kouki, F.; Spearman, P.; Fichou, D.; Nogues, C.; Pan, X.; Garnier, F. Adv. Mater. 1996, 8, 242. (d) Song, Y.; Di, C.; Yang, X.; Li, S.; Xu, W.; Liu, Y. ; Yang, L.; Shuai, Z.; Zhang, D. ; Zhu, D. J. Am. Chem. Soc. 2006, 128, 15940. (e) Schenning, A. P. H. J.; Jonkheijm, p.; Peeters, E.; and Meijer E. W. J. Am. Chem. Soc. 2001, 123, 409-416
    3. (a) Brabec, C. J.; Sariciftci, N. S.; Hummelen, J. C. Adv. Funct. Mater. 2001, 11, 15. (b) Wohrle, D.; Meissner, D. Adv. Mater. 1991, 3, 129. (c) Zheng, Q.; Jung, B. J.; Sun, J.; Katz, H. E. J. Am. Chem. Soc. 2010, 132, 5394. (d) Yang, R.; Tian, R.; Yan, J.; Zhang, Y.; Yang, J.; Hou, Q.; Yang, W.; Zhang, C.; Cao, Y. Macromolecules 2005, 38, 244.
    4. (a) Pisula, W.; Menon, A.; Stepputat, M.; Lieberwirth, I.; Kolb, U.; Tracz, A.; Sirringhaus, H.; Pakula, T.; Müllen, K. Adv. Mater. 2005, 17, 684. (b) Feng, X.; Wu, J.; Ai, M.; Pisula, W.; Zhi, L.; Rabe, J. P.; Müllen, K. Angew. Chem. Int. Ed. 2007, 46, 3033. (c) Elmahdy, M. M.; Dou, X.; Mondeshki, M.; Floudas, G.; Butt, H.-J.; Spiess, H. W.; Müllen, K. J. Am. Chem. Soc. 2008, 130, 5311. (d) Sergey, S.; Pisula, W.; Geerts, Y. H. Chem. Soc. Rev. 2007, 12, 1902.
    5. Winslow, F. H. J. Polym. Sci. 1955, 16, 101.
    6. Scherf, U. J. Mater. Chem. 1999, 9, 1853.
    7. Scherf, U. ; Müllen, K. Adv. In Polym. Sci. 1995, 123, 1.
    8. Scherf, U.; Müllen, K. Makromol. Chem. Rapid Commun. 1991, 12, 489.
    9. Chmil, K.; Scherf, U. Makromol. Chem. Rapid Commun., 1993, 14, 217.
    10. Chmil, K.; Scherf, U. Acta Polym., 1997, 48, 208.
    11. (a) Remmers, M.; Neher, D.; Grüner, J.; Friend, R. H.; Gelinck, G. H.; Warman, J. M.; Quattrocchi, C.; dos Santos, D. A.; Brédas, J.-L. Macromolecules 1996, 29, 7432. (b) Heidenhain, S. B.; Sakamoto, Y.; Suzuki, T.; Miura, A.; Fujikawa, H.; Mori, T.; Tokito, S.; Taga Y. J. Am. Chem. Soc. 2000, 122, 10240. (c) Grem, G.; Leditzky, G.; Ullrich, B.; Leising, G. Adv. Mater. 1992,4, 36.
    12. (a) Leclerc, M. J. Polym. Sci. A: Polym. Chem. 2001, 39, 2867. (b) Dudek, S. P.; Pouderoijen, M.; Abbel, R.; Schenning, A. P. H. J.; Meijer, E. W. J. Am. Chem. Soc. 2005, 127, 11763 (c) Matsumoto, N.; Miyazaki, T.; Nishiyama, M.; Adachi, C. J. Phys. Chem. C 2009, 113, 6261 (d) Zhao, Z.; Xu, X.; Jiang, Z.; Lu, P.; Yu, G.; Yunqi Liu, Y. J. Org. Chem. 2007, 72, 8345
    13. (a)Kreyenschmidt, M.; Uckert, F.; Müllen, K. Macromolecules 1995, 28, 4577–4582. (b) Kim, K. S.; Jeong, S.; Kim, c.; Kim, E.; Kwon, Y.; Kim, H.; Choi, B. D.; Han, Y. S. Synthetic Metals 2010,160, 549.
    14. (a) Scherf, U. J. Mater. Chem. 1999, 9, 1853. (b) Wu, Y.; Zhang, J.; Bo, Z. Org. Lett. 2007, 9, 4435. (c) Jacob, J.; Sax, S.; Piok, T.; List, E. J. W.; Grimsdale, A. C.; Müllen, K. J.Am. Chem. Soc. 2004, 126, 6987. (d) Grem, G.; Paar, C.; Stampfl, J.; Leising, G.; Huber, J.; Scherf, U. Chem. Mater. 1995, 7, 2.
    15. Grimsdale, A. C.; Müllen, K. Adv Polym Sci. 2006, 199, 1.
    16. Mallory, F.B.; Butler, K. E.; Evans, A. C.; Brondyke, E. J.; Mallory, C. W.; Yang, C.; Ellenstein. A. J.Am. Chem. Soc. 1997, 119, 2119.
    17. Mallory, F. B.; Butler, K. E.; Berube, A.; Luzik, Jr. E. D.; Mallory, C. W.; Brondyke, E. J.; Hiremath, R.; Ngo, P.; Caroll, P. J.; Tetrahedron 2001, 57, 3715.
    18. (a) Okamoto, H.; Kawasaki, N.; Kaji, Y.; Kubozono, Y.; Fujiwara, A.; Yamaji, M. J. Am. Chem. Soc. 2008, 130, 10470. (b) Okamoto, H.; Yamaji, M.: Gohda, S.; Kubozono,Y.; Komura,N.; Sato,K.; Sugino, H.; Satake, K. Org. Lett. 2011, 13, 2758.
    19. Goldfinger, M.B.; Swager, T.M.; J. Am. Chem. Soc. 1994, 116, 7895.
    20. Chen, T. A.; Lee, T. J.; Lin, M. Y.; Sohel, S. M. A.; Diau, E. W. G. ; Lush, S. F.; Liu, R. S. Chem. Eur. J. 2010, 16, 1826.
    21. (a) Lambert, C.; Nöll, G. J. Chem. Soc., Perkin Trans. 2 2002, 2039. (b) Scherf, U.; List, E. J. W. Adv. Mater. 2002, 14, 477. (c) Lambert, C.; Schelter, J.; Fiebig, T.; Mank, D.; Trifonov, A. J. Am. Chem. Soc. 2005, 127, 10600. (d) Wu, J.; Baumgarten, M.; Debije, M. G.; Warman, J. M.; Müllen, K. Angew. Chem., Int. Ed. 2004, 43, 5331. (e) Dapper held, S.; Steckhan, E.; Brinkhaus, K.-H. G.; Esch, T. Chem. Ber. 1991, 124, 2557. (f) Coropceanu, V.; Malagoli, M.; André, J. M.; Brédas, J. L. J. Am. Chem. Soc. 2002, 124, 10519. (g) Cremer, J.; Bäuerle, P.; Wienk, M. M.; Janssen, R. A. J. Chem. Mater. 2006, 18, 5832. (h) Szeghalmi, A.; Erdmann, M.; Engel, V.; Schmitt, M.; Amthor, S.; Kriegisch, V.; Nöll, G.; Rainer, S.; Lambert, C.; Leusser, D.; Stalke, D.; Zabel, M.; Popp, J. J. Am. Chem. Soc. 2004, 126, 7834.
    22. Lambert, C.; Nöll, G. J. Am. Chem. Soc. 1999, 121, 8434.
    23. Zhou, G.; Baumgarten, M.; Müllen, K. J. Am. Chem. Soc. 2007, 129, 12211.
    24. (a) Bonvoisin, J.; Launay, J-P.; Auweraer, M. V.; Schryver, F. C.D. J. Phys. Chem. 1994, 98, 5052. (b) Lambert, C.; Nöll, G. Chem. Eur. J. 2002, 8, 3467. (c) Lambert, C.; Nöll, G. Angew. Chem., Int. Ed., 1998, 37, 2107.
    25. (a) Bonvoisin, J.; Launay, J-P.; Verbouwe, W.; Auweraer, M. V.; Schryver, F. C.D. J. Phys. Chem., 1996, 100, 17079. (c) Lambert, C.; Gaschler, W.; Schmälzlin, E.; Meerholz K.; Bräuchle, C. J. Chem. Soc., Perkin Trans. 2, 1999, 0, 577.
    26. Åhman, J.; Buchwald, S. L. Tetrahedron Lett. 1997, 38, 6363.
    27. Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.

    無法下載圖示 全文公開日期 本全文未授權公開 (校內網路)
    全文公開日期 本全文未授權公開 (校外網路)

    QR CODE