多並苯化合物因其具有良好的光電性質，近年來在有機材料研究上佔有重要的地位。多並苯化合物除了穩定度需要解決之外，溶解度也是相當重要的課題，因此本篇論文之目標即在於發展步驟簡單且反應條件溫和的多並苯合成法。所以我們主要做兩種合成法的闡述:第一，採用以隱藏式醛基的方式先進行雙邊烯化延長反應，再利用酸性條件下去保護行Knoevenagel縮合環化反應，而得到高階並苯衍生物；第二，利用分子內碘鋰交換重排並氧化得鄰酮基苯醛，以此化合物雙邊接長以達到目標高階多並苯。此兩種合成法大大改善了合成過程中間體或目標多並苯化合物溶解度不佳的問題。未來預計可銜接上更多官能積來增加高階並苯衍生物的多樣性。

In the past decade, acenes have played an important role in the research of organic materials, owing to their excellent photoelectric properties. However, the stability and solubility problems of acenes compounds are formidable roadblocks to their future applications. The goal of this thesis is to develop simple and mild synthetic reaction to synthesis of acene skeletons. Previously, we developed an iterative elongation protocol consisted of Wittig olefination and Knoevenagel condensation. We hereby describe have two new synthetic method based on our published elongation method. Using reagents carrying differentially protected aldehydes, we first carried out a Wittig olefination to extend the length of conjugation yet without the original cyclization. After the protecting groups are removed, the delayed cyclization can furnish the target acene structure without encountering the solubility or stability problems. Second, by employing intramolecular Fries rearrangement as the key step, we are now able to construct a central unit for bidirectional elongation with solubilizing groups attached. The two new strategies greatly improve the current synthetic efficiency. Their applications in the synthesis of bifunctional and bis-chromophoric systems are also discussed.

(a) Shirakawa, H.; Louis, E. J.; MacDiarmid, A. G.; Chiang, C. K.; Heeger, A. J. J. Chem. Soc., Chem. Commun.1977, 578. (b) Chiang, C. K.; Park, Y. W.; Heeger, A. J.; Shirakawa, H.; Louis, E. J.; MacDiarmid, A. G. Phys. Rev. Lett.1977, 39, 1098. (c) Chiang, C. K.; Druy, M. A.; Gau, S. C.; Heeger, A. J.; Louis, E. J.; MacDiarmid, A. G.; Park, Y. W.; Shirakawa, H. J. Am. Chem. Soc. 1978, 100, 1013-15.

Horowitz, G. Adv. Mater. 1998, 10, 365.

Kertesz, M.; Hoffmann, R. Solid State Commun. 1983, 47, 97.

Kivelson, S.; Chapman, O. L. Phys. Rev. B 1983, 28, 7236.

(a) Brèdas, J. L.; Chance, R. R.; Baughman, R. H. J. Chem. Phys. 1982, 76, 3673. (b) Houk, K. N.; Lee, P. S.; Nendel, M. J. Org. Chem. 2001, 66, 5517.

Mondal, R.; Shah, B. K.; Neckers, D. C. J. Am. Chem. Soc. 2006, 128, 9612.

Bendikov, M.; Duong, H. M.; Starkey, K.; Houk, K. N.; Carter, E. A.; Wudl, F. J. Am. Chem. Soc. 2004, 126, 7416.

Kaur, I.; Jazdzyk, M.; Stein, N. N.; Prusevich, P.; Miller, G. P. J. Am. Chem. Soc. 2010, 132, 1261.

Pope, M.; Kallmann, H. P.; Magnante, P. J. Chem. Phys. 1963, 38, 2042.

Shi, J. H.; Tang, C. W. Appl. Phys. Lett. 2002, 80, 3201.

Odom, S. A.; Parkin, S. R.; Anthony, J. E. Org. Lett. 2003, 5, 4245.

Wolak, M. A.; Melinger, J. S.; Lane, P. A.; Palilis, L. C.; Landis, C. A.; Delcamp, J.; Anthony, J. E.; Kafafi, Z. H. J. Phys. Chem. B 2006, 110, 7928.

(a) Lin, Y. Y.; Gundlach, D. J.; Jackson, T. N.; Nelson, S. F.; Schlom, D. G. IEEE Electron Device Lett. 1997, 18, 87. (b) Mattheus, C. C.; Dros, A. B.; Baas, J.; Oostergetel, G. T.; Meetsma, A.; de Boer, J. L.; Palstra, T. T. M. Synth. Met. 2003, 138, 475.

(a) Ito, K.; Suzuki, T.; Sakamoto, Y.; Kubota, D.; Inoue, Y.; Sato, F.; Tokito, S. Angew. Chem. Int. Ed. 2003, 42, 1159. (b) Laquindanum, J. G.; Katz, H. E.; Lovinger, A. J. J. Am. Chem. Soc. 1998, 120, 664. (c) Payne, M. M.; Parkin, S. R.; Anthony, J. E.; Kuo, C. C.; Jackson, T. N. J. Am. Chem. Soc. 2005, 127, 4986. (d) Podzorov, V.; Sysoev, S. E.; Loginova, E.; Pudalov, V. M.; Gersh- enson, M. E. Appl. Phys. Lett. 2003, 83, 3504. (e) Moon, H.; Zeis, R.; Borkent, E.; Besnard, C.; Lovinger, A. J.; Siegrist, T.; Christian Kloc, C.; Bao, Z. J. Am. Chem. Soc. 2004, 126, 15322. (f) Sakamoto, Y.; Suzuki, T.; Kobayashi, M.; Gao, Y.; Fukai, Y.; Inoue, Y.; Sato, F.; Tokito, S. J. Am. Chem. Soc. 2004, 126, 8138. (g) Meng, H.; Sun, F.; Goldfinger, M. B.; Jaycox, G. D.; Li, Z.; Marshall, W. J.; Blackman, G. S. J. Am. Chem. Soc. 2005, 127, 2406.

Lim, Y.-F.; Shu, Y.; Parkin, S. R.; Anthony, J. E.; Malliaras, G. G. J. Mater. Chem. 2009, 19, 3049.

Kaur, I.; Jia, W.; Kopreski, R. P.; Selvarasah, S.; Dokmeci, M. R.; Pramanik, C.; McGruer, N. E.; Miller, G. P. J. Am. Chem. Soc. 2008, 130, 16274.

Nagano, M.; Hasegawa, T.; Myoujin, N.; Yamaguchi, J.; Itaka, K.; Fukumoto, H.;Yamamoto, T.; Koinuma, H. Jpn. J. Appl. Phys. Part 2-Lett. 2004, 43, 315.

(a) Allinson, G..; Bushby, R. J.; Jesudason, M. V.; Paillaud, J. L.; Taylor, N. J. Chem. Soc., Perkin Trans. 2 1997, 147. (b) Miao, Q.; Chi, X.; Xiao, S.; Zeis, R.; Lefenfeld, M.; Siegrist, T.; Steigerwald, M. L.; Nuckolls, C. J. Am. Chem. Soc. 2006, 128, 1340. (c) Rainbolt, J. E.; Miller, G. P. J. Org. Chem. 2007, 72, 3020.

Sparfel, D.; Gobert, F.; Rigaudy, J. Tetrahedron 1980, 36, 2225.

(a) Konieczny, M.; Harvey, R. G. J. Org. Chem. 1979, 44, 4813. (b) Netka, J.; Crump, S. L.; Rickborn, B. J. Org. Chem. 1986, 51, 1189.

Martin, N.; Behnisch, R.; Hanack, M. J. Org. Chem. 1989, 54, 2563.

Reichwagen, J.; Hopf, H.; Guerzo, A. D.; Desvergne, J. P.; Belin, C.; Laurent, H. B. Org. Lett. 2005, 7, 971.

Reichwagen, J.; Hopf, H.; Guerzo, A. D.; Desvergne, J. P.; Laurent, H. B. Org. Lett. 2004, 6, 1899.

Chan, S. H.; Yick, C. Y.; Wong, Henry N. C. Tetrahedron 2002, 58, 9413.

Takahashi, T.;Kitamura, M.; Shen, B.; Nakajima, K. J. Am. Chem. Soc. 2000, 122, 12876.

(a) Anthony, J. E.; Eaton, D. L.;Parkin, S. R. Org. Lett. 2002, 4, 15. (b) Anthony, J. E.; Brooks, J. S.; Eaton, D. L.; Parkin, S. R. J. Am. Chem. Soc. 2001, 123, 9482.

Payne, M. M.; Parkin, S. R.; Anthony, J. E. J. Am. Chem. Soc. 2005, 127, 8028.

Rodrìguez, D.; Castedo, L.; Domìnguez, D.;Saá, C. Org. Lett. 2003, 5, 3119.

Lin, Y. C.; Lin, C. H. Org. Lett. 2007, 9, 2075.

Mallouli, A.; Lepage, Y. Synthesis, 1980, 9, 689.

Lin, K.-H.; Pal, B.; Tsou, L.-D.; Lin, C.-H. Chem. Comm. 2009, 803.

Uno, H.; Yamashita, Y.; Kikuchi, M.; Watanabe, H.; Yamada, H.; Okujima, T.; Ogawac, T.; Ono, N. Tetrahedron Lett. 2005, 46, 1981.

Yamada, H.; Yamashita, Y.; Kikuchi, M.; Watanabe, H.; Okujima, T.; Uno, H.; Ogawa, T.; Ohara, K.; Ono, N. Chem.-Eur. J. 2005, 11, 6212.

Gabioud, R.; Vogel, P. Tetrahedron 1980, 36, 149.

Schnatter, W. F. K.; Almarsson, O.; Bruice, T. C. Tetrahedron 1991, 47, 8687.

Xie, Z.; Yang, B.; Liu, L.; Li, M.; Lin, D.; Ma, Y.; Cheng, G.; Liu, S. J. Phys. Org. Chem. 2005, 18, 962.

Krawczyk, H.; Wasek, K.; Kedzia, J.; Wojciechowski, J.; Wolf, W. M. Organic and Biomolecular Chemistry 2008, 6, 308.

Gimzewski, J. K.; Joachim, C. Science 1999, 283, 1683.

Chidsey, C. E. D. Science 1991, 251, 919.

(a) Schull, T. L.; Kushmerick, J. G.; Patterson, C. H.; George, C.; Moore, M. H.; Pollack, S. K.; Shashidhar, R. J. Am. Chem. Soc. 2003, 125, 3202. (b) Cygan, M. T.; Dunbar, T. D.; Arnold, J. J.; Bumm, L. A.; Shedlock, N. F.; Burgin, T. P.; Jones, L.; Allara, D. L.; Tour, J. M.; Weiss, P. S. J. Am. Chem. Soc. 1998, 120, 2721.

Reed, M. A.; Zhou, C.; Muller, C. J.; Burgin, T. P.; Tour, J. M. Science 1997, 278, 252.

(a) Finklea, H.; Hanshew, D. D. J. Am. Chem. Soc. 1992, 114, 3173. (b) Weber, K.; Hockett, L.; Creager, S. J. Phys. Chem. B 1997, 101, 8286.

Sikes, H. D.; Smalley, J. F.; Dudek, S. P.; Cook, A. R.; Newton, M. D.; Chidsey, C. E. D.; Feldberg, S. W. Science 2001, 291, 1519.

(a) Ramachangran, G. K.; Tomfohr, J. K.; Li, J.; Sankey, O. F.; Zarate, X.; Primak, A.; Terazono, Y.; Moore, T. A.; Moore, A. L.; Gust, D.; Nagahara, L. A.; Lindsay, S. M. J. Phys. Chem. B 2003, 107, 6126. (b) Rawlett, A. M.; Hopson, T. J.; Nakahara, L. A.; Tsui, R. K.; Ramachangran, G. K.; Lindsay, S. M. Appl. Phys. Lett. 2002, 81, 3043. (c) Blum, A. S.; Kushmerick, J. G.; Pollack, S. K.; Yang, J. C.; Moore, M.; Naciri, J.; Shashidhar, R.; Ratna, B. R. J. Phys. Chem. B 2004, 108, 18124. (d) Xiao, X.; Nagahara, L. A.; Rawlett, A. M.; Tao, N. J. Am. Chem. Soc. 2005, 127, 9235. (e) Selzer, Y.; Cabassi, M. A.; Mayer, T. S.; Allara, D. L. J. Am. Chem. Soc. 2004, 126, 4052.

(a) Horne, S.; Rodrigo, R. J. Chem. Soc. Chem. Commun., 1992, 164. (b) Nicolaou, K.C.; Bunnage, M. E.; Koide, K. J. Am. Chem. Soc. 1994, 116, 8402. (c) Keck, G.; E.; McHardy, S. F.; Murry, J. A. J. Am. Chem. Soc. 1995, 117, 7289. (d) Piettre, A.; Massardier, C.; Chevenier, E.; Gimbert, Y.; Greene, A. E. Synlett, 2002, 12, 2086.

Martin, E. L.; Wheland, R. C. J. Org. Chem. 1975, 40, 3101.

Braun, A.; Tcherniac, J. Berichte der Deutschen Chemischen Gesellschaft, 1907, 40, 2709.

Henri de Diesbach, Edmond von der Weid, Helvetica Chimica Acta, 1927, 10, 886.

(a) Makarov, S.; Litwinski, C.; Ermilov, E. A.; Suvorova, O.; Röder, B.; Wöhrle, D. Chem.-Eur. J. 2005, 12, 1468. (b) Calvete, M. J. F.; Dini, D.; Flom, S.; Hanack, R. M.; Pong, R. G. S.; Shirk, J. S. Eur. J. Org. Chem. 2005, 3499.

Pickaert, G.; Ziessel, R. Synthesis 2004, 16, 2716.