本篇論文主要分為兩部分，將聯伸二苯以及茚并茀化合物兩種平面反芳香性分子透過有機合成的方式，延伸合成出二茚并聯伸二苯化合物。
本實驗室先前合成出具雙自由基性質且穩定度高的二茚并聯伸二苯衍生物5、7。因此本論文在第一部分嘗試以化合物7進行結構衍生合成具有多自由基的二茚并聯伸二苯衍生物。首先利用溴化銅進行氧化耦合反應成功製備八員環前驅物21，並藉由X-ray單晶繞射與MALDI-TOF質譜確認分子結構與分子量。接下來在利用四正丁基氟化銨去除三甲基矽基的步驟上，雖未能順利得到化合物22，但也成功合成出具四自由基性質之八員環化合物24。
第二部分以化合物5進行官能基的修飾，探討碳碳三鍵對於雙自由基性質的影響以及進一步延伸合成多自由基二茚并聯伸二苯衍生物。以有機全合成方式成功合成出具三鍵官能基之化合物9，但在純化過程中，因共振型態使其容易形成多聚物致使難以純化以及進行相關性質的探討。在延伸合成八員環化合物中，未能夠合成出前驅物35、42，但其中在鈀催化劑及DBU的反應條件下，意外地得到聯伸三苯的化合物38並透過X-ray單晶繞射確認分子結構。

Conjugated polycyclic hydrocarbons have caught scientists’ eyes for a long time because of the potential application in optical and electronic devices. Biradical molecules are one of the conjugated polycyclic hydrocarbons which have many particular properties to study further. However, they are very unstable under ambient conditions due to their high reactive unpaired electrons.
Our group have synthesized some new diindeno-fused arenes, and they are air-stable with biradical characteristics. In this study, we would like to synthesize 2,13-dimesityl -2,13-diindeno[2,1-b:2’,1’-h] biphenylene dimer (8), 3,12-bis(2-(triisopropylsilyl)ethynyl)-diindeno [2,1-a:2’,1’-i] biphenylene (9), and 3,12,17,26-tetrakis(2-(triisopropylsilyl) ethynyl)-tetraindeno [2,1-a:2’,1’-i] tetraphenylene (10) to extend π conjugation and explore the effect on biradical characteristics between different substituents base on the previous research.
The tetraradical compound, 2,13-dimesityl-4-trimethylsilyl-2,13-diindeno[2,1-b:2’,1’-h] biphenylene dimer (24), was synthesized and confirmed the structure by single-crystal X-ray diffraction during the synthesis of symmetric product 8. And 9 was successfully synthesized and proven by MALDI-TOF mass. It transforms in p-QDM type structure as transient intermediates by resonance. It will form dimer or react with oxygen randomly because of high reactivity. Therefore, it was hard for us to purify and analyze. Although the synthesis of precursors of 10 is failed, 1-ethoxycarbonyl-8-(2-ethoxycarbonylphenyl)triphenylene (38) can be synthesized by 1,8-Bis(2-ethoxycarbonylphenyl)biphenylene (28) reacting with palladium catalyst and DBU. And The molecular structures was confirmed by single-crystal X-ray diffraction.

1. Toda, F.; Garratt, P. Chem. Rev. 1992, 92, 1685-1707.
2. Fawcett, J. K.; Trotter, J. Acta Cryst. 1966, 20, 87-93.
3. Leung, M.-K.; Balaji Viswanath, M .; Chou, P.-T.; Pu, S.-C.; Lin, H.-C.; Jin, B.-Y. J. Org. Chem. 2005, 70, 3560-3568.
4. Adam, W.; Balci, M.; Kilic, H. J. Org. Chem. 1998, 63, 8544-8546.
5. Lin, S.-C.; Chen, J.-A.; Liu, M.-H.; Oliver Su, Y.; Leung M.-K. J. Org. Chem. 1998, 63, 5059-5063.
6. Lothrop, W. C. J. Am. Chem. Soc. 1941, 63, 1187-1191.
7. (a) Campbell, C. D.; Rees, C. W. J. Chem. Soc. C: Org. 1969, 742-747. (b) Logullo, F. M.; Seitz, A. H.; Friedman L. Org. Synth. 2003, 48, 12.
8. Iyoda,M.; Humayun Kabir, S. M.; Vorasingha, A.; Kuwatani, Y.; Yoshida, M. Tetrahedron Lett. 1998, 39, 5393-5396.
9. (a) Berris, B. C.; Lai, Y.-H.; Vollhardt, K. P. C. J. Chem. Soc., Chem. Commun. 1982, 953-954. (b) Berris, B. C.; Hovakeemian, G. H.; Lai, Y.-H.; Mestdagh, H.; Vollhardt, K. P. C. J. Am. Chem. Soc. 1985, 107, 5670-5687. (c) González Gómez, J. A.; Green, J. R.; Vollhardt, K. P. C. Synlett 2011, 6, 805–808.
10. Wang, S.-L.; Pan, M.-L.; Su, W.-S.; Wu, Y.-T. Angew. Chem. Int. Ed. 2017, 56, 14694–14697.
11. (a) Watson, M. D.; Fechtenko¨tter, A; Mu¨llen, K. Chem. Rev. 2001, 101, 1267−1300. (b) Christensen, M. A.; Parker, C. R.; Sørensen, T. J.; de Graaf, S.; Morsing, T. J.; Brock-Nannestad, T.; Bendix J.; Haley, M. M.; Rapta, P.; Danilov, A.; Kubatkin,S.; Hammerich, O.; Nielsen, M. B. J. Mater. Chem. C, 2014, 2, 10428–10438.
12. Clar, E. Thw Aromatic Sextet; Wiley-VCH: London ,1972.
13. Zhou, Q; Carroll, P. J.; and Swager, T. M. J. Org. Chem. 1994,59, 1294-1301.
14. Chase, D. T.; Rose, B. D.; McClintock, S. P.; Zakharov, L. N.; Haley M. M. Angew. Chem. Int. Ed. 2011, 50, 1127-1130.
15. (a) Chase, D. T.; Fix, A. G.; Rose, B. D.; Weber, C. D.; Nobusue, S.; Stockwell, C. E.; Zakharov, L. N.; Lonergan, M. C.; Haley, M. M. Angew. Chem. Int. Ed. 2011, 50, 11103 –11106. (b) Chase, D. T.; Fix, A. G.; Kang, S. J.; Rose, B. D.;Weber, C. D.; Zhong, Y.; Zakharov, L. N.; Lonergan, M. C.; Nuckolls, C.; Haley, M. M.
J. Am. Chem. Soc. 2012, 134, 10349−10352. (c) Frederickson, C. K.; Zakharov, L. N.; Haley, M. M. J. Am. Chem. Soc. 2016, 138, 16827−16838.
16. (a) Shimizu, A.; Tobe, Y. Angew. Chem. Int. Ed. 2011, 50, 6906 –6910. (b) Shimizu, A.; Kishi, R.; Nakano, M.; Shiomi, D.; Sato, K. Takui, T.; Hisaki, I.; Miyata, M.; Tobe, Y. Angew. Chem. Int. Ed. 2013, 52, 6076–6079.
17. (a) Motta, S. D.; Negri, F.; Fazzi, D.; Castiglioni, C.; Canesi, E. V. J. Phys. Chem. Lett. 2010, 1, 3334–3339. (b) Sun, Z.; Ye, Q.; Chi, C.; Wu, J. Chem. Soc. Rev. 2012, 41, 7857–7889.
18. Ni, Y.; Lee, S.; Son, M.; Aratani, N.; Ishida, M.; Samanta, A.; Yamada, H.; Chang, Y.-T.; Furuta, H.; Kim, D.; Wu, J. Angew. Chem. Int. Ed. 2016, 55, 2815–2819.
19. (a) Varnavski, O.; Abeyasinghe, N.; Aragó, J.; Serrano-Pérez, J. J.; Ortí, E.; Lopez Navarrete, J. T.; Takimiya, K.; Casanova, D.; Casado, J.; Goodson, T. J.Phys. Chem. Lett. 2015, 6, 1375–1384. (b) Minami, T.; Nakano, M. J. Phys. Chem. Lett. 2012, 3, 145–150. (c) Wilson, M. W. B.; Rao, A.; Clark, J.; Kumar, R.S.S.; Brida, D.; Cerullo, G; Friend, R. H. J. Am. Chem. Soc. 2011, 133, 11830–11833. (d) Kubo T. Chem. Lett. 2015, 44, 111–122.
20. Leroux, F. R.; Berthelot, A.; Bonnafoux, L.; Panossian, A.; Colobert, F. Chem. Eur. J. 2012, 18, 14232–14236
21. Greulich, T. W.; Yamaguchi, E.; Doerenkamp, C.; Lübbesmeyer, M.; Daniliuc, C. G.; Fukazawa, A.; Eckert, H.; Yamaguchi, S.; Studer, A. Chem. Eur. J. 2017, 23, 6029–6033.
22. Humayun Kabir, S. M.,; Iyoda, M. Synthesis 2000, 13, 1839–1842.
23. 洪暉祐碩士論文：國立成功大學 民國一百零八年 七月
24. 甄沛耘碩士論文：國立成功大學 民國一百零九年 七月
25. Miyake, Y.; Wu, M.; Jalilur Rahman, M. ; Kuwatani, Y. Iyoda, M. J. Org. Chem. 2006, 71, 6110–6117.
26. Rajca, A.; Safronov, A.; Rajca, S.; Ross, C. R.; Stezowski, J. J.
J. Am. Chem. Soc. 1996, 118, 7272–7279.
27. 王繼欣碩士論文：國立成功大學 民國一百零七年 七月
28. Pünner, F.; Schieven, J.; Hilt, G. Org. Lett. 2013, 15, 4888–4891.
29. Chollet, A.; Mori, G.; Menendez, C.; Rodriguez, F.; Fabing, I.; Pasca, M. R.; Madacki, J.; Korduláková, J.; Constant, P.; Quémard, A.; Bernardes-Génisson, V.; Lherbet, C.; Baltas, M. Eur. J. Med. Chem. 2015, 101, 218–235.
30. Fu, X.; Zhao, D. Org. Lett. 2015, 17, 5694−5697.
31. (a) Brown, C. J.; Farthing, A. C. Nature 1949, 164, 915−916. (b) Trahanovsky, W. S.; Lorimor, S. P. J. Org. Chem. 2006, 71, 1784−1794.
32.馮玠寧博士論文：國立成功大學 民國一百零五年 一月