| 研究生: |
陳光伯 Chen, Kuang-Po |
|---|---|
| 論文名稱: |
一、以醋酸錳(III)進行自由基反應合成1,4-醌類化合物及旋環化合物
二、以離子性方法合成異噁唑化合物及2,3-二氫呋喃化合物 1.Synthesis of 1,4-quinones and spiro compounds via manganese(III) acetate mediated free radical reactions 2.Ionic methodology in synthesis of isoxazoles and 2,3- dihydrofurans |
| 指導教授: |
莊治平
Chuang, Che-Ping |
| 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: | 2013 |
| 畢業學年度: | 101 |
| 語文別: | 中文 |
| 論文頁數: | 202 |
| 中文關鍵詞: | 醋酸錳(III) 、1, 4-蒽二酮 、旋環內醯胺 、異噁唑 、單鍋 、無溶劑 、2,3-二氫呋喃 |
| 外文關鍵詞: | manganese(III) acetate, anthracene-1,4-diones, spirolatam, isoxazoles, one-pot, solvent-free, 2,3-dihydrofurans |
| 相關次數: | 點閱:99 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 |
第一部分 自由基反應
1.以醋酸錳(III)和1,4-醌類化合物32及1,3-雙羰基化合物33進行自由基反應,能夠依所使用的反應條件而選擇性獲得異呋喃化合物34及1,4-蒽二酮化合物35。
2.利用醋酸錳(III)、對甲苯磺酸鈉和N-(β-烯丙基碸基丙醯基)-4-甲氧基萘胺化合物65進行自由基環合反應能夠獲得旋環內醯胺化合物75,而完全無六員環(6-endo-trig)的產物。
第二部分 離子性反應
1.利用α-硝基肉桂酸乙酯化合物60和2-硝基乙酸乙酯在鹼性條件下合成多取代基的異噁唑化合物61。此外,利用2-硝基乙酸乙酯和芳香醛59在鹼性條件下亦能單鍋合成異噁唑化合物。單鍋無溶劑條件也成功合成異噁唑醯胺產物82。
2.利用單鍋多組分反應合成多取代基的2,3-二氫呋喃化合物;並探討無溶劑條件的合成方法。
Part 1 Free radical reaction
1.A free radical reaction medicated by manganese(III) acetate between 2-benzoyl-1,4-benzoquiones and 1,3-dicarbonyl compounds produces benzo[c]furan-4,7-diones 34 and anthracene-1,4-diones 35 with chemoselectivity.
2.A free radical cyclization reaction mediated by Mn3+ between TsNa and N-(β-allylsulfonylpropionyl)-4-methoxy- naphthylamine 65 can produce spirolatam 75 without any 6-endo-trig product.
Part 2 Heterolytic reaction
1.Highly functionalized isoxazoles can be synthesized from ethyl α- nitrocinnamates 60 and ethyl nitroacetate under basic condition.Besides, highly functionalized isoxazoles can also be synthesized from ethyl nitroacetate and aromatic aldehydes under basic condition.
3-Amidoisoxazoles 82 can also be synthesized from ethyl nitroacetate, aromatic aldehydes, morpholine and pyridinium bromide under not only one-pot but solvent-free condition.
2.Highly functionalized 2,3-dihydrofurans 34 can be synthesized by one-pot multicomponent reaction. The solvent-free condition is also effective.
第一章
1. Forbes, M. D. E. “Carbon-centered free radicals and radical cations : structure, reactivity, and dynamics”, Wiley, 2010, p.1-6.
2. Gomberg, M. J. Am. Chem. Soc. 1900, 22, 757.
3. Taylor, H. S. Trans. Faraday Soc. 1926, 21, 560.
4. Hey, D. H.; Waters, W. A. Chem. Rev. 1937, 21, 169.
5. Renaud, P.; Weiheim, M. P. “Radicals in organic synthesis: Basic principles ”, Wiley, 2000, Vol. 1, Ch.1.
6. Giese, B.; “ Radicals in organic synthesis : formation of carbon-carbon bonds ”, Pergamon, 1986, p.13-36.
7. Togo, H. “Advanced free radical reactions for organic synthesis”, Elsever, 2004, Ch. 1.
8. Giese, B. Angew. Chem. Int. Ed. 1983, 22, 753-764.
9. Renaud, P.; Weiheim, M. P. “ Radicals in organic synthesis”, Wiley, 2000, Vol. 2, p.152-176.
10. Bard, R. R.; Bunnett, J. F. J. Org. Chem. 1980, 45, 1547.
11. Citterio, A.; Fancelli, D.; Finzi, C.; Pesce, L. J. Org. Chem. 1989, 54, 2713.
12. Warner, C. R.; Strunk, R. J.; Kuivila, H.G. J. Org. Chem. 1966, 31, 3381.
13. Srikrishna, A.; Sharma, G. V. R. J. Chem. Soc., Perkin Trans. 1 1997, 177.
14. Zhang, W.; Dowd, P. Tetrahdron Lett. 1992, 33, 7307.
15. Denis, R. C.; Gravel, D. Tetrahdron Lett. 1994, 35, 4531.
16. Baldwin, J. E. J. Chem. Soc. Chem. Comm. 1976, 734.
17. Araki, Y.; Endo, T.; Arai, Y.; Tanji, M.; Ishido, Y. Tetrahdron Lett. 1989, 30, 7307.
18. Park, S. -U.; Varick, T. R.; Newcomb, M. Tetrahdron Lett. 1990, 31, 2975.
19. Jung, M. E.; Trifunovich, I. D.; Lensen, N. Tetrahdron Lett. 1992, 33, 6719.
20. Jung, M. E.; Marquez, R.; Houk, K. N. Tetrahdron Lett. 1999, 40, 2661.
21. Fremont, S. L.; Belletire, J. L.; Ho, D. M. Tetrahdron Lett. 1991, 32, 2335.
23. Sato, T.; Chono, N.; Ishibashi, H.; Ikeda, M. J. Chem. Soc., Perkin Trans. 1 1995, 1115.
24. Tsai, Y. -M; Cherng, C. -D. Tetrahdron Lett. 1991, 32, 3515.
25. Tsai, Y. -M; Tang, K. -S.; Jiaang, W.-T. Tetrahdron Lett. 1993, 34, 1303.
26. Andrés, C.; Duque-Soladana, J. P.; Pedrosa, R. J. Org. Chem. 1999, 64, 4282.
27. Hartung, J.; Daniel, K.; Rummey, C.; Bringmann, G. Org. Biomol. Chem., 2006, 4, 4089.
28. Pal, S.; Mukherjee, M.; Podder, D.; Mukherjeec, A. K.; Ghatak, U. R.
J. Chem. Soc. Chem. Comm. 1991, 1591.
29. Ward, D. E.; Gai, Y.; Kaller, B. F. J. Org. Chem. 1995, 60, 7830.
30. Neumann, W. P.; Hillgärtner, H.; Baine, K. M.; Dicke, R.; Vorspohl, K. Tetrahdron 1989, 45, 951.
31. Tsubusaki, T.; Nishino, H. Tetrahdron 2009, 65, 9448.
32. Boger, D. L.; Mathvink, R. J. J. Org. Chem. 1988, 53, 3377.
33. Boeck, B. D.; Herert, N.; Pattenden, G. Tetrahdron Lett. 1998, 39, 6971.
34. Lee, E.; Yoon, C. H. Tetrahdron Lett. 1996, 37, 5929.
35. Gibson, S. E.; Guilloa, N.; Tozer, M. J. Chem. Commun., 1997, 637.
36. Heiba, E. I.; Dessau, R. M.; Koehl, W. J. Jr. J. Am Chem. Soc. 1968, 90, 5905.
37. Corey, E. J.; Gross, A. W. Tetrahdron Lett. 1985, 26, 4291.
38. Snider, B. B.; McCarthy, B. A. J. Org. Chem. 1993, 58, 6217.
39. Zoretic, P. A.; Fang, H. J. Org. Chem. 1998, 63, 7213.
40. Renaud, P.; Weiheim, M. P. “ Radicals in organic synthesis”, Wiley, 2000, Vol. 1, p.219-228.
41. Molander, G. A. Chem. Rev. 1992, 92, 29.
42. Jempty, T. C.; Miller, L. L.; Mazur, Y. J. Org. Chem. 1980, 45, 749.
43. Booker-Milburn, K. I.; Thompson, D. F. J. Chem. Soc., Perkin Trans. 1 1995, 2315.
第二章
1. Thomas, R. H. “Naturally occurring quinones IV”, London, Blackie Academic and Professional 1997, p.14, p.112, p.321 and p.232.
2. Iqbal, J.; Bhatia, B.; Nayyar, N. K. Chem. Rev. 1994, 94, 519.
3. Snider, B. B. Chem. Rev. 1996, 96, 339.
4. Dermir, A. S.; Emull, A. M. Curr. Org. Syn. 2007, 4, 321.
5. Nair, V.; Deepth, A. Chem. Rev. 2007, 107, 1862.
6. Molander, G. A. Chem. Rev. 1992, 92, 29.
7. Wang, S. -F.; Chuang, C. -P.; Lee, J. -H. Heterocycle 1999, 50, 487.
8. Tsai, A. -I.; Wu, Y. -L.; Chuang, C. -P. Tetrahedron 2001, 57, 7829.
9. Chen, H. -L.; Lin, C. -Y.; Cheng, Y. -C.; Tsai, A. -I.; Chuang, C. -P. Synthesis 2005, 977.
10. Lin, C. -Y.; Cheng, Y. -C.; Tsai, A. -I.; Chuang, C. -P. Org. Biomol. Chem. 2006, 4, 1097.
11. 鄭宇志, 國立成功大學化學研究所碩士論文, 2005.
12. 李恆群, 國立成功大學化學研究所碩士論文, 2008.
13. Wu, Y. -L.; Chuang, C. -P.; Lin, P. -Y. Tetrahedron 2000, 56, 6209.
14. 駱集煜, 國立成功大學化學研究所碩士論文, 2006.
已發表文章
“Free radical reaction between 2-benzoyl-1, 4-benzoquinonesand 1, 3-di- carbonyl compounds”, Chen, K. -P.; Lee, H. -Q.; Cheng, Y. -C.; Chuang, C. -P. Org. Biomol. Chem. 2009, 7, 4074.
第三章
1. Quilico, A. Chem. Heterocycl. Comp. 1962, 17, 1.
2. Grigg, R.; Hayes, R.; Jackson, J. L.; King, T. J. J. Chem. Soc. 1973, 349.
3. Jensen, S.; Torssell, K. B. G. Acta Chimica Scandinavica 1995, 45, 53.
4. Satoh, M.; Takeuchi, N.; Fujita, T.; Yamazaki, K.; Tobinaga, S. Chem. Pharm. Bull. 1998, 46, 1501.
5. Beam, C. F.; Dyer, M. C. D.; Schwarz, R. A.; Hauser, C. R. J. Org. Chem. 1970, 35, 1806.
6. Bowden, K.; Crank, G.; Ross, W. J. J. Chem. Soc. C. 1968, 172.
7. Oster, T. A.; Harris, T. M. J. Org. Chem. 1983, 48, 4307.
8. Short, K. M.; Ziegler, C. B. Jr. Tetrahdron Lett. 1993, 34, 75.
9. Umesha, K. B.; Kumar, K. A.; Lokanatha, Rai K. M.; Syn. Comm. 2002, 32, 1841.
10. Yavari, I.; Moradi, L. Tetrahdron Lett. 2006, 47, 1627.
11. Rao, R. J. R.; Bhujanga, A. K. S.; Sreenivas, N.; Suneel, B. S.; Murthy, Y. L. N. J. Kor. Chem. Soc. 2011, 55, 243.
12. Ballini, R.; Bosica, G.; Fiorini, D.; Palmieri, A.; Petrini, M. Chem. Rev. 2005, 105, 933.
13. Im, Y. J.; Lee, K. Y.; Kim, T. H.; Kim, J. N. Tetrahdron Lett. 2002, 43, 4675.
14. 陳裕君, 國立成功大學化學所碩士論文, 2009.
15. Shinmon, N.; Cava, M. P.; Brown, R. F. C. J. Chem. Soc., Chem. Comm. 1980, 1020.
16. Chen, K. -P.; Chen, Y. -J.; Chuang, C. -P. Eur. J. Org. Chem. 2010, 5292. Ref. 13.
17. Ratts, K. W.; Howe, R. K.; Pillips, W. G. J. Am. Chem. Soc. 1969, 91, 22, 6115.
已發表文章
“Ethyl α-nitrocinnamates in the synthesis of highly functionalized isoxazoles”, Chen, K. -P.; Chen, Y. -J.; Chuang, C. -P. Eur. J. Org. Chem. 2010, 5292.
第四章
1. Melikyan, G. G.; Sargsyan, A. B.; Mkrtchyan, D. A.; Azaryan, G. Kh.; Badanyan, Sh. O. Chem. Heterocycl. Comp. 1992, 392.
2. Schoop, A.; Greiving, H.; Göhrt, A. Tetrahedron Lett. 2000, 41, 1913.
3. Sammes, P. G.; Jaxa-Chamiec, A. A.; Kennewell, P. D. J. Chem. Soc., Perkin Trans. 1 1980, 170.
4. Yamamoto, I.; Saikai, T.; Ohta, K.; Matsuzaki, K.; Fukuyama, K. J. Chem. Soc., Perkin Trans. 1 1985, 2785.
5. Mélot, J. M.; Texier-Boullet, F.; Foucaud, A. Tetrahedron 1988, 44, 2215.
6. Hagiwara, H.; Sato, K.; Suzuki, T.; Ando, M. Tetrahedron Lett. 1997, 38, 2103.
7. Antonioletti, R; Malancona, S; Bovicelli, P. Tetrahedron 2002, 58, 8825.
8. Jiang, Y.; Ma, D. Tetrahedron: Asymmetry 2002, 13, 1033.
9. Chuang, C. -P.; Tsai, A. -I. Synthesis 2006, 675.
10. Heiba, E. I.; Dessau, R. M. J. Org. Chem. 1974, 39, 3456.
11. Corey, E. J.; Ghosh, A. K. Chem. Lett. 1987, 223.
12. Nair, V.; Mathew, J.; Radhakrishnan, K. V. J. Chem. Soc., Perkin Trans. 1 1996, 1487.
13. Davies, Huw M. L.; Ahmed, G.; Calvo, R. L.; Churchill, M.R.; Churchill, D. G. J. Org. Chem. 1998, 63, 2641.
14. Alonso, M. E.; Morales, A.; Chitty, A. W. J. Org. Chem. 1982, 47, 3747.
15. Wang, Q. -F.; Hou, H.; Hui, L.; Yan C. -G. J. Org. Chem. 2009, 74, 7403.
16. Sahu, D. P.; Giri, S. K.; Varshney, V.; Kumar, S. Synth. Commun.
2009, 39, 3406.
17. Zhong, C.; Liao, T.; Tuguldur, O.; Shi, X. Org. Lett. 2010, 12, 2064.
18. Chuang, C. -P.; Chen, K. -P.; Hsu, Y. -L.; Tsai, A. -I.; Liu, S. -T. Tetrahedron 2008, 64, 7511.
19. Tsuge, O.; Kanemasa, S.; Takenaka, S. Bull. Chem. Soc. Jpn. 1985, 58. 3137.
20. Tanaka, K.; Toda, F. Chem. Rev. 2000, 100, 1025.
21. Toda, F.; Suzuki, T.; Higa, S. J. Chem. Soc., Perkin Trans. 1 1998, 3521.
22. Ren, Z.; Cao, W.; Tong, W. Synth. Commun. 2002, 32, 3475.
已發表文章
“N-Phenacylpyridinium bromides in the one-pot synthesis of 2, 3-di- hydrofurans”, Chuang, C. -P.; Chen, K. -P. Tetrahedron 2012, 68, 1401.
校內:2016-02-01公開