| 研究生: |
沈韋翰 Shen, Wei-Han |
|---|---|
| 論文名稱: |
自由基環合反應合成3-鹵素-2-喹啉酮類衍生物之研究 Synthesis of 3-Halogeno-2-Quinolinone Derivatives via Free Radical Cyclization Reaction |
| 指導教授: |
莊治平
Chuang, Che-Ping |
| 學位類別: |
碩士 Master |
| 系所名稱: |
理學院 - 化學系 Department of Chemistry |
| 論文出版年: | 2018 |
| 畢業學年度: | 106 |
| 語文別: | 中文 |
| 論文頁數: | 128 |
| 中文關鍵詞: | 自由基 、胺類 、氯化鈷 、2-喹啉酮 |
| 外文關鍵詞: | Free radical, Amine, Cobalt(II) chloride |
| 相關次數: | 點閱:97 下載:1 |
| 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 |
自由基反應在有機化學上扮演重要的腳色,主要是因為其廣泛用於有機合成上,而利用自由基進行環合反應的合成方法已經十分常見。在本篇我們將利用胺類和鈷金屬催化進行自由基環合反應合成一系列2-喹啉酮類化合物。
本論文分成三個部分,第一部分為利用有機胺類三丙胺或氯化鈷金屬與N-取代-[2-(乙炔基)苯基]-2,2,2-三氯乙醯胺類化合物進行自由基環合反應合成3-氯-2-喹啉酮類化合物。
第二部分利用氯化鈷金屬搭配氧化劑過氧化叔丁醇與N-取代-[2-(乙炔基)苯基]-2,2-二溴-2-取代乙醯胺類化合物進行自由基反應得到3-取代-2-喹啉酮類化合物
第三部分則是擴展第二部分的研究,將鈷金屬催化搭配氧化劑的方法應用在N-取代-[2-(乙烯基)苯基]-2,2,2-三取代乙醯胺類化合物上,合成對應之3-取代-2-喹啉酮類化合物。
According to the literature, organic amines are known to work as electron donors in single electron transfer (SET) reaction, and they have been used for many organic reactions via radical mechansim. In this thesis, we have developed an efficient but low costs method for synthesis of 3-halogeno-2-quinolinones by using tri-n-propylamine (TPA). This reaction demonstrated a broad tolerance toward a variety of functional group in excellent yields. In addition to amine method, we also used cobalt (II) chloride with TBHP (tert-butyl hydroperoxide) as an oxidant to synthesize a series of 2-quinolinones derivatives, which also showed wide functionality tolerance in moderate to good yields.
1. J. E. Neve, H. P. Wijesekera, S. Duffy, I. D. Jenkins, J. A. Ripper, S. J. Teague, M. Campitelli, A. Garavelas, G. Nikolakopoulos, P. V. Le, P. A. Leone, N. B. Pham, P. Shelton, N. Fraser, A. R. Carroll, V. M. Avery, C. McCrae, N. Williams and R. J. Quinn, J. Med. Chem., 2014, 57, 1252.
2. G. A. Freeman, C. W. Andrews, A. L. Hopkins, G. S. Lowell, L. T. Schaller, J. R. Cowan, S. S. Gonzales, G. W. Koszalka, R. J. Hazen, L. R. Boone, R. G. Ferris, K. L. Creech, G. B. Roberts, S. A. Short, K. Weaver, D. J. Reynolds, J. Milton, J. Ren, D. I. Stuart, D. K. Stammers and J. H. Chan, J. Med. Chem., 2004, 47, 5923.
3. Z. Wang and J. Wu, Tetrahedron, 2008, 64, 1736.
4. H. Hayashi, Y. Miwa, I. Miki, S. Ichikawa, N. Yoda, A. Ishii, M. Kono and F. Suzuki, J. Med. Chem., 1992, 35, 4893.
5. Y. Ikuma, H. Hochigai, H. Kimura, N. Nunami, T. Kobayashi, K. Uchiyama, Y. Furuta, M. Sakai, M. Horiguchi, Y. Masui, K. Okazaki, Y. Sato and H. Nakahira, Bioorg. Med. Chem., 2012, 20, 5864.
6. Y. Aoki, M. Ishiwara, A. Koda and H. Takagaki, Eur. J. Pharmacol., 2000, 409, 325.
7. L. Knorr, Justus Liebigs Ann. Chem., 1886, 236, 69.
8. E. A. Fehnel, J. Heterocycl. Chem., 1967, 4, 565.
9. K. Inamoto, T. Saito, K. Hiroya and T. Doi, J. Org. Chem., 2010, 75, 3900
10. R. Manikandan and M. Jeganmohan, Org. Lett., 2014, 16, 3568
11. A. C. Mantovani, A. C. Goulart, D. F. Back, P. H. Menezes and G. Zeni, J. Org. Chem., 2014, 79, 10526.
12. A. Ogawa, H. Yokoyama, K. Yokoyama, T. Masawaki, N. Kambe and N. Sonoda, J. Org. Chem., 1991, 56, 5721.
13. C. Wetter, K. Jantos, K. Woithe and A. Studer, Org. Lett., 2003, 5, 2899.
14. C.-Y. Lu and C.-P. Chuang, Synthesis, 2015, 47, 3687
15. C.-P. Chuang and Y.-J. Chen, Tetrahedron, 2016, 72, 1911.
16. F. Zhang, P. Du, J. Chen, H. Wang, Q. Luo and X Wan, Org. Lett., 2014, 16, 1932.
17. P. Du, H. Li, Y. Wang, J. Cheng and X. Wan, Org. Lett., 2014, 16, 6350.
18. C. Liu, E. Shi, F. Xu, Q. Luo, H. Wang, J. Chena and X. Wan, Chem. Commun., 2015, 51, 1214.
19. J. Yu, D. Zhang-Negrerie and Y. Du, Eur. J. Org. Chem., 2016, 562.
20. Y.-C. Cheng, Y.-Yu Chen and C.-P. Chuang, Org. Biomol. Chem., 2017, 15, 2020.
21. H. Ishibashi, S. Haruki, M. Uchiyama, O. Tamura and J. Matsuo, Tetrahedron, 2006, 47, 6263.
22. H. Ishibashi, M. Sasaki and T. Taniguchi, Tetrahedron, 2008, 64, 7771.
23. T. Taniguchi, T. Fujii, A. Idota and H. Ishibashi, Org. Lett., 2009, 11, 3298.
24. W.-J. Xiao and H. Alper, J. Org. Chem., 1999, 64, 9646.
25. P. Ivashkin, S. Couve-Bonnaire, P. Jubault and X. Pannecoucke, Org. Lett., 2012, 14, 2270.
26. Q. Yao, E. P. Kinney and Z. Yang, J. Org. Chem., 2003, 68, 7528.