喹啉在天然物以及還有藥物活性的成分中，扮演著重要的角色。在某些研究中，屬於喹啉衍生的生物鹼對於抑制在淋巴細胞上病毒的轉移有非常大的效果，使得喹啉結構的化合物受到關注。此種化合物常被做為多種有機化合物的起始物，例如可以合成金屬螯合劑、殺蟲劑；或被當作萜烯(Terpene)、樹脂(resin)的溶劑，引起許多的科學家對於喹啉相關衍生物有相當大的興趣，開始研究喹啉合成方式和相關的藥物活性研究。
本論文分為兩個部份，第一部份主要探討利用非金屬催化的點擊反應，以硝基喹啉做為起始物，與疊氮化鈉反應進行1,3-偶極環加成，可得到有2H-1,2,3-三唑結構的喹啉化合物，並有著理想的產率；在反應中繼續加入1-氟-2-硝基苯及碳酸銫，進行芳香環親核取代反應，即可得到2,4,5-三取代三唑結構的喹啉化合物。本反應所得產物，在目前的研究中以顯示出多樣的抗真菌、抗癌及抗發炎等不同的生物活性，此反應提供快速且高產率之帶有三唑化合物並帶有喹啉結構，希望往後能在各種有機合成中應用。
第二部份中，主要探討使用磷試劑將硝基還原為氨基，並不以金屬為催化劑；將硝基喹啉做為起始物，與三苯基磷在微波加熱下進行反應，可在短時間內得到理想產率的亞胺基膦烷中間產物，接著直接進行水解，可得到帶有氨基的喹啉化合物，並且能夠以萃取的方式簡單純化；此反應所得之中間物多應用於各種不同有機合成中，具有進行各種反應的潛力；此外苯反應也可在非金屬的催化下，將硝基進行還原，避免某些還原反應使保護基脫落，期望未來能應用於有機合成領域中。

The dissertation is divided into two parts summarizing the results base on the experimental works performed during the course of study. The first part include a convenient procedure for the synthesis of 2,4,5-trisubstisute 1,2,3-triazole derivatives via 1,3-Huisgen cycloaddition of sodium azide and quinolone derivatives gives 1,2,3-triazole compound, than reacted with 1-fluoro-2-nitrobenzene and caesium carbonate in one pot by nucleophilic aromatic substitution to form 2,4,5-trisubstisute 1,2,3-triazole derivatives. 1,2,3-triazole play important roles in anticancer、anti-inflammatory and antimicrobial, etc. , it can also be synthesized natural product, being a building block of drugs. Here we provide an efficient and high yield method to synthesis triazole products.
The second part describes a one pot reduction of nitro group without metal on the quinoline by triphenylphosphine. This reaction involving a cadogan reaction of nitro group and from an iminophosphorane intermediate, adding some acids for hydrolysis, and get the products with amine group. quinline is an important compound with a biological activities structure, for example quinine is one of the quinolone derivatives medication used to treat malaria and babesiosis. Iminophosphorane is important and ubiquitous motif structure which show diverse application in material chemistry, agricultural chemistry and medicine, etc. Here we give a convenient and high yield method for reduction of nitro group and the synthesis of iminophosphorane.

1-5、參考文獻

1. Rees, C.W.; Smithen, C.E. Adv. Heterocycl. Chem. 1964, 3, 57.
2. Laurence, B. D.; Michaël, J.; Ann, M. P.; Kim, K.W.; Daniel, G. V.; Norman, G. L. Nat. Prod. Rep., 2008, 25, 1015.
3. Genin, M. J.; Allwine, D. A.; Barbachyn, M. R. J. Med. Chem., 2000, 43, 953.
4. Sivakumar, K.; Xie, F.; Cash, B. M.; Long, S.; Barnhill, H. N.; Wang, Q. Org. Lett. 2004, 6, 4603.
5. Manetsch, R.; Krasiski, A.; Radi, Z.; Raushel, J.; Taylor, P.; Sharpless, K. B.; Kolb, H. C. J. Am. Chem. Soc. 2004, 126, 12809.
6. Aucagne, V.; Hanni, K. D.; Leigh, D. A.; Lusby, P. J.; Walker, D. B. J. Am. Chem. Soc. 2006, 128, 2186.
7. Wacharasindhu, S.; Bardhan, S.; Wan, Z.-K.; Tabei, K.; Mansour, T. S. J. Am. Chem. Soc. 2009, 131, 4174.
8. (a) Anderson, J. C.; Schultz, P. G.; J. Am. Chem.Soc. 2003, 125, 11782; (b) Buckle, D. R.; Rockell, C. J. M.; J. Am. Chem.Soc. 2009, 131, 4174; (c) Tron, G. C.; Pirali, T.; Billington, R. A.; Canonico, P. L.; Sorba, G.; Genazzani, A. A. Med. Res. Rev. 2008, 28, 278;
9. Speers, A. E.; Gregory, C. A.; Benjamin, F. C. J. Am. Chem.Soc. 2003, 125, 4686
10. Genin, M. J.; Allwine, D. A.; Anderson, D. J.; Barbachyn, M. R.; Emmert, D. E.; Garmon, S. A.; Graber, D. R.; Grega, K. C.; Hester, J. B.; Hutchinson, D. K.; Morris, J.; Reischer, R. D.; Stper, D.; Yagi, B. H. J. Med. Chem. 2000, 43, 953.
11. Alvarez, R.; Velazquez, S.; San-Felix, A.; Aquaro, S.; De Clercq, E.; Perno, C.-F.; Karlsson, A.; Balzarini, J.; Camarasa, M. J. J. Med. Chem. 1994, 37, 4194.
12. Masoudim, N. A.; Soud, Y. A. Tetrahedron Lett. 2002, 43, 4021.
13. Wamhoff, H.; 1,2,3-Triazoles In ComprehensiVe Heterocyclic Chemistry; 1984, 5, 669.
14. Buckle, D. R.; Rockell, C. J. M.; Smith, H.; Spicer, B. A. J. Med. Chem. 1986, 29, 2262.
15. Dimorth, O.; Fester, G. Ber. 1910, 43, 2219.
16. Journet, M.; Cai, D.; Kowal, J. J.; Larsen, R. D. Tetrahedron Lett. 2001, 42, 9117.
17. Ykman, P.; L'abbe, G.; Smets, G.Tetrahedron Letters 1970, 60, 5225.
18. Campbell-Verduyn, L.; Elsinga, P. H.; Mirfeizi, L.; Dierckx, R. A.; Feringa, B. L. Org. Biomol. Chem. 2008, 6, 3461.
19. Julian, A. C.; Jeremy, M. B.; Nicholas, J. A.; Carolyn, R. B. J. Am. Chem. Soc., 2008, 130, 11486.
20. Stanislav, A. B.; Svetlana, M. B,; Tanja, W.; Maedot, G,; Karl A. W.; Richard, R. T. J. Med. Chem. 2010, 53, 254.
21. Kristin, O.; Edmund, A. H.; Trond, Vi. H. Tetrahedron Letters, 2007, 48, 2097.
22. Wang, X. K.; Kuang, C. X.; Yang, Q. Eur. J. Org. Chem. 2012, 5, 424
23. Haribabu, A.; Ed, B. Tetrahedron Letters, 2009, 50, 4677.
24. Kolb, H. C.; Finn, M. C.; Sharpless, K. B.; Angew. Chem. Int. Ed. 2001, 40, 2004
25. Barral, K.; Moorhouse, A. D.; Moses, J. E. Org. Lett., 2007, 9, 1809.
26. Christopher, D. H.; Liu, X. M.; Wang, D. Pharmaceutical Research, 2008, 25, 2216.
27. Moore, N.M.; Lin, N. J.; Gallant, N. D.; Becker, M. L.; Biomaterials 2010, 31, 1604.
28. Rostovtsev, V. V. ; Green, L. G.; Fokin, V. V.; Sharpless, K. B. Angew. Chem. Int. Ed., 2002, 41, 2596.
29. Boren, B. C.; Narayan, S.; Rasmussen, L. K.; Zhang, L.; Zhao, H.; Lin, Z.; Jia, G.; Fokin, V. V. J. Am. Chem. Soc., 2008, 130, 8923.

2-5 參考文獻

1. Quin, L. D.; A Guide to Organophosphorus Chemistry, 2000.
2. Su, L. Y.; at. ; J. Plant Physiol. 1992, 140, 168.
3. Yang, S.; Wang,J.; Huo, S. Q.; Wang, M.; Cheng,L. F. Ind. Eng. Chem. Res. 2015, 54, 7777.
4. King, Andrew M.; Aaron, Cynthia K. Organophosphate and Carbamate Poisoning, Emergency Medicine Clinics of North America., 2015, 33, 133.
5. Shandong Weitian Fine Chemical Technology Co., Lte., PATENT: N105330691
A, 2016.
6. Rauhut, M. M.; Hechenbleikner, I.; Currier, H. A.; Schaefer, F. C.; Wystrach, V. P. J. Am. Chem. Soc. 1959, 81, 1103.
7. Gusarova, N. K.; Trofimov, B. A.; Malysheva, S. F.; Shaikhudinova, S. I.; Belogorlova, N.A.; Arbuzova, S. N.; Nepomnyashchikh, K. V.; Dmitriev, V. I. Zh. Obshch. Khim. 1997, 67,70. [Russ. J. Gen. Chem. 1997, 67, 65 (Engl Transl)].
8. Yerushalmi, Roie.; Ho, J. C.; Fan, Z. Y.; Javey A. Angew. Chem. Int. Ed. 2008, 47, 4440.
9. (a) Kasukhin, L. F.; Gololobov, Y. G. Tetrahedron, 1992, 48, 1353; (b) Gusar, N. I.; Russian Chemical Reviews, 1991, 285.
10. Staudinger, H.; Meyer, J. Helv. Chim. Acta, 1919, 2, 635.
11. Gololobov, Y. G., Tetrahedron, 1981, 37, 437.
12. Wittig, G.; Scholkopf, U. Ber. 1954, 87, 1318.
13. Vidal, J.; Guy, L.; StBrin, S.; Collet, A. J. Org. Chem. 1993, 58, 4791.
14. F. Palacios et al. Tetrahedron, 2003, 59, 2617.
15. Schwesinger, R.; Schlemper, H. Angew. Chem. Int. Ed. 1987, 26, 1167.
16. Suzawa, K.; Ueno, M.; Andrew E. H.; Wheatley ; Kondo,Y. Chem. Commun., 2006, 4850.
17. Blackstone, V.; Lough, A.J.; Murray, M.; Manners, I.; J. Am. Chem. Soc. 2009, 131, 3658.
18. J. García-Álvarez et al. J. Org. Chem. 2014, 751, 792.
19. Molina, P.; Aller, E.; Lorenzo, A.; Lo´pez-Cremades, P.; Rioja, I.; Ubeda, A.; Terencio, M. C.; Alcaraz, M. J. J. Med. Chem. 2001, 44, 1011.
20. Blache, Y.; Hichour, M.; Blasi, G.; Chezal, J. M.; Viols, H.; Chavignon, O.; Teulade, J. C.; Chapat, J. P. Heterocycles, 1999 , 51, 1003.
21. Ai, Y.; Yang, G. Z.; Liu, J. C.; Leid, X. X. Magn. Reson. Chem. 2010, 48, 955.
22. Adib *, M.; Sheikhi, E.; Deljoush , A. Tetrahedron, 2011, 67, 4137.
23. Horner, L.; Oediger, H.; Justus Liebigs Ann. Chem. 1959, 627, 142.
24. Heesing, A.; Steinkamp, H. Tetrahedron Lett., 1981, 22, 3827.
25. Łukasik, E.; Wróbel, Z.; Synlett, 2014, 25, 217.
26. Wang, Y. S.; He, H. P.; Shen, Y. M.; Hong, X.; Hao, X. J. J. Nat. Prod. 2003, 66, 416.
27. Morin, J. F.; Leclerc, M. Macromolecules, 2001, 34, 4680.
28. (a) Moskalev, N. V. Khim. Geterotsikl. Soedin., 1990, 2, 187.;(b) Zhu, Z.; Moore, J. S. J. Org. Chem., 2000, 65, 116.
29. Cadogan, J. I. G.; Cameron-Wood, M. Proc. Chem. Soc. 1962, 361.
30. Cadogan, J. I. G.; Cooper A. J. Chem. Soc. 1969, B, 883.
31. Bouchard, J.; Wakim, S.; Leclerc, M. J. Org. Chem. 2004, 69, 5705
32. Li,B.; Pai, R.; Cardinale, S. C.; Butler, M. M.; Peet, N. P.; Moir, D. T.; Bavari, S.; Bowlin, T. L. J. Med. Chem. 2010, 53, 2264.