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博碩士論文 etd-0720111-210435 詳細資訊
Title page for etd-0720111-210435
論文名稱
Title
利用二價汞化合物催化環化反應合成3-醯基苯并[b]噻吩之研究
Synthesis of 3-Acylbenzo[b]thiophenes via Mercury (II)-Catalyzed Cyclization reaction
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
191
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2011-06-13
繳交日期
Date of Submission
2011-07-20
關鍵字
Keywords
苯并噻吩、二價汞化物、Pummerer type 環化反應、亞碸
mercury dichloride, benzo[b]thiophene, sulfoxide, Pummerer type cyclization reaction
統計
Statistics
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中文摘要
本論文研究以鄰位具炔類取代基之亞碸化合物,經二價汞化物催化反應,以苯為溶媒,加熱迴流反應24 小時,得到三號位置具醯基取代基之苯并噻吩化合物。比較炔類結構上具不同取代基之亞碸反應物,則取代基為推電子基者,所得之苯并噻吩產率較高;拉電子基取代基
則降低苯并噻吩之產率。其它亞碸反應物,以benzyl 取代原本硫原子所具有之甲基取代基,則增進反應之產率。同位素效應之研究,發現該反應途徑為Pummerer type 環化反應。
Abstract
Treatment of 1-(methylsulfinyl)-2-(phenylethynyl)benzene with 10 mol % of mercury dichloride and 1 equivalent of
2,3-dichloro-5,6-dicyano-1,4-benzoquinone in refluxing benzene gave benzo[b]thiophene in good yields. This method tolerated various functional
groups in phenylethynyl moiety, including electron donating groups and electron withdrawing groups. Useing
1-(benzylsulfinyl)-2-(phenylethynyl)benzene as reaction substrate increased the yields of benzo[b]thiophene derivatives. Isotope effect showed that this cyclization reaction belong to Pummerer type cyclization
reaction.
目次 Table of Contents
中文摘要.......................................................................................................ii
Abstract ........................................................................................................iii
圖目錄..........................................................................................................vi
表目錄.........................................................................................................vii
第一節 緒論................................................................................................. 1
1.1 苯并噻吩的介紹............................................................................. 1
1.2 二、三號位有取代基的苯並噻吩合成......................................... 5
1.3 近十年苯并噻吩一步驟的合成反應............................................. 9
(I) 自由基環化反應....................................................................... 9
(II) 親電性金金屬合成................................................................ 10
(III) Pummerer type 的環化反應................................................. 10
1.4 金化物催化之缺類加成反應....................................................... 12
1.4.1 前言..................................................................................... 12
1.4.2 Hydroamination of alkyne.................................................... 12
1.4.3 Hydroalkoxylation of alkyne................................................ 12
1.4.4 Cyclization of b-ynones........................................................ 13
1.4.5 以sulfoxide 當作nucleophile ............................................ 13
第二節 結果與討論................................................................................... 16
2.1 研究動機....................................................................................... 16
v
2.2 起始物製備................................................................................... 17
2.3 最佳化條件之尋找....................................................................... 20
2.4 3-Acylbenzothiophenes 之合成..................................................... 27
2.5 同位素氘取代探討反應機構....................................................... 29
第三節 結論............................................................................................... 31
第四節 參考文獻....................................................................................... 32
第五節 實驗部份....................................................................................... 35
5.1 儀器部分....................................................................................... 35
5.2 藥品............................................................................................... 36
5.3 實驗步驟....................................................................................... 38
光譜資料...................................................................................................................... 74
參考文獻 References
1. Thomas, J. B.; Rodney, G. Z. J. Org. Chem. 1970, 35, 1729
2. Perry, N. B.; Blunt , J. W.; Munro, M. H. G. Tetrahedron. 1988, 44,
1727.
3. Barrows, L. R.; Radisky, D. C.; Copp, B. R.; Swaffar, D. S.; Kramer, R.
A.; Warters, R. L.; Ireland, C. M. Anti-Cancer Drug Des. 1993, 8, 333
4. Basha, A.; Rdtajczyk, J. D.; Brooks, D. W. Tetrahedron Lett. 1991, 32,
3783
5. Marcial, M. M.; Cuberes, M. R.; Palacin, C.; Raga, M.; Castello, J. M.;
Ortiz, J. A. Eur. J. Med. Chem. 1988, 23, 477.
6. Martel, A. M.; Prous, J.; Castaner-Prous, J. Drug. Future 1997, 22, 386.
7. Bridges, A. J.; Lee, A.; Schwartz, C. E.; Towle, M. J.; Littlefield, B. A.
Bioorg. Med. Chem. 1993, 1, 403.
8. Bleavins, M. R.; de la Iglesia, F. A.; McCay, J. A.; White, L.; Kimber, L.;
Munson. A. E. Toxicology, 1995, 98, 1 I I.
9. Tron, G.; Pirali, T.; Sorba, G.; Pagliai, F.; Busacca, S.; Genazzani, J. Med.
Chem., 2006, 49, 3033.
10. Flynn, B. L.; Hamel, E. Jung, M. K. J. Med. Chem. 2002, 45, 2670.
11. Jones, C. D.; Jevnikar, M. G.; Pike, A. J.; Peters, M. K.; Black, L. J.;
Thompson, A. R.; Falcone, J. F.; Clemens, J. A. J. Med. Chem. 1984,
27, 1057.
12. Grese, T. A.; Cho, S.; Finley, D. R.; Godfrey, A. G.; Jones, C. D.;
Lugar III, C. W.; Martin, M. J.; Matsumoto, K.; Pennington, L. D.
Winter, M. A.; Adrian, M. D.; Cole, H. W.; Magee, D. E.; Phillips, D.
L.; Rowley, E. R.; Short, L. L.; Glasebrook, A. L.; Bryant, H. U. J. Med.
Chem. 1997, 40, 146.
33
13. Palkowitz, A. D.; Glasebrook, A. L.; Thrasher, K. J.; Hauser, K. L.;
Short, L. L.; Phillips, D. L.; Muehl, B. S.; Sato, M.; Shetler, P. K.;
Cullinan, G. J.; Pell, T. R.; Bryant, H. U. J. Med. Chem 1997, 40, 1407
14. Singh, P. P.; Yadav, A. K.; Ila, H.; Junjappa, H. J. Org. Chem. 2009, 74,
5496.
15. Nakamura, I.; Sato, T.; Yamamoto, Y. Angew. Chem. Int. Ed. 2006, 45,
4473.
16. Yoshida, S.; Yorimitsu, H.; Oshima, K. Org. Lett. 2007, 9, 5573.
17. Mizushima, E.; Hayashi, T.; Tanaka, M. Org. Lett., 2003, 5, 3349.
18. Antoniotti, S.; Genin, E.; Michelet, V.; Gene, J. P. J. Am. Chem.
Soc, 2005, 127, 9976
19. Hashmi, A. S. K.; Schwarz, L.; Choi, J. H.; Frost, T. M. Angew. Chem.
2000, 112, 2382
20. Shapiro, N. D.; Toste, F. D. J. Am. Chem. Soc. 2007, 129, 4160
21. Li, G.; Zhang, L. Angew. Chem. Int. Ed. 2007, 46, 5156
22 Li, C. W.; Pati, K.; Lin, G. Y.; Hung, H. H.; Liu, R. S. Angew. Chem.
Int. Ed. 2010, 49, 9891
23. Mezailles, N.; Ricard, L.; Gagosz, F. Org. Lett., 2005, 7, 4133
24. Shapiro, N. D.; Toste, F. D. J. Am. Chem. Soc. 2007, 129, 4160.
25. Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 16,
4467
26. Motto, J. M.; Montemayer, L. K.; Sheepwash, E. E.; Schwan, A. L.;
Castillo, A.; Greer, A. Tetrahedron, 2011, 67, 1002.
27. a) Leseurre, L. ; Toullec, P. Y. ; Genêt, J. P. ; Michelet, V. Org. Lett.,
2007, 9 , 4049.
b) Gorin, D. J.; Davis, N. R.; Toste, F. D. J. Am. Chem. Soc., 2005, 127,
11260.
34
28. Li, Z.; Brouwer, C.; He, C. Chem. Rev., 2008, 108, 3239
29. a) Ye, L.; Chen, Q.; Zhang, J.; Michelet, V. J. Org. Chem., 2009, 74,
9550.
b) Das, A.; Chang, H. K.; Yang, C.H.; Liu, R. S. Org. Lett., 2008, 10,
40614
c) Sun, J.; Conley, M. P.; Zhang, L.; Kozmin, S. A. J. Am. Chem. Soc.,
2006, 128, 9705.
30. Xu, C. F.; Xu, M.; Jia, Y. X.; Li, C. Y. Org. Lett., 2011, 13, 1556.
31. Hilt, G.; Smolko, K. I. Angew. Chem. Int. Ed., 2003, 42, 2795.
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