研究生: |
吳易儒 Yih-Ru Wu |
---|---|
論文名稱: |
共軛硝基烯類與有機硼及有機鋁試劑反應之探討 |
指導教授: |
姚清發
Yao, Ching-Fa |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2004 |
畢業學年度: | 92 |
語文別: | 中文 |
論文頁數: | 136 |
中文關鍵詞: | 共軛硝基烯類 、三乙基硼 、自由基反應 、有機鋁試劑 、乙基自由基 、氧化 |
英文關鍵詞: | nitrile oxide, triethylborane, oxime, radical reaction |
論文種類: | 學術論文 |
相關次數: | 點閱:155 下載:5 |
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 |
氧化系列物(nitrile oxides)1a-1n在開放系統下,可與三乙基硼(triethylborane)試劑反應進行自由基加成反應而生成(oxime)。反應機構首先由乙基自由基進行加成反應後再從水溶液中得到氫。此反應在含有氧氣的幫助下十分容易發生;而加入自由基之抑制劑如galvinoxyl時,則明顯地抑制或減少類的生成,其結果足以證明是屬於自由基的反應機構。
Reaction of nitrile oxides 1a-1n with triethylborane under the open system undergo free radical addition reaction to generate oxime. The mechanism is proposed to be a free-radical reaction via ethyl radical addition and then undergo protonlysis in aqueous solution. The reaction is stimulated by the presence of oxygen and is also retarded or inhibited by the presence of galvinoxyl in the solution.
(1) (a) Grundmann, C. in Houben-Weyl. Methoden der Organischen Chemie, 10:3.; Mller, E.; Ed.; Georg Thieme Verlag, Stuttgart, 1965; p 837; E5:2, Falbe, J.; Ed.; 1985, pp1585. (b) W. Rundel in Houben-Weyl. Methoden der Organischen Chemie, 10:4.; Mller, E.; Ed.; Georg Thieme Verlag, Stuttgart, 1968; p 311. (c) Quilico, A. Experientia 1970, 26, 1169. (d) Grundmann, C.; Grnanger, P. in The Nitrile Oxides, Springer-Verlag, Berlin, 1971. (e) Caramella, P.; Grnanger, P. in 1,3-Dipolar Cycloaddition Chemistry, Padwa, A.; Ed.; Vol. 1, Wiley, New York, 1984, pp 291. (f) Kozikowski, A. P. Acc. Chem. Rev. 1984, 17, 410. (g) Torsell, K. B. G. Nitrile Oxides, Nitrones and Nitronates in Organic Synthesis, VCH, New York, 1988. (h) Mulzer, J. in Organic Synthesis Highlights, VCH, Weinheim, 1991, p 77. (i) Wade, P. A. in Comprehensive Organic Synthesis, Trost, B. M., Ed.; Pergamon Press. Oxford, 1991, Vol 3, p 1111. (j) Jager, V.; Muller, R.; Leibold, T.; Hein, M.; Schwartz, M, Fengler, M.; Jarskova, L. Patzel, M.; LeRoy, P. Y. Bull. Soc. Chim. Bel. 1994, 103, 490. (k) Namboothiri, I. N. N.; Hassner, A Top. Curr. Chem. 2001, 216, 1. (l) Ono, N. in The Nitro Group in Organic Synthesis, WILEY-VCH, New York, 2001.
(2) Christl, M.; Huisgen, R. Chem. Ber. 1873, 106, 3345.
(3) Wener, A.; Buss, H. Chem. Ber. 1894, 127, 2193.
(4) Lee, G. A. Synthesis 1982, 508.
(5) Grundmann, C. Richter, R. J. Org. Chem. 1968, 33, 476.
(6) Mukaiyama, T.; Hoshino, T. J. Am. Chem. Soc. 1960, 82, 5339.
(7) Chen, Y.-J.; Li, C.-N. J. Chin. Chem. Soc. 1993, 40, 203.
(8) Christl, M.; Huisgen, R. Chem. Ber. 1873, 106, 3345.
(9) Hasser, A.; Murthy, K. S. J. Org. Chem. 1989, 54, 5227.
(10) Beebe, X.; Chiappari, Cynthia, L. J. Org. Chem. 1993, 58, 7320.
(11) Hassner, A.; Dehaen, W. Chem. Ber. 1991, 1181.
(12) Kumaran, G.; Kulkarni, G. H. J. Org. Chem. 1997, 62, 1516.
(13) Yao, C.-F.; Chen, W.-C.; Lin, Y.-M. Tetrahedron Lett. 1996, 37, 6339.
(14) 劉作融, 2004年碩士班論文.
(15) Grundmann, C.; Richter, R. J. Org. Chem. 1967, 32, 2308.
(16) Just, G.; Dahl, K. Tetrahedron 1976, 24, 5251.
(17) Dondoni, A. J. Org. Chem. 1972, 37, 3196.
(18) Curran, D. P.; Scanga, S. A.; Fenk, C. J. J. Org. Chem. 1984, 49, 3473.
(19) Grundmann, C.; Frommeld, H. D. J. Org. Chem. 1966, 31, 157.
(20) Kim, J. N.; Kim, H. R.; Ryu, E. K. Tetrahedron Lett. 1993, 34, 5117.
(21) 方惠玉, 2001年碩士班論文; compound 1a-1h; in Table 2, entry 1-9為方惠玉同學所完成.
(22) (a) Wade, P. A.; Hinney, H. R.; J. Am. Chem. Soc. 1979, 101, 1319. (b) Kozikowski, A. P.; Ghosh, A. K. J. Org. Chem. 1985, 50, 778. (c) Kozikowski, A. P.; Ghosh, A. K. Tetrahedron Lett. 1983, 24, 2623.
(23) Rabjohn, N. In Organic Syntheses, 2nd ed.; Blatt, A. H., John Wiley & Sons: New York, 1963; Vol Ⅳ, p 573.
(1) (a) Buckley, G. D. J. Chem. Soc. 1947, 1494. (b) Buckley, G. D.; Ellery, E. J. J. Chem. Soc. 1947, 1497. (c) Ashwood, M. S.; Bell, L. A.; Houghton, P. G. Wright, S. H. B. Synthesis 1988, 379.
(2) (a) Bedford, C. D.; Nielsen, A. T. J. Org. Chem. 1978, 43, 2460. (b) Hayama, T.; Tomoda, S.; Takeuchi, Y.; Nomura, Y. Tetrahedron Lett. 1983, 24, 2795. (c) Seebach, D.; Knochel, P. Helv. Chim. Acta 1984, 67, 261.
(3) (a) Retherford, C.; Yeh, M.-C. P.; Schipor, I.; Chen, H. G.; Knochel, P. J. Org. Chem. 1989, 54, 5200. (b) Retherford, C.; Knochel, P. Tetrahedron Lett. 1991, 32, 411. (c) Jubert, C.; Knochel, P. J. Org. Chem. 1992, 57, 5425.
(4) (a) Pecunioso, A.; Menicagli, R. Tetrahedron 1987, 43, 5411. (b) Pecunioso, A.; Menicagli, R. J. Org. Chem. 1988, 53, 45. (c) Pecunioso, A.; Menicagli, R. J. Org. Chem. 1988, 53, 2614. (d) Pecunioso, A.; Menicagli, R. J. Org. Chem. 1989, 54, 2391.
(5) Yao, C.-F.; Chen, W.-C.; Lin, Y.-M. Tetrahedron Lett. 1996, 37, 6339.
(6) Meyer, V.; Wurster, C.; Chem. Ber. 1873. 6, 1168.
(7) Nef, J. U. Justus Liebigs Ann. 1894, 280, 263.