研究生: |
王曄 Wang Yeh |
---|---|
論文名稱: |
2,2-雙取代-1-硝基烯之簡易製備法 The easy method for the preparation of 2,2-disubstituted-1-nitroalkenes |
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: | 2000 |
畢業學年度: | 88 |
語文別: | 中文 |
論文頁數: | 172 |
中文關鍵詞: | 2,2-雙取代-1-硝基烯類 、亨利反應 |
英文關鍵詞: | 2,2-disubstituted 1-nitroalkenes, Henry reaction |
論文種類: | 學術論文 |
相關次數: | 點閱:480 下載:8 |
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 |
酮類(ketones)1a-e可與硝基甲烷(nitromethane)2在催化量的piperidine 3存在下與trapping reagents 4(thiophenol 4a、α-toluenthiol 4b或allyl mercaptan 4c)反應產生β-nitroalkylsulfides(5a-d、6a-e或7a-e)。於0 ℃條件下用CH2Cl2為溶劑,m-chloroperoxybenzoic acid (m-CPBA) 8 可將β-nitroalkylsulfides(5a-d、6a-e或7a-e)氧化成β-nitroalkylsulfoxides(9a-d、10a-e或11a-e),然後再用CCl4為溶劑在迴流的條件下脫去PhSOH產生2,2-雙取代-1-硝基烯類12a-e。其反應機構之不可逆性除了可克服亨利反應(Henry reaction)中在合成2,2-雙取代-1-硝基烯類12a-b時之不實用性(可逆反應)外,亦可由環酮類合成環外硝基烯類12c-e。由此簡易改良法可將12a-e產率提昇至中等至高產率,在類似的反應條件下5-substituted adamantan-2-ones 16a-f和2及催化量的3亦可得到5-substituted-2-nitromethylene-admantanes 18a-f。同時發現β-nitroalkylsulfoxides(9b、10c、10d、11c或11e)在鹼性水溶液處理下亦可得到12b-e,但產率約在25-65%之間,比上述之熱解反應之產率稍低。
Ketones 1a-e、nitromethane 2 can react with the trapping reagents 4(thiophenol 4a, α-toluenthiol 4b or allyl mercaptan 4c)in the presence of catalytic amount of piperidine 3 to produce β-nitroalkylsulfides(5a-d, 6a-e or 7a-e). By the use of CH2Cl2 as solvent and at 0 ℃, β-nitroalkylsulfides(5a-d, 6a-e or 7a-e)can be oxidized by m-chloroperoxybenzoic acid (m-CPBA) 8 to produce β-nitroalkyl sulfoxides(9a-d、10a-e or 11a-e)and subsequently elimination to produce 2,2-disubstituted 1-nitroalkenes 12a-e. The irreversibility of the synthetic mechanism not only could overcome the impracticability of the Henry reaction in the synthesis of 2,2-disubstituted 1-nitroalkenes 12a-b but also could produce the major product "exo-nitroolefins" 12c-e when cyclic ketones were used. By using this improved and easy methodology to prepare 2,2-disubstituted-1-nitroalkenes 12a-e, the yields of the products are medium to high. Under similar reaction conditions 5-substituted adamantan-2-ones 16a-f can also react with 2 in the presence of catalytic amount of piperidine 3 to produce 5-substituted-2-nitromethylene-admantanes 18a-f. 12b-e Also can be produced when β-nitroalkylsulfoxides(9b, 10c, 10d, 11c , and 11e)are treated with dilute aqueous basic solution, but the yields are lower than those of pyrolysis condition.
(1) (a) Corey, E. J.; Estreicher, H. J. Am. Chem. Soc. 1978, 100, 6294.
(b) Seebach, D.; Colvin, E. W.; Well, T. Chimia 1979, 33, 1.
(c) Barrett, A. G. M.;Graboski, G. G. Chem. Rev. 1986, 86, 751.
(d) Rosini, G.; Ballini, R. Synthesis 1988, 833.
(e) Several articles in Tetrahedron Symposia-in-Print 41, "Nitroalkanes and Nitroalkenes in Synthesis", Tetrahedron 1990, 46 (21), Barrett, A. G. M. Ed.
(f) Barrett, A. G. M. Chem. Soc. Rev. 1991, 20, 95.
(2) (a) Buckly, G. D.; Caife, C. W. J. Chem. Soc. 1947, 1471.
(b) Melton, J.; McMurry, J .E. J. Org. Chem. 1975, 40, 2138.
(c) Knochel, P.; Seebach, D. Synthesis 1982, 1017.
(d) Knochel, P.; Seebach, D. Tetrahedron Lett. 1982, 23, 3879.
(e) Seebach, D.; Knochel, P. Helv. Chim. Acta 1984, 67, 261.
(f) Ballini, R.; Catagnani, R.; Petrini, M. J. Org. Chem. 1992, 57, 2160.
(g) Varma, R. S.; Dahiya, R.; Sudhir, K. Tetrahedron Lett. 1977, 38, 5131.
(h) Stanetty, P.; Kremslehner, M. Tetrahedron Lett. 1998, 39, 811.
(3) (a) Rossine, G. In Comprehensive Organic Synthesis, Part 2;
Additions to c-x π-Bonds; Trost, B. N., Fleming, I. Eds.; Pergamon Press ; Oxford, 1991; vol. 2, 329.
(b) Matsumoto, K. Angew. Chem. Int. Ed. Engl. 1984, 18, 617.
(c) Tamura, R.; Sato, M.; Oda, D. J. Org. Chem. 1986, 51, 4368.
(4) Derrand, J. C.; Schneider,R.; Grardin, P.; Loubinoux, B. Synth. Commun. 1996, 26, 4329.
(5) (a) Retherord, C.; Knochel, P. Tetrahedron Lett. 1991, 32, 441.
(b) Jubert, C.; Knochel, P. J. Org. Chem. 1992, 57, 5425.
(c) Jubert, C.; Knochel, P. Ibid. 1992, 57, 5431.
(6) (a) Sakahibara, T.; Takai, I.; Ohara, E.; Sudoh, R. J. Chem. Soc.,
Chem. Commun. 1981, 261.
(b) Sakahibara, T.; Ikuta, S.; Sudoh, R. Synthesis 1982, 261.
(7) Denmark, S. E.; Marcin, L. R. J. Org. Chem. 1993, 58, 3850.
(8) March, J. in Advanced Organic Chemistry : Reactions, Mechanisms, and Structure, 4th ed., Wiley-Interscience, New York, 1992, p 1021.
(9) (a) Kingsbury, C. A.; Cram, D. J. J. Am. Cham. Soc. 1960, 82, 1810.
(b) Walling, C.; Bollyky, L. J. Org. Chem. 1964, 29, 2699.
(c) Yoshimura, T.; Tsukurimichi, E.; Iisuka, U.; Mizuno, H.; Ksaji,
H.; Shimasaki, C. Bull. Chem. Soc. Jpn. 1989, 62, 1891.
(10) (a) Trost, B. M.; Salzmann, T. N.; Hiroi, K. J. Am. Chem. Soc. 1976,
98, 4887.
(b) Trost, B. M. Acc. Chem. Res. 1978, 11, 453.
(11) Carrol, F. I.; White, J. D.; Wall, M. E. J. Org. Chem. 1963, 28, 5277.
(12) (a)Eckstein, Z.; Sacha, A.; Urbanki, T. Bull. Acad. Polon. Sci. 1957,
Classe III 5, 213.
(b) C.A. 1957, 51, 16318.
(13) Houben-Weyl. Methoden der Organischen Chemie, 4th ed.; Muller, E., Ed.; Georg Thieme Verlag: Stuttgart, 1971; Vol. X, Part 1, pp 336-338.
(14) Bear, H. H.; Urbas, L. In The Chemistry of the Nitro and Nitroso Groups; Feuer, H., Ed.; Interscience Publishers: New York, 1970; Part 2, pp 112-115.
(15) Jones, G. Org. React. (N.Y.) 1967, 15, 204.
(16) Hassner, A.; Dehaen, W. J. Org. Chem. 1990, 55, 5505.
(17) Parham, W. E.; Ramp, F. L. J. Am. Chem. Soc. 1951, 73, 1293.
(18) (a) Barton, D. H. R.; Motherwell, W. B.; Zard, S. Z. Bull. Soc. Chim. Fr. EN, 1983, 2, 61. (b) Leonova, M. V.; Klimochkin, Y. N.; Kovalev, V. V.; Moiseev, I. K. Russ. J. Org. Chem. EN, 1993, 29, 11, 1921. Zh. Org. Khim. RU, 1993, 29, 2312.
(c) Klimochkin, Y. N.; Leonova, M. V.; Moiseev, I. K. Russ. J. Org. Chem. EN, 1998, 34, 494. Zh. Org. Khim. RU, 1998, 34, 528.
(d) Klimochkin, Y. N.; Leonova, M. V.; Moiseev, I. K. Russ. J. Org. Chem. EN, 1998, 34, 34. Zh. Org. Khim. RU, 1998, 34, 46.
(19) Geluk, H. W. Synthesis 1972, 374.
(20) (a) Chung, W. S.; Liu, Y. D.; Wang, N. J. J. Chem. Soc. Perkin Trans. 2, 1995, 581-586.
(b) Xie, M.; le Nobel, W. J. J. Org. Chem. 1989, 54, 3839.
(c) Tabushi, I.; Aoyama, Y. J. Org. Chem. 1973, 38, 3447.
(21) Guluk, H. W.; Schlatmann, J. L. M. A. Tetrahedron 1968, 24, 5369.
(22) Klein, H.; Wiartalla, R. Synth. Commun. 1979, 9, 825.
(23) Adcock, W.; Trout, N. A. J. Org. Chem. 1991, 56, 3229.