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研究生: 王育瑄
論文名稱: 利用楚加耶夫反應的原理將一級硝基烷與醛肟轉換為腈類化合物
The Transformation of Primary Nitroalkanes and Oximes into Nitrile Compounds by Applying the Chugaev Reaction
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: 2013
畢業學年度: 101
語文別: 中文
論文頁數: 375
中文關鍵詞: 楚加耶夫反應硝基烷醛肟腈類化合物
英文關鍵詞: Chugaev Reaction, Nitroalkane, Oxime, Nitrile
論文種類: 學術論文
相關次數: 點閱:75下載:3
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  • 腈類化合物在有機化學領域中已被廣泛地應用,不僅可作為合成天然物、藥物、染料或高分子材料的關鍵步驟中的中間化合物;同時,腈類官能基也存在於許多的天然物的結構中。因此,化學家對腈類化合物已進行廣泛地研究。
    本論文的研究目的在利用楚加耶夫反應的原理,在室溫的條件下,以二氯甲烷為溶劑,使用二硫化碳、烯丙基溴(或甲基碘)與DBU,將一級硝基烷轉換為腈類化合物,並經由純化後的產物來推測反應進行時的可能反應機構。
    因此,綜合上述敘述,本論文呈現此反應具有操作簡單、反應時間短、高效率及高產率來製備腈類化合物的特色。

    Nitrile compounds have been widely utilized in the synthetic organic chemistry. It is the key intermediate for generating amides, amines, ketones, esters, or carboxylic acids. It is also present many natural products and synthetic compounds which exhibits variety of biological activities. Hence, developing rapid and simple method for the synthesis of nitriles compounds in one pot is an important research topic in the present scenario.
    A facile route for the synthesis of nitrile compounds by functional group transformation has been developed in this project. This newly development method is based on the Chugaev reaction where the primary nitroalkane can transformed into nitrile compound by the treatment of carbon disulfide, allyl bromide(or iodomethane), and DBU in dichloromethane at room temperature. This synthetic methodology is highly efficient and simply operation with high yield in short time. Furthermore, the plausible mechanistic route was proposed based on literature reports and different controlled experiments.

    1.前言 1 1.1腈類化合物的簡介 1 1.2腈類化合物的合成 4 1.3楚加耶夫反應 8 2.研究目標 10 3.實驗結果與討論 11 3.1探討楚加耶夫反應的試劑與化學結構鑑定 11 3.2探討楚加耶夫反應的試劑 17 3.3使用楚加耶夫反應的試劑合成腈類化合物 20 3.4一鍋化合成腈類化合物 24 3.5改良楚加耶夫反應的試劑 25 3.6使用改良的楚加耶夫反應的試劑合成腈類化合物 32 3.7合成腈類化合物的應用 38 3.8醛肟化物的應用 49 4.結論 56 5.實驗部分 57 5.1分析儀器及基本實驗操作 57 5.2實驗步驟 60 6.參考資料 62 7.光譜資料 65 光譜資料 65 Spectrum 94 X-ray 318

    1. (a) Scheele, C. W. Kungliga Svenska Vetenskapsakademiens handlingar 1782, 3, 264–275. (b) Scheele, C. W. Opuscula Chemica et Physica 1782, 2, 148–174.
    2. (a) Gay-Lussac, J. L. Annales de chimie 1811, 44, 128–133. (b) Gay-Lussac, J. L. Ann. Chim. Phys. 1815, 96, 136.
    3. Wöhler, F.; Liebig, J. von. Ann. 1832, 3, 267–268.
    4. David T. Mowry. Chem. Rev. 1948, 42, 189–283.
    5. Pelouze, T. J. Annalen der Pharmacie 1834, 10, 249.
    6. H. Fehling. Annalen der Chemie and Pharmacie 1844, 49, 91–97.
    7. (a) Jun, P.; Ko, N. U.; English, J. D.; Dowd, C. F.; Halbach, V. V.; Higashida, R. T.; Lawton, M. T. AJNR Am J Neuroradiol. 2010, 31, 1911–1916. (b) Drislane, F.; Benatar, M.; Chang, B. S.; Acosta, J.; Tarulli, A. Blueprints Neurology. Lippincott Williams & Wilkins. 2010, pp. 71. (c) Bannister, R. M.; Brookes, M. H.; Evans, G. R.; Katz, R. B.; Tyrrell, N. D. Org. Proc. Res. Dev. 2000, 4, 467–472. (d) Mcllhenny, H. M. J. Med. Chem. 1971, 14, 1178–1184. (e) Theodore, L. J.; Nelson, W. L. J. Org. Chem. 1987, 52, 1309–1315.
    8. (a) Shaunta' D, M.; Maha, S. I.; Kimi, S. V. The Ann. Pharmacother. 2006, 40, 1822–1828. (b) Torphy, T. J.; Barnette, M. S.; Underwood, D. C.; Griswold, D. E.; Christensen, S. B.; Murdoch, R. D.; Nieman, R. B.; Compton, C. H. Pulm Pharmacol Ther. 1999, 12, 131–135. (c) Ochiai, H.; Ohtani, T.; Ishida, A.; Kusumi, K.; Kato, M.; Kohno, H.; Kishikawa, K.; Obata, T.; Nakai, H.; Toda, M. Bioorg Med Chem Lett. 2004, 14, 207–210.
    9. (a) Marco, F.; Mario, S.; Eric, E. C. Plant Physiol. 1990, 94, 28–34. (b) Akgul, Y.; Ferreira, D.; Abourashed, E.; Khan, I. Fitoterapia. 2004, 75, 612–614.
    10. (a) Arai, T.; Takahashi, K.; Kubo, A. J. Antibiot. 1977, 30, 1015–1018. (b) Arai, T.; Takahashi, K.; Nakahana, S.; Kubo, A. Experientia 1980, 36, 1025–1028. (c) Arai, T.; Takahashi, K.; Ishiguro, K.; Mikami, Y. Gann(Tokyo), 1980, 71, 790–796. (d) Arai, T.; Mikami, Y.; Okamoto, K.; Tokita, H.; Terao, K. Advances in Cancer Chemtherapy; JapanScientific Society Press, Tokyo/ University Park Press: Baltimore, 1978, 235–251. (e)Li, L.; Deng, W.; Song, J.; Ding, W.; Zhao, Q. F.; Peng, C.; Song, W. W.; Tang, G. L.; Liu, W. J. Bacteriol. 2008, 190, 251–263.
    11. Gaspar, B.; Carreira, E. M. Angew. Chem. Int. Ed. 2007, 46, 4519–4522
    12. Lilly, E., Chem.Abstr., 1971, 75, 48707.
    13. Denis, J. N.; Krief, A. J. Chem. Soc., Chem. Comm. 1980, 544–545.
    14. Arrieta, A.; Aizpurua, J. M.;, Palomo, C. Tetrahedron Lett. 1984, 25, 3365–3368.
    15. Wehrli, P. A.; Schaer, B. J. Org. Chem. 1977, 42, 3956–3958.
    16. Olah, G. A.; Narang, S. C.; Field, L. D.; Fung, A. P. J. Org. Chem. 1983, 48, 2766–2767.
    17. Urpi, F.; Vilarras, J. Tetrahedron Lett. 1990, 31, 7497–7498.
    18. Texier-Boullet, F.; Villemin, D.; Ricard, M.; Moison, H.; Foucaud, A. Tetrahedron 1985, 41, 1259-1266.
    19. 郭俊偉,第二章 磷化物在有機合成上之應用,國立台灣師範大學化學系博士論文,民96[2007]。
    20. (a) Jack Li. Name Reactions. A Collection of Detailed Reaction Mechanisms. 2nd ed, Germany: Springer-Verlag, 2003, pp. 71. (b) Czakó, B.; Kürti, L. Strategic Applications of Named Reactions in Organic Synthesis. Elsevier, 2005, pp. 82–83.
    21. Fu, X.; Cook, J. M. Tetrahedron Lett. 1990, 31, 3409–3412.
    22. Hagiwara, H.; Kobayashi, K.; Miya, S.; Hoshi, T.; Suzuki, T.; Ando, M. Org. Lett. 2001, 3, 251–254.
    23. Meulemans, T. M.; Stork, G. A.; Macaev, F. Z.; Jansen, B. J. M. J. Org. Chem. 1999, 64, 9178–9188.
    24. (a) Benkeser, R. A.; Hazdra, J. J.; Burrous, M. L. J. Org. Chem. 1959, 81, 5374–5379. (b) Cram, D. J.; Elhafez, F. A. A. J. Org. Chem. 1952, 74, 5828-5835. (c) Kawata, T.; Harano, K.; Taguchi, T. Chem. Pharm. Bull. 1973, 21, 604. (d) Harano, K.; Taguchi, T. Chem. Pharm. Bull. 1975, 23, 467–472.
    25. (a) Barton, D. H. R.; Parekh, S. I.; Tse, C. L. Tetrahedron Lett. 1993, 34, 2733–2736. (b) Lee, A. W. M.; Chan, W. H.; Wong, H. C.; Wong, M. S. Synth. Commun. 1989, 19, 547–552. (c) O’Connor, G. L.; Nace, H. R. J. Am. Chem. Soc. 1952, 74, 5454-5459. (d) Benkesser, R. A.; Hazdra, J. J. J. Am. Chem. Soc. 1959, 1, 228–231.
    26. 施妤璇,第一章 利用1,5-雙氟基-2,4-二硝基苯作為脫水劑在合成異噁唑類衍生物的研究,國立台灣師範大學化學系碩士論文,民98[2009]。
    27. (a) Weiping, Y.; Junye, X.; Tan, C. T.; Tan, C. H. Tetrahedron Lett. 2005, 46, 6875-6878. (b) Poe, S. L.; Kobaslija, M.; McQuade, D. Tyler. J. Am. Chem. Soc. 2005, 129, 9216–9221.
    28. (a) Taber, D. T. J. Org. Chem. 1976, 41, 2649–3650. (b) Hughes, S.; Griffiths, G.; Stirling, Charles J. M. J. Chem. Soc., Perkin Trans. 2, 1987, 1253–1264.
    29. (a) Anderson, A. W.; Merckling, N. G. Polymeric bicycle[2.2.1]hept-
    2-ene. US 2721189, 1955 (E. I. du Pont de Nemours & Co.). (b) Calderon, N.; Chen, H. Y.; Scott, K. W. Tetrahedron Lett. 1967, 34, 3327–3329.
    30. 官巧之,利用雙官能基硫脲為有機催化劑及1,5-雙氟基-2,4-二硝基苯來合成掌性異噁唑類衍生物的研究,國立台灣師範大學化學系碩士論文,民100[2011]。
    31. Hoveyda, H. R.; Marsault, E.; Gagnon, R.; Mathieu, A. P.;Vézina, M.; Landry, A.; Wang, Z.; Benakli, E.; Beaubien, S.; Saint-Louis, C.; Brassard, M.; Pinault, J. F.; Ouellet, L.; Bhat, S.; Ramaseshan, M.; Peng, X.; Foucher, L.; Beauchemin, S.; Bhérer, P.; Veber, D. F.; Peterson, M. L.; Fraser, G. L. J. Med. Chem., 2011, 54, 8305–8320.
    32. Chio, Y. L.; Lim, H. S.; Lim, H. J.; Heo, J. N. Org. Lett. 2012, 14, 5102–5105.
    33. Habib, P. M.; Kavala, V.; Kuo, C. W.; Raihan, M. J.; Yao, C. F. Tetrahedron 2010, 66, 7050–7056.
    34. Chakrabarti, J. K.; Hotten, T. M. J. Chem. Soc., Chem. Commun. 1972, 1226–1227.
    35. Li, Y. T.; Liao, B. S.; Chen, H. P.; Liu, S. T. Synthesis. 2011, 16, 2639–2643.
    36. (a) Marsden, S. P. Nat. Chem. 2009, 1, 685–687. (b) Fairlamb, I. J. S. ChemSusChem 2009, 2, 1021–1024. (c) McGonagle, A. E.; Marsden, S. P.; McKever-Abbas, B. Org. Lett. 2008, 10, 2589–2591.
    37. O’Brien, C. J.; Tellez, J. L.; Nixon, Z. S.; Kang, L. J.; Carter, A. L.; Kunkel, S. R.; Przeworski, K. C.; Chass, C. G. Angew. Chem. Int. Ed. 2009, 48, 6836–6839.
    38. Harris, J. R.; Haynes, M. T.; Thomas, A. M.; Woerpel, K. A. J. Org. Chem. 2010, 75, 5083–5091.
    39. (a) Denton, R. M.; An, J.; Adeniran, B. Chem. Commun. 2010, 3025–3027. (b) Denton, R. M.; An, J.; Adeniran, B.; Blake, A. J.; Lewis, W.; Poulton, A. J. Org. Chem. 2011, 76, 6749–6767. (c) Denton, R. M.; Tang, X.; Przelack, A. Org. Lett. 2010, 12, 4678–4681.
    40. van Kalkeren, H. A.; Leenders, S. H. A. H.; Hommersom, C. R. A.; Rutjes, F. P. J. T.; van Delft, F. L. Chem. Eur. J. 2011, 17, 11290–11295.
    41. Denton, R. M.; An, J.; Lindovska, P.; Lewis, W. Tetrahedron 2012, 68, 2899–2905.
    42. Damljanović, I.; Vukićević, M.; Vukićević, R.D. Monatashefte für Chemie 2006, 137, 301–305.

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