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Skraup喹啉合成2019-03-02

苯胺,甘油,硫酸和氧化剂 (如PhNO2)反应制备喹啉的反应。

反应机理

甘油在酸性条件下先生成丙烯醛,苯胺对其进行共轭加成β -苯胺基丙醛,关环脱水得到二氢喹啉,氧化得到产物。

反应实例

参考文献

1. (a) Skraup, Z. H. Monatsh. Chem. 1880, 1, 316. Zdenko Hans Skraup (1850-1910) was born in Prague, Czechoslovakia. He apprenticed under Lieben at the University of Vienna. (b) Skraup, Z. H. Ber. 1880, 13, 2086.【Zdenko Hans Skraup (1850-1910)生于捷克斯洛伐克的布拉格。在维亚纳大学师从Lieben。】

2. Manske, R. H. F.; Kulka, M. Org. React. 1953, 7, 80-99. (Review).

3. Bergstrom, F. W. Chem. Rev. 1944, 35, 77-277. (Review).

4. Eisch, J. J.; Dluzniewski, T. J. Org. Chem. 1989, 54, 1269-1274.

5. Oleynik, I. I.; Shteingarts, V. D. J. Fluorine Chem. 1998, 91, 25-26.

6. Fujiwara, H.; Kitagawa, K. Heterocycles 2000, 53, 409-418.

7. Ranu, B. C.; Hajra, A.; Dey, S. S.; Jana, U. Tetrahedron 2003, 59, 813-819.

8. Panda, K.; Siddiqui, I.; Mahata, P. K.; Ila, H.; Junjappa, H. Synlett 2004, 449-452.

9. Moore, A. Skraup Doebner–von Miller Reaction. In Name Reactions in Heterocyclic Chemistry; Li, J. J., Ed.; Wiley: Hoboken, NJ, 2005, pp 488-494. (Review).

10. Denmark, S. E.; Venkatraman, S. J. Org. Chem. 2006, 71, 16681676. Mechanistic study using 13C-labelled α ,β -unsaturated ketones.

11. Vora, J. J.; Vasava, S. B.; Patel, Asha D.; Parmar, K. C.; Chauhan, S. K.; Sharma, S. S. E. J. Chem. 2009, 6, 201-206.

12. Fotie, J.; Kemami Wangun, H. V.; Fronczek, F. R.; Massawe, N.; Bhattarai, B. T. Rhodus, J. L.; Singleton, T. A.; Bohle, D. S. J. Org. Chem. 2012, 77, 2784-2790.

编译自:Name Reactions (A Collection of Detailed Reaction Mechanisms), Jie Jack Li, Skraup quinoline synthesis,page 562-563.

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