Erlenmeyer-Plöchl吖内酯合成

在乙酸酐存在下酰基甘氨酸发生分子内缩合得到5-恶唑酮（吖内酯）的反应。5-恶唑酮通常会和芳醛进行羟醛缩合得到4-arylideneoxazolones（4），恶唑酮4可以水解得到氨基酸。

反应机理

反应实例

【Org. Synth. Coll. II, 1943, 55】

【Tetrahedron Lett. 1992, 33, 6419-6422】

Bis-oxazolone (6). A mixture of hippuric acid 1 (2.15 g, 12.0 mmol) and Pb(OAc)2 (650 mg, 2.0 mmol)in Ac2O (5 mL) was heated with stirring until a clear orange solution was obtained. This was added to asolution of dialdehyde 5 (512 mg, 2.0 mmol) in Ac2O (10 mL) under N2. More Ac2O (5 mL) was addedand the reaction mixture was refluxed (138 ℃) under N2 for 24 h. It was then cooled in an ice bath and filtered to get a heavy yellow precipitate which was washed with cold Ac2O. The yellow amorphous solid was dissolved in CHCl3 (750 mL), washed with water, dried over Na2SO4 and concentrated to a yellow paste which was triturated with EA to afford 6 (746 mg, 69%). mp 279–281 ℃.

【J Org Chem., 1999, 64, 2500】

【J. Fluorine Chem. 2002, 115, 27-32】

【Tet Lett., 2010, 51, 1533】

【Tetrahedron 2012, 68, 5898-5907】

Emil Erlenmeyer, Jr.（1864-1921）出生于德国海德堡，是海德堡大学著名的化学教授Emil Erlenmeyer, Sr.（1825-1909）的儿子。他在斯特拉斯堡担任化学教授期间研究了 Erlenmeyer-Plöchl吖内酯的合成。Erlenmeyer flasks（锥形瓶）是化学实验室里随处可见的一种仪器（百度上查的是1861年发明的，应该是老Emil Erlenmeyer发明的）。

【Emil Erlenmeyer, Jr. (1864-1921) was born in Heidelberg, Germany to Emil Erlenmeyer, Sr. (1825-1909), a famous chemistry professor at the University of Heidelberg. He investigated the Erlenmeyer-Plöchl azlactone synthesis while he was a Professor of Chemistry at Strasburg. The Erlenmeyer flasks  are ubiquitous in chemistry laboratories.】

相关文献

1. (a) Plöchl, J. Ber. 1884, 17, 1616-1624. (b) Erlenmeyer, E., Jr. Ann. 1893, 275, 1-3.

2. Buck, J. S.; Ide, W.S. Org. Synth. Coll. II, 1943, 55.

3. Carter, H. E. Org. React. 1946, 3, 198-239. (Review).

4. Baltazzi, E. Quart. Rev. Chem. Soc. 1955, 9, 150-173. (Review).

5. Filler, R.; Rao, Y. S. New Development in the Chemistry of Oxazolines, In Adv. Heterocyclic Chem; Katritzky, A. R.; Boulton, A. J., Eds; Academic Press, Inc: New York, 1977, Vol. 21, pp 175-206. (Review).

6. Mukerjee, A. K.; Kumar, P. Heterocycles 1981, 16, 1995-2034. (Review).

7. Mukerjee, A. K. Heterocycles 1987, 26, 1077-1097. (Review).

8. Combs, A. P.; Armstrong, R. W. Tetrahedron Lett. 1992, 33, 6419-6422.

9. Konkel, J. T.; Fan, J.; Jayachandran, B.; Kirk, K. L. J. Fluorine Chem. 2002, 115, 27-32.

10. Brooks, D. A. ErlenmeyerPlöchl Azlactone Synthesis. In Name Reactions in Heterocyclic Chemistry; Li, J. J., Ed.; Wiley: Hoboken, NJ, 2005, pp 229-233. (Review).

11. Lee, C.-Y.; Chen, Y.-C.; Lin, H.-C.; Jhong, Y.; Chang, C.-W.; Tsai, C.-H.; Kao, C.-L.; Chien, T.-C. . Tetrahedron 2012, 68, 5898-5907.

参考文献

一、Name Reactions （A Collection of Detailed Reaction Mechanisms）, Jie Jack Li, Erlenmeyer-Plöchl azlactone synthesis， page 229-230.

二、Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 140.