原标题：Allen膦重排反应

环膦化合物通过烷基化或酰基化得到环膦盐，接着在碱性条件下重排扩环，得到多一个碳的环氧膦化合物的反应。此反应也被称为Allen–Millar–Trippett反应。

反应机理

反应实例

9-Methyl-9,10-dihydro-9-phosphaphenanthrene-9-oxide (3).1 The phosphonium salt 2 (R = Me, 0.7 g, 1.5 mmol) in aq acetone containing KOH solution was heated to reflux for 2 h. Extraction of the cold mixture with CHCl3, evaporation of the solvent and silica gel chromatography via elution with EA:EtOH (7:3) afforded 0.24 g, 71% of 3.

【Allen DW, Millar IT, Chem Ind, 1967, 2178】

Hydroxyphosphine oxide (8).6 Benzoyl chloride (10 g, 71.1 mmol) was added to 4 (7.53 g, 40 mmol) and Et3N (20 mL) in Et2O (300 mL). After 3 h stirring under reflux 5 was hydrolyzed with water (150 mL) for 2 h. The precipitates thus formed were removed by filtration and the resulting filtrate dried over MgSO4. Evaporation of the solvent and recrystallization from PhCH3 afforded 10.8 g of 8 (87%).

【Mathey F, Tetrahedron,1973, 29, 707】

相关文献

1， Allen DW, Millar IT, Chem Ind, 1967, 2178

2， Trippett S, Chem Comm, 1967, 1113

3， Allen DW, Millar IT, J Chem Soc C, 1969, 252

4， Tebby JC, J Chem Soc C, 1971, 1064

5， Mathey F, Tetrahedron, 1972, 28, 4171

6， Mathey F, Tetrahedron, 1973, 29, 707

7， Allen DW, J Chem Soc Perkin 1, 1976, 2050

8， Markl G, Angew Chem Int, 1987, 26, 1134

9， Keglevich Gy, J Org Chem, 1990, 55, 6361

10， Keglevich Gy, Synthesis, 1993, 931

11，R Savignac P, Eur J Org Chem, 2000, 3103

12， Mapp AK, J Am Chem Soc, 2006, 128, 4576

13， Vignolle J, Tet Lett, 2007, 48, 685

编译自：Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 7-8。返回搜狐，查看更多

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