反应 #95463

反应方程式

2-acetyl-6-(trimethylsilyl)-5-hexynoic acid ethyl ester

sodium hydride

→

2-acetyl-2-fluoro-6-(trimethylsilyl)-5-hexynoic acid ethyl ester

溶剂

toluene

反应条件

后处理

1. 1
   温度the reaction mixture was cooled to -10°
2. 2
   其他was bubbled through the reaction mixture at such a rate that the internal temperature never exceeded 0° C
3. 3
   workup.ADDITIONThe perchloryl fluoride addition
4. 4
   其他Argon was bubbled through the mixture as it
5. 5
   其他The reaction mixture was partitioned between hexane and water
6. 6
   其他the organic phase was dried
7. 7
   其他(MgSO4) and condensed
8. 8
   其他by rotary evaporation
9. 9
   其他to give an oil
10. 10
    其他The components of the oil were separated by silica gel chromatography

实验过程

2-acetyl-6-(trimethylsilyl)-5-hexynoic acid ethyl ester (7.1 g) was added to a suspension of sodium hydride (1.0 g) in toluene under a positive argon atmosphere. After stirring for 1 hour, the reaction mixture was cooled to -10° and a mixture of perchloryl fluoride and argon gases was bubbled through the reaction mixture at such a rate that the internal temperature never exceeded 0° C. The perchloryl fluoride addition was discontinued when it ceased to be exothermic. Argon was bubbled through the mixture as it was allowed to warm to room temperature. The reaction mixture was partitioned between hexane and water and the organic phase was dried (MgSO4) and condensed by rotary evaporation to give an oil. The components of the oil were separated by silica gel chromatography using 30% ethyl acetate/hexane as the eluant to give 5.9 g of 2-acetyl-2-fluoro-6-(trimethylsilyl)-5-hexynoic acid ethyl ester. There was also obtained 0.25 g of 2-fluoro-6-(trimethylsilyl)-5-hexynoic acid ethyl ester.

来源