Sodium hydride → 2-Acetyl-2-fluoro-6-(trimethylsilyl)-5-hexynoic acid ethyl ester

HRID 615553Notes

Reaction equation

HRID 615553 reaction equation
[CH2:1]([O:3][C:4](=[O:17])[CH:5]([C:14](=[O:16])[CH3:15])[CH2:6][CH2:7][C:8]#[C:9][Si:10]([CH3:13])([CH3:12])[CH3:11])[CH3:2].[H-].[Na+].Cl([F:24])(=O)(=O)=O>C1(C)C=CC=CC=1>[CH2:1]([O:3][C:4](=[O:17])[C:5]([C:14](=[O:16])[CH3:15])([F:24])[CH2:6][CH2:7][C:8]#[C:9][Si:10]([CH3:11])([CH3:13])[CH3:12])[CH3:2]

Participants

4

Reactant 2

HCID 24758Sodium hydrideHCID 130449582-Acetyl-6-(trimethylsilyl)-5-hexynoic acid ethyl ester

Product 1

HCID 133930802-Acetyl-2-fluoro-6-(trimethylsilyl)-5-hexynoic acid ethyl ester

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

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 postive 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.

Workup

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

Sources & evidence

ORD record
ord-40bd283e64174a998a76355236c7326a
Source dataset
uspto-grants-1985_02
Patent number
US04500462

Reaction notes

Loading…