Sodium hydride → HCID 14302346, compound

HRID 622788Notes

Reaction equation

HRID 622788 reaction equation
[H-].[Na+].[C:3]([CH2:5][C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])#[N:4].[F:13][C:14]1[C:22]([F:23])=[C:21]([F:24])[C:20]([F:25])=[CH:19][C:15]=1[C:16](Cl)=[O:17]>O1CCCC1>[C:3]([CH:5]([C:16](=[O:17])[C:15]1[CH:19]=[C:20]([F:25])[C:21]([F:24])=[C:22]([F:23])[C:14]=1[F:13])[C:6]([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7])#[N:4]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 70693tert-Butyl cyanoacetateHCID 27336892,3,4,5-Tetrafluorobenzoyl chloride

Product 1

HCID 14302346HCID 14302346, compoundYield 93%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A 60% dispersion of sodium hydride in mineral oil (12.8 g) was added to tetrahydrofuran (400 ml) and the mixture cooled with stirring using an ice bath. tert-Butyl cyanoacetate (22.8 g) was added dropwise over a 20 minute period with continued ice bath cooling such that the temperature remained below 10° C. 2,3,4,5-Tetrafluorobenzoyl chloride (34 g) was then added dropwise over a one hour period while maintaining the temperature between -5° C. and 0° C. using an ice-acetone bath. The cooling bath was removed and stirring continued for another 30 minutes while the mixture was warmed to room temperature. The mixture was concentrated to dryness under reduced pressure. Water (1.5 liter) and toluene (100 ml) were added with stirring. The layers were separated and the aqueous layer extracted again with toluene (100 ml). The aqueous layer was acidified to pH 1 using 36% hydrochloric acid. The crystals were collected and washed with excess water and dried under vacuum at room temperature to give tert-butyl 2-cyano-3-oxo-3-(2,3,4,5-tetrafluorophenyl)propionate (47 g, 93%), mp 90°-92° C.

Workup

  1. temperaturethe mixture cooled
  2. temperaturecooling such that the temperature
  3. customremained below 10° C
  4. temperaturewhile maintaining the temperature between -5° C. and 0° C.
  5. customThe cooling bath was removed
  6. stirringstirring
  7. concentrationThe mixture was concentrated to dryness under reduced pressure
  8. additionWater (1.5 liter) and toluene (100 ml) were added
  9. stirringwith stirring
  10. customThe layers were separated
  11. extractionthe aqueous layer extracted again with toluene (100 ml)
  12. customThe crystals were collected
  13. washwashed with excess water
  14. customdried under vacuum at room temperature

Sources & evidence

ORD record
ord-8062f6dcff69441dab06df53e23368c8
Source dataset
uspto-grants-1988_09
Patent number
US04772706

Reaction notes

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