Ethyl 2-chloroacetoacetate → HCID 13646804, compound

HRID 1982441Notes

Reaction equation

HRID 1982441 reaction equation
[H-].[Na+].[Cl:3][CH:4](C(C)=O)[C:5]([O:7]CC)=[O:6].Br[CH2:14][C:15]1[O:19][C:18]([CH3:20])=[N:17][C:16]=1[C:21]1[CH:26]=[CH:25][C:24]([Cl:27])=[CH:23][CH:22]=1>CN(C)C=O>[Cl:3][CH:4]([CH2:14][C:15]1[O:19][C:18]([CH3:20])=[N:17][C:16]=1[C:21]1[CH:26]=[CH:25][C:24]([Cl:27])=[CH:23][CH:22]=1)[C:5]([OH:7])=[O:6]

Participants

5

Reactant 3

HCID 11858Ethyl 2-chloroacetoacetateHCID 24758Sodium hydrideHCID 132932935-(Bromomethyl)-4-(4-chlorophenyl)-2-methyl-1,3-oxazole

Product 1

HCID 13646804HCID 13646804, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

60% Suspension of sodium hydride (1.08 g) in oil was added portionwise to a solution of ethyl 2-chloroacetoacetate (4.4 g) in N,N-dimethylformamide (70 ml) under stirring and ice-cooling. After stirring for 10 minutes, a solution of 5-bromomethyl-4-(4-chlorophenyl)-2-methyloxazole (7.0 g) in N,N-dimethylformamide (10 ml) was added dropwise under ice-cooling to the mixture. The mixture was stirred under ice-cooling for 30 minutes, and then diluted with ice-water and extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was then distilled off. The residue was dissolved in ethanol (40 ml), added to an aqueous 2N sodium hydroxide solution (40 ml) under stirring and ice-cooling, and stirred for further 30 minutes. The solution was then diluted with water, washed with ethyl ether and the aqueous layer was adjusted to pH 2 with 2N hydrochloric acid to give crystals of 2-chloro-3-[4-(4-chlorophenyl)-2-methyl- 5-oxazolyl]propionic acid, yield 5.9 g (80.4 %). Recrystallization from methanol gave colorless prisms, m.p. 208°-209° C.

Workup

  1. temperatureice-cooling
  2. stirringAfter stirring for 10 minutes
  3. temperaturecooling to the mixture
  4. stirringThe mixture was stirred under ice-
  5. temperaturecooling for 30 minutes
  6. extractionextracted with ethyl acetate
  7. washThe ethyl acetate layer was washed with water
  8. dry with materialdried over anhydrous magnesium sulfate
  9. distillationThe solvent was then distilled off
  10. dissolutionThe residue was dissolved in ethanol (40 ml)
  11. additionadded to an aqueous 2N sodium hydroxide solution (40 ml)
  12. stirringunder stirring
  13. temperatureice-cooling
  14. stirringstirred for further 30 minutes
  15. additionThe solution was then diluted with water
  16. washwashed with ethyl ether

Sources & evidence

ORD record
ord-d95fbe4daaa34aad8f9438441d517a87
Source dataset
uspto-grants-1986_06
Patent number
US04596816

Reaction notes

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