Ethyl Acrylate → Ethyl 1-benzyl-5-(1,3-dithiol-2-ylidene)-4,6-dioxopiperidine-3-carboxylate

HRID 977953Notes

Reaction equation

HRID 977953 reaction equation
[H-].[Na+].[S:3]1[CH:7]=[CH:6][S:5][C:4]1=[C:8]([C:14](=[O:23])[NH:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:9]([O:11]CC)=O.[C:24]([O:28][CH2:29][CH3:30])(=[O:27])[CH:25]=[CH2:26]>CN(C)C=O>[CH2:16]([N:15]1[C:14](=[O:23])[C:8](=[C:4]2[S:3][CH:7]=[CH:6][S:5]2)[C:9](=[O:11])[CH:25]([C:24]([O:28][CH2:29][CH3:30])=[O:27])[CH2:26]1)[C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1

Participants

5

Reactant 3

HCID 8821Ethyl AcrylateHCID 24758Sodium hydrideHCID 20204019ethyl 2-(1,3-dithiol-2-ylidene)-2-(N-benzylcarbamoyl)acetate

Product 1

HCID 13934862Ethyl 1-benzyl-5-(1,3-dithiol-2-ylidene)-4,6-dioxopiperidine-3-carboxylateYield 75%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Procedure

Sodium hydride (a 60% dispersion in oil) (1.50 g) is suspended in N,N-dimethylformamide (100 ml) and a solution of ethyl 2-(1,3-dithiol-2-ylidene)-2-(N-benzylcarbamoyl)acetate (10.0 g) in dimethylformamide (250 ml) is added dropwise thereto at 4° to 5° C. The mixture is stirred at the same temperature for 30 minutes. A solution of ethyl acrylate (4.1 ml) in dimethylformamide (100 ml) is added dropwise to the mixture, and the mixture is stirred at the same temperature for one hour and then at room temperature for 5 hours. The mixture is poured into ice-water, and the aqueous solution is extracted with ethyl acetate. The extract is washed with water, dried and then evaporated to remove the solvent. The residue is recrystallized from a mixture of n-hexane and ethyl acetate, whereby ethyl 1-benzyl-5-(1,3-dithiol-2-ylidene)-4,6-dioxopiperidine-3-carboxylate (8.76 g ) is obtained as pale yellow needles. Yield: 75%.

Workup

  1. customat 4° to 5° C
  2. stirringthe mixture is stirred at the same temperature for one hour
  3. waitat room temperature for 5 hours
  4. extractionthe aqueous solution is extracted with ethyl acetate
  5. washThe extract is washed with water
  6. customdried
  7. customevaporated
  8. customto remove the solvent
  9. customThe residue is recrystallized from a mixture of n-hexane and ethyl acetate

Sources & evidence

ORD record
ord-80759b6916004bb7bbee9c74aca4efa6
Source dataset
uspto-grants-1987_05
Patent number
US04663319

Reaction notes

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