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

HRID 977956Notes

Reaction equation

HRID 977956 reaction equation
[H-].[Na+].[CH2:3]([N:10]1[C:15](=[O:16])[C:14](=[C:17]2[S:21][CH:20]=[CH:19][S:18]2)[C:13](=[O:22])[CH:12]([C:23]([O:25][CH2:26][CH3:27])=[O:24])[CH2:11]1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[CH3:28]I.O>CN(C)C=O>[CH2:3]([N:10]1[C:15](=[O:16])[C:14](=[C:17]2[S:18][CH:19]=[CH:20][S:21]2)[C:13](=[O:22])[C:12]([CH3:28])([C:23]([O:25][CH2:26][CH3:27])=[O:24])[CH2:11]1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

6

Reactant 4

HCID 962WaterHCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 13934862Ethyl 1-benzyl-5-(1,3-dithiol-2-ylidene)-4,6-dioxopiperidine-3-carboxylate

Product 1

HCID 20204022Ethyl 1-benzyl-5-(1,3-dithiol-2-ylidene)-3-methyl-4,6-dioxopiperidine-3-carboxylateYield 85.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

Sodium hydride (60% dispersion in oil, 175 mg) is suspended in dimethylformamide (10 ml), and thereto is added dropwise a solution of ethyl 1-benzyl-5-(1,3-dithiol-2-ylidene)-4,6-dioxopiperidine-3-carboxylate (1.3 g) in dimethylformamide (30 ml) under ice-cooling. The mixture is stirred at the same temperature for 20 minutes. Methyl iodide (0.7 ml) is added to the mixture, and the mixture is stirred under ice-cooling for 1.5 hours and then at room temperature for 1.5 hours. The mixture is poured into water and extracted with ethyl acetate. The extract is washed with a saturated sodium chloride solution, dried and then distilled to remove the solvent. The residue is recrystallized from a mixture of ethyl acetate and n-hexane to give ethyl 1-benzyl-5-(1,3-dithiol-2-ylidene)-3-methyl-4,6-dioxopiperidine-3-carboxylate (1.15 g, 85.2%) as pale yellow needles, m.p. 111°-113° C.

Workup

  1. temperaturecooling
  2. stirringthe mixture is stirred under ice-
  3. temperaturecooling for 1.5 hours
  4. waitat room temperature for 1.5 hours
  5. extractionextracted with ethyl acetate
  6. washThe extract is washed with a saturated sodium chloride solution
  7. customdried
  8. distillationdistilled
  9. customto remove the solvent
  10. customThe residue is recrystallized from a mixture of ethyl acetate and n-hexane

Sources & evidence

ORD record
ord-ae998045c7944fd6b2fca58f223b81e1
Source dataset
uspto-grants-1987_05
Patent number
US04663319

Reaction notes

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