Carbon Disulfide → 1-Benzyl-3-(1,3-dithiolan-2-ylidene)-2,4-dioxopiperidine

HRID 977948Notes

Reaction equation

HRID 977948 reaction equation
[CH2:1]([N:8]1[CH2:13][CH2:12][C:11](=[O:14])[CH2:10][C:9]1=[O:15])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:16](=[S:18])=[S:17].[OH-].[K+].[CH2:21](Br)[CH2:22]Br>CS(C)=O.O>[CH2:1]([N:8]1[CH2:13][CH2:12][C:11](=[O:14])[C:10](=[C:16]2[S:18][CH2:22][CH2:21][S:17]2)[C:9]1=[O:15])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 6348Carbon DisulfideHCID 78391,2-DibromoethaneHCID 14797Potassium HydroxideHCID 224955411-Benzylpiperidine-2,4-dione

Product 1

HCID 136065741-Benzyl-3-(1,3-dithiolan-2-ylidene)-2,4-dioxopiperidineYield 35.5%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolvent2×HCID 962WaterSolvent

Procedure

1-Benzyl-2,4-dioxopiperidine (2.03 g) and carbon disulfide (760 mg) are dissolved in dimethylsulfoxide (20 ml), and thereto is added dropwise a solution of potassium hydroxide (1.1 g) in water (3 ml) at room temperature. The mixture is stirred for 30 minutes and thereto is added dropwise a solution of 1,2-dibromomethane (1.87 g) in dimethylsulfoxide (3 ml). The mixture is stirred at room temperature for 2 hours and further at 60° C. for 1 hour. The reaction mixture is poured onto water and extracted with benzene-ethyl acetate. The extract is washed with water, dried and distilled to remove the solvent. The residue is purified by silica gel column chromatography (solvent, benzene:ethyl acetate=8:2) and is recrystallized from ethanol to give 1-benzyl-3-(1,3-dithiolan-2-ylidene)-2,4-dioxopiperidine (1.08 g) as pale yellow needles. m.p. 148°-150° C.

Workup

  1. stirringThe mixture is stirred at room temperature for 2 hours and further at 60° C. for 1 hour
  2. additionThe reaction mixture is poured onto water
  3. extractionextracted with benzene-ethyl acetate
  4. washThe extract is washed with water
  5. customdried
  6. distillationdistilled
  7. customto remove the solvent
  8. customThe residue is purified by silica gel column chromatography (solvent, benzene:ethyl acetate=8:2)
  9. customis recrystallized from ethanol

Sources & evidence

ORD record
ord-03e15b0ff1324a03b24d4ca67a8d83ca
Source dataset
uspto-grants-1987_05
Patent number
US04663319

Reaction notes

Loading…