Dibromomethane → 1-(4-Chlorophenyl)-2-(1,3-dithietan-2-ylidene)-2-(4-pyridinyl)ethanone

HRID 1060954Notes

Reaction equation

HRID 1060954 reaction equation
[N:1]1[CH:6]=[CH:5][C:4]([CH2:7][C:8]([C:10]2[CH:15]=[CH:14][C:13]([Cl:16])=[CH:12][CH:11]=2)=[O:9])=[CH:3][CH:2]=1.BrCBr.[C:20](=[S:22])=[S:21].[C:23](=O)([O-])[O-].[K+].[K+]>CC(C)=O>[Cl:16][C:13]1[CH:12]=[CH:11][C:10]([C:8](=[O:9])[C:7](=[C:20]2[S:22][CH2:23][S:21]2)[C:4]2[CH:5]=[CH:6][N:1]=[CH:2][CH:3]=2)=[CH:15][CH:14]=1

Participants

6

Reactant 4

HCID 3024DibromomethaneHCID 6348Carbon Disulfide2×HCID 11430Potassium Carbonate2×HCID 103990241-(4-Chloro-phenyl)-2-pyridin-4-YL-ethanone

Product 1

HCID 155168911-(4-Chlorophenyl)-2-(1,3-dithietan-2-ylidene)-2-(4-pyridinyl)ethanoneYield 81.7%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

To a solution of 2-(4-pyridyl)-1-(4-chlorophenyl)ethanone (70.0 g, 0.3 mol) prepared in a similar manner as the compound of Step 1 of Example A-19, dibromomethane (200 mL) and carbon disulfide (25.9 g, 0.34 mol) in acetone (800 mL) was added potassium carbonate (83.0 g, 0.6 mol). The reaction mixture was stirred at room temperature for 24 hours. An additional two equivalents of potassium carbonate and one equivalent of carbon disulfide was added and the stirring was continued for another 24 hours. Solvent was removed and the residue was partitioned between dichloromethane and water. The organic layer was washed with brine, dried over magnesium sulfate and filtered. The filtrate was concentrated and the crude was stirred with 1000 mL of a mixture of ethyl acetate and ether (1:9) to give 78.4 g of pure product, 1-(4-chlorophenyl)-2-(1,3-dithietan-2-ylidene)-2-(4-pyridinyl)ethanone, as a yellow solid (82%), mp: 177-179° C. Anal. Calc'd. for C15H10ClNOS2: C, 56.33; H, 3.15; N, 4.38. Found: C, 55.80; H, 2.84; N, 4.59.

Workup

  1. waitthe stirring was continued for another 24 hours
  2. customSolvent was removed
  3. customthe residue was partitioned between dichloromethane and water
  4. washThe organic layer was washed with brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated
  8. stirringthe crude was stirred with 1000 mL of a mixture of ethyl acetate and ether (1:9)

Sources & evidence

ORD record
ord-86684e5c5aa64a749e8fb9527dba5d80
Source dataset
uspto-grants-2003_02
Patent number
US06525059B1

Reaction notes

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