Dichloromethane → Pyriprole

HRID 2222263Notes

Reaction equation

HRID 2222263 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=[C:4]([Cl:12])[C:3]=1[N:13]1[C:17]([NH:18][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][N:21]=2)=[CH:16][C:15]([C:26]#[N:27])=[N:14]1.ClCCl.[F:31][CH:32]([F:35])[S:33]Cl>C(OCC)(=O)C>[Cl:1][C:2]1[CH:7]=[C:6]([C:8]([F:10])([F:11])[F:9])[CH:5]=[C:4]([Cl:12])[C:3]=1[N:13]1[C:17]([NH:18][CH2:19][C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][N:21]=2)=[C:16]([S:33][CH:32]([F:35])[F:31])[C:15]([C:26]#[N:27])=[N:14]1

Participants

5

Reactant 3

HCID 6344Dichloromethane2×HCID 114184771-(2,6-Dichloro-4-trifluoromethylphenyl)-5-(pyridin-2-ylmethylamino)pyrazole-3-carbonitrileHCID 22618524(Chlorosulfanyl)(difluoro)methane

Product 1

HCID 12056859PyriproleYield 90%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

Under a nitrogen atmosphere, 500 mg (1.21 mmol) of 1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(pyridin-2-ylmethylamino)pyrazole-3-carbonitrile was suspended into 5.0 mL of dried dichloromethane, and 2.0 mL of dried dichloromethane containing 180 mg (1.52 mmol, 1.25 eq.) of difluoromethylsulfenyl chloride was added dropwise thereto under stirring at room temperature, followed by reaction for 2 hours. Ethyl acetate (100 mL) was added thereto, and the organic layer was washed successively with 20 mL of a saturated aqueous sodium hydrogen carbonate solution and 20 mL of water, followed by drying over anhydrous magnesium sulfate. After magnesium sulfate was filtered off, the solvent was removed by distillation under reduced pressure and the crude product was recrystallized from a mixed solvent of hexane/ethyl acetate (3/1) to thereby obtain 535 mg of 1-(2,6-dichloro-4-trifluoromethylphenyl)-4-difluoromethylthio-5-(pyridin-2-ylmethylamino)pyrazole-3-carbonitrile (yield: 90%, purity: 96%).

Workup

  1. additionwas added dropwise
  2. customfollowed by reaction for 2 hours
  3. washthe organic layer was washed successively with 20 mL of a saturated aqueous sodium hydrogen carbonate solution and 20 mL of water
  4. dry with materialby drying over anhydrous magnesium sulfate
  5. filtrationAfter magnesium sulfate was filtered off
  6. customthe solvent was removed by distillation under reduced pressure
  7. customthe crude product was recrystallized from a mixed solvent of hexane/ethyl acetate (3/1)

Sources & evidence

ORD record
ord-5875112d14ee409783e3c709833b32c0
Source dataset
uspto-grants-2008_05
Patent number
US07371768B2

Reaction notes

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