Acetic Acid → 4-(2,4-Dichlorophenyl)-N-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine

HRID 514235Notes

Reaction equation

HRID 514235 reaction equation
C(O)(=O)C.[CH3:5][NH:6][NH2:7].[C:8]([CH:11]([C:23]1[CH:28]=[CH:27][C:26]([Cl:29])=[CH:25][C:24]=1[Cl:30])[C:12](=S)[NH:13][C:14]1[CH:19]=[CH:18][C:17]([F:20])=[CH:16][C:15]=1[F:21])(=O)[CH3:9]>C(O)C.C(OCC)(=O)C>[Cl:30][C:24]1[CH:25]=[C:26]([Cl:29])[CH:27]=[CH:28][C:23]=1[C:11]1[C:8]([CH3:9])=[N:7][N:6]([CH3:5])[C:12]=1[NH:13][C:14]1[CH:19]=[CH:18][C:17]([F:20])=[CH:16][C:15]=1[F:21]

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 6061MethylhydrazineHCID 86660671alpha-acetyl-2,4-dichloro-N-(2,4-difluorophenyl)benzeneethanethioamide

Product 1

HCID 666123474-(2,4-Dichlorophenyl)-N-(2,4-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

Acetic acid (50 μL) and methylhydrazine (41 μL) were added to a stirred suspension of α-acetyl-2,4-dichloro-N-(2,4-difluorophenyl)benzeneethanethioamide (238 mg, 0.64 mmol) in ethanol (4 mL). The reaction mixture was heated at reflux for 2 h and allowed to cool. Then the reaction mixture was diluted with ethyl acetate (10 mL) and washed with 1 N aqueous NaOH (10 mL), water (10 mL) and brine (10 mL), dried over MgSO4, and concentrated to leave a solid residue. The residue was purified by column chromatography on 5 g of silica gel with a gradient of hexanes/ethyl acetate (2:1 to 1:1) to give the title compound as a solid (170 mg).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for 2 h
  3. temperatureto cool
  4. washwashed with 1 N aqueous NaOH (10 mL), water (10 mL) and brine (10 mL)
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated
  7. customto leave a solid residue
  8. customThe residue was purified by column chromatography on 5 g of silica gel with a gradient of hexanes/ethyl acetate (2:1 to 1:1)

Sources & evidence

ORD record
ord-e917105394e24e7ba06158edd1a67a6e
Source dataset
uspto-grants-2015_08
Patent number
US09107412B2

Reaction notes

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