Oxalyl chloride → 1-[(4-Methoxy)phenyl]-3-(trifluoromethyl)-4-cyano-1H-pyrazole

HRID 2186251Notes

Reaction equation

HRID 2186251 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([N:9]2[C:13](C(O)=O)=[C:12]([C:17]#[N:18])[C:11]([C:19]([F:22])([F:21])[F:20])=[N:10]2)=[CH:5][CH:4]=1.C(Cl)(=O)C(Cl)=O>C(Cl)Cl.CN(C)C=O.CN(C)C1C=CN=CC=1.C(OCC)(=O)C>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]([N:9]2[CH:13]=[C:12]([C:17]#[N:18])[C:11]([C:19]([F:22])([F:20])[F:21])=[N:10]2)=[CH:7][CH:8]=1

Participants

7

Reactant 2

HCID 65578Oxalyl chlorideHCID 179399401-[(4-Methoxy)phenyl]-3-(trifluoromethyl)-4-cyano-pyrazole-5-carboxylic acid

Product 1

HCID 538204911-[(4-Methoxy)phenyl]-3-(trifluoromethyl)-4-cyano-1H-pyrazoleYield 170.1%

Reagents, catalysts & solvents 4

HCID 6228DimethylformamideCatalystHCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 1-[(4-methoxy)phenyl]-3-(trifluoromethyl)-4-cyano-pyrazole-5-carboxylic acid (0.41 g, 1.32 mmol) in 20 mL of methylene chloride was added oxalyl chloride (0.17 mL, 1.98 mmol) and 2 drops of dimethylformamide. The reaction was stirred at ambient temperature for 6 h and then the volatiles were removed in vacuo. The residue was dissolved in 20 mL of methylene chloride and then there was added 4-dimethylaminopyridine (0.48 g, 3.96 mmol). The reaction was stirred for 10 min and then there was added (2′-methylsulfonyl-3-fluoro-[1,1′]-biphen-4-yl)amine hydrochloride (0.47 g, 1.45 mmol). The resulting mixture was allowed to stir at ambient temperature for 16 h. The reaction was diluted with ethyl acetate and the organics were washed with 10% aq HCl, sat'd aq NaHCO3 and brine, dried (MgSO4), filtered through a pad of silica gel and concentrated to afford 0.6 g (81%) of the title compound as a tan solid. LRMS (ES+): 581.3 (M+Na)+.

Workup

  1. customthe volatiles were removed in vacuo
  2. dissolutionThe residue was dissolved in 20 mL of methylene chloride
  3. stirringThe reaction was stirred for 10 min
  4. stirringto stir at ambient temperature for 16 h
  5. washthe organics were washed with 10% aq HCl
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered through a pad of silica gel
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-c120a7085479483eb2786bd8f38eee75
Source dataset
uspto-grants-2002_06
Patent number
US06403620B1

Reaction notes

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