Hydrochloric Acid → Methyl 3-(2-chloro-6-fluoro-4-trifluoromethylphenyloxy)-5-methylpyrazole-1-carboxylate

HRID 499991Notes

Reaction equation

HRID 499991 reaction equation
[OH:1][C:2]1[CH:6]=[C:5]([CH3:7])[N:4]([C:8]([O:10][CH3:11])=[O:9])[N:3]=1.C(=O)([O-])[O-].[K+].[K+].[Cl:18][C:19]1[CH:20]=[C:21]([C:27]([F:30])([F:29])[F:28])[CH:22]=[C:23]([F:26])[C:24]=1F.Cl>CS(C)=O>[Cl:18][C:19]1[CH:20]=[C:21]([C:27]([F:28])([F:29])[F:30])[CH:22]=[C:23]([F:26])[C:24]=1[O:1][C:2]1[CH:6]=[C:5]([CH3:7])[N:4]([C:8]([O:10][CH3:11])=[O:9])[N:3]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 11430Potassium CarbonateHCID 2736496Benzene, 1-chloro-2,3-difluoro-5-(trifluoromethyl)-HCID 178501941Methyl 5-methyl-3-oxo-2,3-dihydro-1H-pyrazole-1-carboxylate

Product 1

HCID 57548572Methyl 3-(2-chloro-6-fluoro-4-trifluoromethylphenyloxy)-5-methylpyrazole-1-carboxylateYield 45.4%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
40 °C

Procedure

To a DMSO (15 mL) solution of methyl 3-hydroxy-5-methylpyrazole-1-carboxylate (1.56 g, 10.0 mmol) and potassium carbonate (1.38 g, 10.0 mmol) was added 3-chloro-4,5-difluorobenzotrifluoride (2.21 g, 10.0 mmol), and the mixture was stirred under heating at 40° C. for 8 hours. After completion of the reaction, the reaction mixture was poured into 2 mol/L hydrochloric acid (30 mL) and extracted with ethyl acetate. The organic layers combined were washed with water, and dried over anhydrous magnesium sulfate, and the solvent was distilled off. The thus-obtained residue was purified by silica gel column chromatography (ethyl acetate:hexane=1:5) to give a white solid of methyl 3-(2-chloro-6-fluoro-4-trifluoromethylphenyloxy)-5-methylpyrazole-1-carboxylate (1.60 g, yield: 45.4%). Melting point: 123˜125° C., 1H-NMR (CDCl3, TMS, ppm): δ2.55 (d, J=0.8 Hz, 3H), 3.94 (s, 3H), 5.87 (d, J=0.8 Hz, 1H), 7.38 (dd, J=2.0 Hz, JHF=9.4 Hz, 1H), 7.50˜7.60 (m, 1H).

Workup

  1. customAfter completion of the reaction
  2. extractionextracted with ethyl acetate
  3. washThe organic layers combined were washed with water
  4. dry with materialdried over anhydrous magnesium sulfate
  5. distillationthe solvent was distilled off
  6. customThe thus-obtained residue was purified by silica gel column chromatography (ethyl acetate:hexane=1:5)

Sources & evidence

ORD record
ord-7af6c45f2ff94ede8cfd9a1e54615a08
Source dataset
uspto-grants-2010_08
Patent number
US07767827B2

Reaction notes

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