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

HRID 499992Notes

Reaction equation

HRID 499992 reaction equation
[OH:1][C:2]1[CH:6]=[C:5]([CH3:7])[N:4]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[N:3]=1.C(=O)([O-])[O-].[K+].[K+].[Cl:19][C:20]1[CH:21]=[C:22]([C:28]([F:31])([F:30])[F:29])[CH:23]=[C:24]([F:27])[C:25]=1F.Cl>CS(C)=O>[Cl:19][C:20]1[CH:21]=[C:22]([C:28]([F:29])([F:30])[F:31])[CH:23]=[C:24]([F:27])[C:25]=1[O:1][C:2]1[CH:6]=[C:5]([CH3:7])[N:4]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[N:3]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 11430Potassium CarbonateHCID 2736496Benzene, 1-chloro-2,3-difluoro-5-(trifluoromethyl)-HCID 178473420Ethyl 5-methyl-3-oxo-2,3-dihydro-1H-pyrazole-1-carboxylate

Product 1

HCID 57548573Ethyl 3-(2-chloro-6-fluoro-4-trifluoromethylphenyloxy)-5-methylpyrazole-1-carboxylateYield 72.9%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
40 °C

Procedure

To a DMSO (15 mL) solution of ethyl 3-hydroxy-5-methylpyrazole-1-carboxylate (1.36 g, 8.0 mmol) and potassium carbonate (1.1 g, 8.0 mmol) was added 3-chloro-4,5-difluorobenzotrifluoride (1.77 g, 8.0 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=1:7˜1:5) to give a white solid of ethyl 3-(2-chloro-6-fluoro-4-trifluoromethylphenyloxy)-5-methylpyrazole-1-carboxylate (2.14 g, yield: 72.9%). Melting point: 127˜129° C., 1H-NMR (CDCl3, TMS, ppm): δ1.40 (t, J=7.1 Hz, 3H), 2.53 (d, J=0.8 Hz, 3H), 4.41 (q, J=7.1 Hz, 2H), 5.81 (d, J=0.8 Hz, 1H), 7.38 (dd, J=2.1 Hz, JHF=9.5 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=1:7˜1:5)

Sources & evidence

ORD record
ord-3c0fe6d0abc24a68b3166de2320de22f
Source dataset
uspto-grants-2010_08
Patent number
US07767827B2

Reaction notes

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