Hydrochloric Acid → N-vinyl-3-(3-chloro-5-trifluoromethylpyridin-2-yloxy)-5-methylpyrazole-1-carbothioamide

HRID 644899Notes

Reaction equation

HRID 644899 reaction equation
C(=O)([O-])[O-].[K+].[K+].Br[CH2:8][CH2:9][N:10]=[C:11]=[S:12].[Cl:13][C:14]1[C:15]([O:24][C:25]2[CH:29]=[C:28]([CH3:30])[NH:27][N:26]=2)=[N:16][CH:17]=[C:18]([C:20]([F:23])([F:22])[F:21])[CH:19]=1.Cl>CN(C=O)C>[CH:9]([NH:10][C:11]([N:27]1[C:28]([CH3:30])=[CH:29][C:25]([O:24][C:15]2[C:14]([Cl:13])=[CH:19][C:18]([C:20]([F:23])([F:22])[F:21])=[CH:17][N:16]=2)=[N:26]1)=[S:12])=[CH2:8]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 11430Potassium CarbonateHCID 1370262-Bromoethyl isothiocyanateHCID 178624573-(3-Chloro-5-trifluoromethylpyridin-2-yloxy)-5-methylpyrazole

Product 1

HCID 17862433N-vinyl-3-(3-chloro-5-trifluoromethylpyridin-2-yloxy)-5-methylpyrazole-1-carbothioamideYield 6.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Potassium carbonate (0.76 g, 5.5 mmol) and 2-bromoethyl isothiocyanate (0.83 g, 5 mmol) were added to a solution of 3-(3-chloro-5-trifluoromethylpyridin-2-yloxy)-5-methylpyrazole (1.39 g, 5.0 mmol) in DMF (15 ml), and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the reaction mixture was poured into 2N hydrochloric acid (30 ml) and extracted with ethyl acetate (30 ml×3). An organic layer was washed with water, dried over anhydrous magnesium sulfate and filtered to remove a desiccant, and the solvent was distilled off from the filtrate under reduced pressure. The resultant crude product was purified with a silica gel column (ethyl acetate/hexane=1/20→1/10), to give a white solid of N-vinyl-3-(3-chloro-5-trifluoromethylpyridin-2-yloxy)-5-methylpyrazole-1-carbothioamide (0.11 g, yield: 5.0%). mp: 90-92° C.; 1H-NMR (CDCl3, TMS, ppm): δ 2.87 (d, J=0.8 Hz, 3H), 4.79 (d, J=8.6 Hz, 1H), 5.00 (dd, J=0.9 and 15.7 Hz, 1H), 6.19 (q, J=0.8 Hz, 1H), 7.45 (ddd, J=0.9, 8.6 and 15.7 Hz, 1H), 8.04 (d, J=2.1 Hz, 1H), 8.36 (m, 1H), 10.15-10.55 (m, 1H).

Workup

  1. customAfter completion of the reaction
  2. extractionextracted with ethyl acetate (30 ml×3)
  3. washAn organic layer was washed with water
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. customto remove a desiccant, and the solvent
  7. distillationwas distilled off from the filtrate under reduced pressure
  8. customThe resultant crude product was purified with a silica gel column (ethyl acetate/hexane=1/20→1/10)

Sources & evidence

ORD record
ord-64d5ffd002b340f5879e323febff5091
Source dataset
uspto-grants-2010_04
Patent number
US07700786B2

Reaction notes

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