Diphosgene → N-s-butyl-3-(3-chloro-5-trifluoromethylpyridin-2-yloxy)-5-methylpyrazole-1-carboxamide

HRID 644905Notes

Reaction equation

HRID 644905 reaction equation
ClC([O:4][C:5](Cl)(Cl)Cl)=O.[Cl:9][C:10]1[C:11]([O:20][C:21]2[CH:25]=[C:24]([CH3:26])[NH:23][N:22]=2)=[N:12][CH:13]=[C:14]([C:16]([F:19])([F:18])[F:17])[CH:15]=1.[CH:27]([NH2:31])([CH2:29][CH3:30])[CH3:28].C(=O)([O-])[O-].[K+].[K+]>C(Cl)(Cl)Cl>[CH:27]([NH:31][C:5]([N:23]1[C:24]([CH3:26])=[CH:25][C:21]([O:20][C:11]2[C:10]([Cl:9])=[CH:15][C:14]([C:16]([F:18])([F:19])[F:17])=[CH:13][N:12]=2)=[N:22]1)=[O:4])([CH2:29][CH3:30])[CH3:28]

Participants

6

Reactant 4

HCID 10426DiphosgeneHCID 11430Potassium CarbonateHCID 24874Sec-ButylamineHCID 178624573-(3-Chloro-5-trifluoromethylpyridin-2-yloxy)-5-methylpyrazole

Product 1

HCID 17862456N-s-butyl-3-(3-chloro-5-trifluoromethylpyridin-2-yloxy)-5-methylpyrazole-1-carboxamideYield 25.5%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

Trichloromethyl chloroformate (0.49 g, 2.5 mmol) was added to a solution of 3-(3-chloro-5-trifluoromethylpyridin-2-yloxy)-5-methylpyrazole (0.69 g, 2.5 mmol) in chloroform (10 ml) at 0° C., and while the mixture was allowed to have room temperature gradually, it was further stirred at room temperature for 3 hours. Sec-butylamine (0.22 g, 3.0 mmol) and potassium carbonate (0.42 g, 3.0 mmol) were added to the reaction mixture, and the mixture was stirred at 50° C. for 8 hours. After completion of the reaction, the reaction mixture was poured into ice water and extracted with chloroform (20 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=1/7), to give a colorless viscous substance of N-s-butyl-3-(3-chloro-5-trifluoromethylpyridin-2-yloxy)-5-methylpyrazole-1-carboxamide (0.24 g, yield: 25.5%). 1H-NMR (CDCl3, TMS, ppm): δ 0.96 (t, J=7.5 Hz, 3H), 1.22 (d, J=6.6 Hz, 3H), 1.45-1.65 (m, 2H), 2.65 (s, 3H), 3.75-4.00 (m, 1H), 6.04 (s, 1H), 6.75-7.05 (m, 1H), 8.02 (d, J=1.8 Hz, 1H), 8.30-8.40 (m, 1H).

Workup

  1. customto have room temperature
  2. stirringthe mixture was stirred at 50° C. for 8 hours
  3. customAfter completion of the reaction
  4. extractionextracted with chloroform (20 ml×3)
  5. washAn organic layer was washed with water
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. customto remove a desiccant, and the solvent
  9. distillationwas distilled off from the filtrate under reduced pressure
  10. customThe resultant crude product was purified with a silica gel column (ethyl acetate/hexane=1/7)

Sources & evidence

ORD record
ord-bbe858543b60491fb3edd5dc1e2b4d55
Source dataset
uspto-grants-2010_04
Patent number
US07700786B2

Reaction notes

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