Hydrochloric Acid → Cyclaniliprole

HRID 1641456Notes

Reaction equation

HRID 1641456 reaction equation
[Br:1][C:2]1[CH:6]=[C:5]([C:7]([NH:9][C:10]2[CH:15]=[CH:14][C:13]([Cl:16])=[CH:12][C:11]=2[C:17](=[O:24])[NH:18][CH:19]([CH:21]2[CH2:23][CH2:22]2)[CH3:20])=[O:8])[N:4]([C:25]2[C:30]([Cl:31])=[CH:29][CH:28]=[CH:27][N:26]=2)[N:3]=1.[H-].[Na+].[Br:34]Br.Cl>CN(C)C=O>[Br:1][C:2]1[CH:6]=[C:5]([C:7]([NH:9][C:10]2[C:11]([C:17]([NH:18][CH:19]([CH:21]3[CH2:23][CH2:22]3)[CH3:20])=[O:24])=[CH:12][C:13]([Cl:16])=[CH:14][C:15]=2[Br:34])=[O:8])[N:4]([C:25]2[C:30]([Cl:31])=[CH:29][CH:28]=[CH:27][N:26]=2)[N:3]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 24408BromineHCID 24758Sodium hydrideHCID 667361933-bromo-N-(4-chloro-2-(1-cyclopropylethylcarbamoyl)phenyl)-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide

Product 1

HCID 24822142CyclaniliproleYield 72.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A mixed solution comprising 0.24 g of 3-bromo-N-(4-chloro-2-(1-cyclopropylethylcarbamoyl)phenyl)-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide and 5 ml of dimethylformamide was cooled with ice, 46 mg of 60% sodium hydride was added, and the temperature was returned to room temperature, followed by stirring for 25 minutes. The reaction liquid was cooled with ice again, and a mixed solution comprising 0.15 g of bromine and 1 ml of dimethylformamide was dropwise added over a period of 1 minute, followed by reaction at room temperature for 2 hours and 45 minutes. After completion of the reaction, the reaction liquid was slowly added to 60 ml of diluted hydrochloric acid. The mixed liquid was subjected to extraction with ethyl acetate, and the organic layer was washed with a saturated sodium hydrogen carbonate aqueous solution and with a sodium chloride aqueous solution and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate=8/2 to 0/1) to obtain 0.20 g of the desired product (melting point: 244 to 247° C.) in the form of white crystals.

Workup

  1. additionwas added
  2. customwas returned to room temperature
  3. customThe reaction liquid
  4. temperaturewas cooled with ice again
  5. additionwas dropwise added over a period of 1 minute
  6. customfollowed by reaction at room temperature for 2 hours and 45 minutes
  7. customAfter completion of the reaction
  8. customthe reaction liquid
  9. extractionThe mixed liquid was subjected to extraction with ethyl acetate
  10. washthe organic layer was washed with a saturated sodium hydrogen carbonate aqueous solution and with a sodium chloride aqueous solution
  11. dry with materialdried over anhydrous sodium sulfate
  12. distillationThe solvent was distilled off under reduced pressure
  13. customthe residue was purified by silica gel column chromatography (eluent: n-hexane/ethyl acetate=8/2 to 0/1)

Sources & evidence

ORD record
ord-a5844d4c84bc416a8b8e61ee3b765549
Source dataset
uspto-grants-2012_02
Patent number
US08115006B2

Reaction notes

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