Water → HCID 86644504, compound

HRID 2404564Notes

Reaction equation

HRID 2404564 reaction equation
[C:1]([NH:4][C:5]1[N:9]([C:10]2[CH:15]=[C:14]([S:16][CH2:17][C:18]([F:21])([F:20])[F:19])[C:13]([CH3:22])=[CH:12][C:11]=2[F:23])[N:8]=[C:7]([O:24][C:25]([F:40])([F:39])[C:26]([F:38])([F:37])[C:27]([F:36])([F:35])[C:28]([F:34])([F:33])[C:29]([F:32])([F:31])[F:30])[CH:6]=1)(=O)C.[H-].[Na+].CI.O>CN(C)C=O>[F:23][C:11]1[CH:12]=[C:13]([CH3:22])[C:14]([S:16][CH2:17][C:18]([F:21])([F:20])[F:19])=[CH:15][C:10]=1[N:9]1[C:5]([NH:4][CH3:1])=[CH:6][C:7]([O:24][C:25]([F:40])([F:39])[C:26]([F:37])([F:38])[C:27]([F:35])([F:36])[C:28]([F:34])([F:33])[C:29]([F:32])([F:31])[F:30])=[N:8]1

Participants

6

Reactant 4

HCID 962WaterHCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 86644500HCID 86644500, compound

Product 1

HCID 86644504HCID 86644504, compoundYield 90.7%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

0.45 g of 5-acetylamino-1-{2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl}-3-(1,1,2,2,3,3,4,4,5,5,5-undecafluoropentyloxy)pyrazole was dissolved in 5 mL of N,N-dimethylformamide, the solution was dropwise added to a suspension having 40 mg of sodium hydride suspended in 10 mL of N,N-dimethylformamide under cooling with ice, and after completion of the dropwise addition, stirring was carried out at room temperature for 30 minutes. The reaction solution was cooled with ice again, and 0.15 g of methyl iodide was added, followed by stirring at room temperature for one hour. Then, water was injected, extraction with ethyl acetate was carried out, followed by washing with water, and the organic layer was dried over anhydrous magnesium sulfate. Then, the solvent was distilled off under reduced pressure, the obtained residue was dissolved in 10 mL of ethanol, and 10 mL of a 35 mass % hydrochloric acid aqueous solution was added, followed by stirring under reflux with heating for one hour. Then, the reaction mixture was poured into water, extraction with ethyl acetate was carried out, followed by washing with water, and the organic layer was dried over anhydrous magnesium sulfate. Then, the solvent was distilled off under reduced pressure, and the obtained residue was purified by column chromatography (developing solvent ethyl acetate:hexane=1:4) to obtain 0.39 g of 1-{2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl}-5-methylamino-3-(1,1,2,2,3,3,4,4,5,5,5-undecafluoropentyloxy)pyrazole.

Workup

  1. additionthe solution was dropwise added to a suspension
  2. temperatureunder cooling with ice
  3. additionafter completion of the dropwise addition
  4. temperatureThe reaction solution was cooled with ice again
  5. stirringby stirring at room temperature for one hour
  6. extractionextraction with ethyl acetate
  7. washby washing with water
  8. dry with materialthe organic layer was dried over anhydrous magnesium sulfate
  9. distillationThen, the solvent was distilled off under reduced pressure
  10. dissolutionthe obtained residue was dissolved in 10 mL of ethanol
  11. addition10 mL of a 35 mass % hydrochloric acid aqueous solution was added
  12. stirringby stirring
  13. temperatureunder reflux
  14. temperaturewith heating for one hour
  15. additionThen, the reaction mixture was poured into water, extraction with ethyl acetate
  16. washby washing with water
  17. dry with materialthe organic layer was dried over anhydrous magnesium sulfate
  18. distillationThen, the solvent was distilled off under reduced pressure
  19. customthe obtained residue was purified by column chromatography (developing solvent ethyl acetate:hexane=1:4)

Sources & evidence

ORD record
ord-78d4ccf0820342058a9a364b0ed74e0d
Source dataset
uspto-grants-2014_08
Patent number
US08802713B2

Reaction notes

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