Dimethylformamide → HCID 131731766, compound

HRID 2404543Notes

Reaction equation

HRID 2404543 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([S:9][CH2:10][C:11]([F:14])([F:13])[F:12])=[CH:4][C:3]=1[N:15]1[C:19]([C:20](O)=O)=[CH:18][C:17]([O:23][CH2:24][C:25]([F:31])([F:30])[C:26]([F:29])([F:28])[F:27])=[N:16]1.C(Cl)(=O)C(Cl)=O.C[N:39](C)[CH:40]=[O:41]>ClCCl>[F:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([S:9][CH2:10][C:11]([F:14])([F:13])[F:12])=[CH:4][C:3]=1[N:15]1[C:19]([CH2:20][C:40]([NH2:39])=[O:41])=[CH:18][C:17]([O:23][CH2:24][C:25]([F:31])([F:30])[C:26]([F:29])([F:27])[F:28])=[N:16]1

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 65578Oxalyl chlorideHCID 86644474HCID 86644474, compound

Product 1

HCID 131731766HCID 131731766, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

0.84 g of 1-{2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl}-3-(2,2,3,3,3-pentafluoropropoxy)pyrazole-5-carboxylic acid was dissolved in 10 mL of dichloromethane, and 0.2 mL of oxalyl dichloride and N,N-dimethylformamide in a catalytic amount were added, followed by stirring at room temperature for 1 hour. Then, the solvent was distilled off under reduced pressure, and the resulting product was dissolved in 10 mL of tetrahydrofuran, and the solution was dropwise added to a mixed solution comprising 30 mL of a 25 mass % ammonia water and 40 mL of tetrahydrofuran at −30° C. Then, stirring was carried out for 12 hours while the temperature was slowly increased to room temperature. Then, the solvent was distilled off under reduced pressure, extraction with ethyl acetate was carried out, the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the obtained residue was purified by column chromatography (developing solvent ethyl acetate:hexane=1:3) to obtain 0.80 g of 1-{2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl}-3-(2,2,3,3,3-pentafluoropropoxy)pyrazole-5-carboxyamide.

Workup

  1. distillationThen, the solvent was distilled off under reduced pressure
  2. dissolutionthe resulting product was dissolved in 10 mL of tetrahydrofuran
  3. additionthe solution was dropwise added to a mixed solution
  4. customat −30° C
  5. stirringThen, stirring
  6. waitwas carried out for 12 hours while the temperature
  7. temperaturewas slowly increased to room temperature
  8. distillationThen, the solvent was distilled off under reduced pressure, extraction with ethyl acetate
  9. dry with materialthe organic layer was dried over anhydrous sodium sulfate
  10. distillationthe solvent was distilled off under reduced pressure
  11. customthe obtained residue was purified by column chromatography (developing solvent ethyl acetate:hexane=1:3)

Sources & evidence

ORD record
ord-b98141ea7f2e401ca14849fbaae97826
Source dataset
uspto-grants-2014_08
Patent number
US08802713B2

Reaction notes

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