Dimethylformamide → HCID 86644477, compound

HRID 2404546Notes

Reaction equation

HRID 2404546 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:21])=[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.CN(C)C=O>ClCCl>[F:1][C:2]1[CH:7]=[C:6]([CH3:8])[C:5]([S:9][CH2:10][C:11]([F:13])([F:12])[F:14])=[CH:4][C:3]=1[N:15]1[C:19]([CH2:20][OH:21])=[CH:18][C:17]([O:23][CH2:24][C:25]([F:30])([F:31])[C:26]([F:27])([F:28])[F:29])=[N:16]1

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 65578Oxalyl chlorideHCID 86644474HCID 86644474, compound

Product 1

HCID 86644477HCID 86644477, compoundYield 78.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

3.97 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 60 mL of dichloromethane, and 0.93 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, the resulting product was dissolved in 50 mL of tetrahydrofuran, and 1.56 g of sodium borohydride was added, followed by cooling to −20° C. 20 mL of water was slowly dropwise added, and 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=1:2) to obtain 3.01 g of 1-{2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl}-5-hydroxymethyl-3-(2,2,3,3,3-pentafluoropropoxy)pyrazole.

Workup

  1. distillationThen, the solvent was distilled off under reduced pressure
  2. dissolutionthe resulting product was dissolved in 50 mL of tetrahydrofuran
  3. addition1.56 g of sodium borohydride was added
  4. temperatureby cooling to −20° C
  5. addition20 mL of water was slowly dropwise added
  6. stirringstirring
  7. waitwas carried out for 12 hours while the temperature
  8. temperaturewas slowly increased to room temperature
  9. distillationThen, the solvent was distilled off under reduced pressure, extraction with ethyl acetate
  10. dry with materialthe organic layer was dried over anhydrous sodium sulfate
  11. distillationthe solvent was distilled off under reduced pressure
  12. customthe obtained residue was purified by column chromatography (developing solvent ethyl acetate:hexane=1:2)

Sources & evidence

ORD record
ord-f6c60c74d1f1466e9c34d861950ab683
Source dataset
uspto-grants-2014_08
Patent number
US08802713B2

Reaction notes

Loading…