Ethanol → HCID 178469375, compound

HRID 2404572Notes

Reaction equation

HRID 2404572 reaction equation
C(O)C.[O-]CC.[Na+].C(O)C.[F:11][C:12]1[CH:17]=[C:16]([CH3:18])[C:15]([S:19][CH2:20][C:21]([F:24])([F:23])[F:22])=[CH:14][C:13]=1[NH:25][NH2:26].[C:27](OCC)(=[O:35])/[CH:28]=[CH:29]\[C:30]([O:32][CH2:33][CH3:34])=[O:31]>C(O)(=O)C>[F:11][C:12]1[CH:17]=[C:16]([CH3:18])[C:15]([S:19][CH2:20][C:21]([F:23])([F:24])[F:22])=[CH:14][C:13]=1[N:25]1[C:29]([C:30]([O:32][CH2:33][CH3:34])=[O:31])=[CH:28][C:27]([OH:35])=[N:26]1

Participants

6

Reactant 4

HCID 702EthanolHCID 5271566Diethyl MaleateHCID 23706232Ethanol sodium ethoxideHCID 66842008HCID 66842008, compound

Product 1

HCID 178469375HCID 178469375, compoundYield 25.5%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

14 g of a 20 mass % sodium ethoxide ethanol solution was added to 20 mL of ethanol, and 10 g of 2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenylhydrazine was rapidly added under reflux with heating. After stirring for 30 seconds, 7.8 g of diethyl maleate was dropwise added, followed by stirring under reflux with heating for 10minutes. The reaction solution was cooled to 50° C. or below, and 4.5 g of acetic acid was added. 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, and the solvent was distilled off under reduced pressure. The obtained residue was dissolved in 80 mL of toluene, 0.68 g of tetra n-butyl ammonium bromide was added, and 3.5 g of a 10 mass % aqueous solution of potassium permanganate was gradually added. After completion of the reaction, ethyl acetate and 20 mL of a saturated aqueous solution of citric acid were added, and the solution was washed with an aqueous sodium thiosulfate solution and then 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=1:1) to obtain 3.80 g of ethyl 1-{2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl}-3-hydroxypyrazole-5-carboxylate.

Workup

  1. additionwas rapidly added
  2. temperatureunder reflux
  3. temperaturewith heating
  4. stirringby stirring
  5. temperatureunder reflux
  6. temperaturewith heating for 10minutes
  7. temperatureThe reaction solution was cooled to 50° C. or below
  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. dissolutionThe obtained residue was dissolved in 80 mL of toluene
  12. addition0.68 g of tetra n-butyl ammonium bromide was added
  13. addition3.5 g of a 10 mass % aqueous solution of potassium permanganate was gradually added
  14. customAfter completion of the reaction, ethyl acetate and 20 mL of a saturated aqueous solution of citric acid
  15. additionwere added
  16. washthe solution was washed with an aqueous sodium thiosulfate solution
  17. dry with materialdried 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=1:1)

Sources & evidence

ORD record
ord-9ac9c6a7bd2842899d6f8fe96b48cf09
Source dataset
uspto-grants-2014_08
Patent number
US08802713B2

Reaction notes

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