Methylhydrazine → HCID 22288404, compound

HRID 1296475Notes

Reaction equation

HRID 1296475 reaction equation
C[O-].[Na+].[C:4]([C:7]1[CH:8]=[C:9]([CH:20]=[CH:21][CH:22]=1)[NH:10][C:11](=[O:19])[C:12]1[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][CH:13]=1)(=O)[CH3:5].[F:23][C:24]([F:31])([F:30])[C:25](OCC)=O.[CH3:32][NH:33][NH2:34]>C(O)C.C(O)(=O)C.O.CO>[Cl:18][C:15]1[CH:16]=[CH:17][C:12]([C:11]([NH:10][C:9]2[CH:20]=[CH:21][CH:22]=[C:7]([C:4]3[CH:5]=[C:25]([C:24]([F:31])([F:30])[F:23])[N:33]([CH3:32])[N:34]=3)[CH:8]=2)=[O:19])=[CH:13][CH:14]=1

Participants

9

Reactant 4

HCID 6061MethylhydrazineHCID 9794Ethyl trifluoroacetateHCID 673728TIMTEC-BB SBB001086HCID 10942334Sodium Methoxide

Product 1

HCID 22288404HCID 22288404, compound

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 702EthanolSolventHCID 887MethanolSolventHCID 962WaterSolvent

Procedure

Sodium methoxide (257 mg) was added to a mixture of 3′-acetyl-4-chlorobenzanilide (1.00 g) and methanol (10 ml) under ice-cooling, followed by stirring at room temperature for 2 hours. Ethyl trifluoroacetate (0.522 ml) was added to the reaction solution under ice-cooling, followed by stirring under heat reflux for 3 days. Water (50 ml) was added to the reaction mixture, the thus formed product was extracted with ethyl acetate and then the extract was washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate and then concentrated under a reduced pressure. The resulting residue was purified by silica gel column chromatography (eluent; n-hexane:ethyl acetate=2:1-1:1) to give a light yellow oil. A mixture of this oil with methyl hydrazine (0.122 ml), acetic acid (1 ml) and ethanol (10 ml) was stirred under heat reflux for 15 hours. After spontaneous cooling, the reaction solution was concentrated under a reduced pressure. After adding ethyl acetate, the thus obtained residue was washed with saturated sodium bicarbonate aqueous solution and saturated brine in that order. The organic layer was dried over anhydrous sodium sulfate and then concentrated under a reduced pressure. The resulting residue was purified by silica gel column chromatography (eluent; n-hexane:ethyl acetate=6:1) and then recrystallized from a mixed solvent of ethyl acetate and n-hexane to give 4-chloro-3′-(1-methyl-5-trifluoromethyl-1H-pyrazol-3-yl)benzanilide (60 mg) as colorless powder crystals.

Workup

  1. temperaturecooling
  2. temperaturecooling
  3. stirringby stirring
  4. temperatureunder heat
  5. temperaturereflux for 3 days
  6. extractionthe thus formed product was extracted with ethyl acetate
  7. washthe extract was washed with saturated brine
  8. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  9. concentrationconcentrated under a reduced pressure
  10. customThe resulting residue was purified by silica gel column chromatography (eluent; n-hexane:ethyl acetate=2:1-1:1)
  11. customto give a light yellow oil
  12. stirringwas stirred
  13. temperatureunder heat
  14. temperaturereflux for 15 hours
  15. concentrationAfter spontaneous cooling, the reaction solution was concentrated under a reduced pressure
  16. additionAfter adding ethyl acetate
  17. washthe thus obtained residue was washed with saturated sodium bicarbonate aqueous solution and saturated brine in that order
  18. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  19. concentrationconcentrated under a reduced pressure
  20. customThe resulting residue was purified by silica gel column chromatography (eluent; n-hexane:ethyl acetate=6:1)
  21. customrecrystallized from a mixed solvent of ethyl acetate and n-hexane

Sources & evidence

ORD record
ord-652555d671764435a2c2bfc0929ab265
Source dataset
uspto-grants-2007_07
Patent number
US07247635B2

Reaction notes

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