Nitric Acid → HCID 15767491, compound

HRID 362641Notes

Reaction equation

HRID 362641 reaction equation
[NH2:1][C:2]1[N:6]([C:7]2[CH:11]=[C:10]([O:12][CH:13]([F:15])[F:14])[N:9]([CH3:16])[N:8]=2)[N:5]=[CH:4][CH:3]=1.C(OC(=O)C)(=O)C.[N+:24]([O-])([OH:26])=[O:25]>C(O)(=O)C>[NH2:1][C:2]1[N:6]([C:7]2[CH:11]=[C:10]([O:12][CH:13]([F:14])[F:15])[N:9]([CH3:16])[N:8]=2)[N:5]=[CH:4][C:3]=1[N+:24]([O-:26])=[O:25]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 7918Acetic Anhydride2×HCID 15767490HCID 15767490, compound

Product 1

HCID 15767491HCID 15767491, compound

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

15 g (0.065 mol) 5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)pyrazole was dissolved in 60 ml acetic acid and treated with 7.35 g (0.072 mol) acetic anhydride. After stirring at room temperature for 3 hours, the reaction mixture was cooled to 10° C. 4.95 g (0.078 mol) Fuming nitric acid was added dropwise and the mixture treated with 8.0 g (0.078 mol) acetic anhydride. After stirring for 18 hours at room temperature, the reaction mixture was added to 500 ml ice-water. It was extracted three times with ethyl acetate, the organic phases were washed with water and concentrated. The residue was treated with 80 ml ethanol and 40 ml concentrated hydrochloric acid. After heating for 8 hours under reflux, the ethanol was removed and the residue extracted with ethyl acetate. The concentrated ethyl acetate phases were washed with saturated aqueous sodium hydrogen carbonate, dried over magnesium sulfate and concentrated. The residue was recrystallised from diisopropyl ether and ethyl acetate.

Workup

  1. temperaturethe reaction mixture was cooled to 10° C
  2. additionwas added dropwise
  3. stirringAfter stirring for 18 hours at room temperature
  4. extractionIt was extracted three times with ethyl acetate
  5. washthe organic phases were washed with water
  6. concentrationconcentrated
  7. additionThe residue was treated with 80 ml ethanol and 40 ml concentrated hydrochloric acid
  8. temperatureAfter heating for 8 hours
  9. temperatureunder reflux
  10. customthe ethanol was removed
  11. extractionthe residue extracted with ethyl acetate
  12. washThe concentrated ethyl acetate phases were washed with saturated aqueous sodium hydrogen carbonate
  13. dry with materialdried over magnesium sulfate
  14. concentrationconcentrated
  15. customThe residue was recrystallised from diisopropyl ether and ethyl acetate

Sources & evidence

ORD record
ord-ec6bff223ecb42bfb5580eaab49ea7fa
Source dataset
uspto-grants-1999_02
Patent number
US05869686

Reaction notes

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