Methanol → 2,5-bis(2-fluorophenyl)-4-hydrazinylidenepyrazol-3-one

HRID 241987Notes

Reaction equation

HRID 241987 reaction equation
[N+:1](=[C:3]1[C:7]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[F:14])=[N:6][N:5]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2[F:21])[C:4]1=[O:22])=[N-:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CO.C(=O)(O)[O-].[Na+]>C(#N)C.[Cl-].[Na+].O.O>[F:21][C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=1[N:5]1[C:4](=[O:22])[C:3](=[N:1][NH2:2])[C:7]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=2[F:14])=[N:6]1

Participants

8

Reactant 4

HCID 887MethanolHCID 11776TriphenylphosphineHCID 516892Sodium BicarbonateHCID 178514319HCID 178514319, compound

Product 1

HCID 1785143202,5-bis(2-fluorophenyl)-4-hydrazinylidenepyrazol-3-one

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

4-Diazo-2,5-bis(2-fluorophenyl)-2,4-dihydro-3H-pyrazol-3-one [(Example 18, Step 2) 213 mg, 0.714 mmol] was dissolved in acetonitrile (10 mL) and treated with triphenylphosphine (225 mg, 0.857 mmol, 1.2 equiv). After stirring for 30 minutes at ambient temperature, the mixture was treated with methanol (5 mL) and water (5 mL) and warmed to 60° C. for 1 hour. The mixture was cooled to ambient temperature, poured into brine (50 mL) and sodium bicarbonate (20 mL, aqueous saturated) and extracted with ethyl acetate (2×100 mL). The combined organic extracts were dried with sodium sulfate, filtered and concentrated in vacuo. The residue was purified by silica gel gradient chromatography (100:0 to 70:30; hexanes:ethyl acetate), providing the titled compound.

Workup

  1. temperaturewarmed to 60° C. for 1 hour
  2. temperatureThe mixture was cooled to ambient temperature
  3. extractionextracted with ethyl acetate (2×100 mL)
  4. dry with materialThe combined organic extracts were dried with sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by silica gel gradient chromatography (100:0 to 70:30; hexanes:ethyl acetate)

Sources & evidence

ORD record
ord-fbc3ae3b06e344f9861f4d12d8266dc0
Source dataset
uspto-grants-2014_02
Patent number
US08653079B2

Reaction notes

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