1-[(4-Methoxy)phenyl]-3-(trifluoromethyl)-4-cyano-5-(2-furyl)pyrazole → 1-[(4-Methoxy)phenyl]-3-(trifluoromethyl)-4-cyano-1H-pyrazole 5-(2-furyl)pyrazole

HRID 394813Notes

Reaction equation

HRID 394813 reaction equation
FC(F)(F)C1C(C#N)=C(C(O)=O)NN=1.[CH3:15][O:16][C:17]1[CH:22]=[CH:21][C:20]([N:23]2[C:27]([C:28]3[O:29][CH:30]=[CH:31][CH:32]=3)=[C:26]([C:33]#[N:34])[C:25]([C:35]([F:38])([F:37])[F:36])=[N:24]2)=[CH:19][CH:18]=1.C(Cl)(Cl)(Cl)Cl.C(#N)C.O.I([O-])(=O)(=O)=O.[Na+]>O.[Ru](Cl)(Cl)Cl>[CH3:15][O:16][C:17]1[CH:18]=[CH:19][C:20]([N:23]2[CH:27]=[C:26]([C:33]#[N:34])[C:25]([C:35]([F:38])([F:36])[F:37])=[N:24]2)=[CH:21][CH:22]=1.[O:29]1[CH:30]=[CH:31][CH:32]=[C:28]1[C:27]1[NH:23][N:24]=[CH:25][CH:26]=1

Participants

6

Reactant 4

HCID 179399701-[(4-Methoxy)phenyl]-3-(trifluoromethyl)-4-cyano-5-(2-furyl)pyrazoleHCID 22592919water acetonitrile CCl4HCID 23667635Sodium periodateHCID 178510177HCID 178510177, compound

Product 1

HCID 696950671-[(4-Methoxy)phenyl]-3-(trifluoromethyl)-4-cyano-1H-pyrazole 5-(2-furyl)pyrazoleYield 102.6%

Reagents, catalysts & solvents 1

HCID 6093376Ruthenium trichloride hydrateCatalyst

Procedure

1-(4-Methoxy)phenyl]-3-(trifluoromethyl)-4-cyano-pyrazole-5-carboxylic acid. To a solution of 1-[(4-methoxy)phenyl]-3-(trifluoromethyl)-4-cyano-5-(2-furyl)pyrazole (0.68 g, 2.04 mmol) in 4:4:6 carbon tetrachloride/acetonitrile/water was added sodium periodate (1.96 g, 9.2 mmol) and ruthenium (III) chloride monohydrate (42 mg, 0.20 mmol). The resulting biphasic reaction was stirred vigorously at ambient temperature for 24 h. The reaction was quenched with 10% aq HCl and diluted with ethyl acetate. The organics were washed with brine, dried (MgSO4), filtered through a pad of Celite and concentrated. The residue was dissolved in 1:1 hexanes/ethyl acetate and extracted with sat'd aq Na2CO3 (2 times). The combined aqueous extracts were acidified and extracted with ethyl acetate. The ethyl acetate extracts were washed with brine, dried (MgSO4) and concentrated to afford 0.42 g (67%) of the title compound as a solid. LRMS (ES−): 310.0 (M−H)−.

Workup

  1. customThe resulting biphasic reaction
  2. customThe reaction was quenched with 10% aq HCl
  3. additiondiluted with ethyl acetate
  4. washThe organics were washed with brine
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered through a pad of Celite
  7. concentrationconcentrated
  8. dissolutionThe residue was dissolved in 1:1 hexanes/ethyl acetate
  9. extractionextracted with sat'd aq Na2CO3 (2 times)
  10. extractionextracted with ethyl acetate
  11. washThe ethyl acetate extracts were washed with brine
  12. dry with materialdried (MgSO4)
  13. concentrationconcentrated

Sources & evidence

ORD record
ord-4b974a9b010d47c9abb4649bdc43c2ab
Source dataset
uspto-grants-2003_08
Patent number
US06602895B2

Reaction notes

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