Formic Acid → 4-(1H-Pyrazol-1-yl)benzaldehyde

HRID 2117614Notes

Reaction equation

HRID 2117614 reaction equation
[N:1]1([C:6]2[CH:13]=[CH:12][C:9]([C:10]#N)=[CH:8][CH:7]=2)[CH:5]=[CH:4][CH:3]=[N:2]1.C(O)=[O:15]>[Ni]>[N:1]1([C:6]2[CH:13]=[CH:12][C:9]([CH:10]=[O:15])=[CH:8][CH:7]=2)[CH:5]=[CH:4][CH:3]=[N:2]1

Participants

4

Reactant 2

HCID 284Formic AcidHCID 120796294-(1-Pyrazolyl)benzonitrile

Product 1

HCID 27764774-(1H-Pyrazol-1-yl)benzaldehyde

Reagents, catalysts & solvents 1

HCID 935NickelCatalyst

Procedure

To a solution of 4-pyrazol-1-yl-benzonitrile (1.6 g, 9.47 mmol), prepared in Step A of Preparation 42, in 75% aqueous formic acid (36 mL) was added Raney nickel alloy (1.6 g). The reaction was heated at reflux for 1.25 h and was cooled to room temperature. The solids were removed by filtration through Celite with the aid of hot EtOH. The solution was diluted with water and CHCl3. The aqueous layer was washed with CHCl3 (3×). To the organic solution was carefully added aqueous NaHCO3 until a pH of about 8 was achieved. The organic layer was dried (MgSO4), filtered, and concentrated. Purification by medium pressure chromatography (2:1 hexanes:EtOAc) provided the title compound (1.44 g) as a white solid. 1H NMR (400 MHz, CDCl3) δ 9.99 (s, 1H), 8.01 (d, 1H), 7.96 (d, 2H), 7.87 (d, 2H), 7.76 (d, 1H), 6.51 (m, 1H); MS 173 (M+1).

Workup

  1. temperatureThe reaction was heated
  2. temperatureat reflux for 1.25 h
  3. customThe solids were removed by filtration through Celite with the aid of hot EtOH
  4. additionThe solution was diluted with water and CHCl3
  5. washThe aqueous layer was washed with CHCl3 (3×)
  6. dry with materialThe organic layer was dried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customPurification by medium pressure chromatography (2:1 hexanes:EtOAc)

Sources & evidence

ORD record
ord-2e6bea7d70dd4d3da8cff896594f0ebe
Source dataset
uspto-grants-2008_10
Patent number
US07442702B2

Reaction notes

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