Formic Acid → 4-Amino-3-bromo-2,5-difluorobenzaldehyde

HRID 389520Notes

Reaction equation

HRID 389520 reaction equation
[NH2:1][C:2]1[C:9]([F:10])=[CH:8][C:5]([C:6]#N)=[C:4]([F:11])[C:3]=1[Br:12].C(O)=[O:14]>[Ni]>[NH2:1][C:2]1[C:9]([F:10])=[CH:8][C:5]([CH:6]=[O:14])=[C:4]([F:11])[C:3]=1[Br:12]

Participants

4

Reactant 2

HCID 284Formic AcidHCID 146210194-Amino-3-bromo-2,5-difluorobenzonitrile

Product 1

HCID 146210204-Amino-3-bromo-2,5-difluorobenzaldehydeYield 71%

Reagents, catalysts & solvents 1

HCID 935NickelCatalyst

Conditions

Temperature
80 °C

Procedure

To a solution of 4-amino-3-bromo-2,5-difluoro-benzonitrile (7 g, 30 mmol) in 95-97% formic acid (40 mL) was added Raney nickel (7 g, previously washed with water and methanol). The reaction mixture was heated to 75-85° C. for 2 h. The reaction was then cooled to room temperature and filtered through Celite, washing with dichloromethane and water. The dichloromethane layer was washed with aqueous sodium bicarbonate and brine, dried over sodium sulfate, filtered, and concentrated to afford 5 g (71%) of the title compound. 1H NMR (300 MHz, CDCl3): δ 10.15 (s, 1H), 7.41-7.49 (m, 1H), 4.9 (br. s, 2H).

Workup

  1. washpreviously washed with water and methanol)
  2. temperatureThe reaction was then cooled to room temperature
  3. filtrationfiltered through Celite
  4. washwashing with dichloromethane and water
  5. washThe dichloromethane layer was washed with aqueous sodium bicarbonate and brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-7944c7328a8948838f13833457449723
Source dataset
uspto-grants-2013_02
Patent number
US08378104B2

Reaction notes

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