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

HRID 595020Notes

Reaction equation

HRID 595020 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 83%

Reagents, catalysts & solvents 1

HCID 935NickelCatalyst

Conditions

Temperature
85 °C

Procedure

Raney nickel (5.3 g, 50% slurry in water) was added to a solution of 4-amino-3-bromo-2,5-difluoro-benzonitrile (4.0 g, 17.2 mmol) in formic acid (60 mL). After heating for 1 h at 85° C., the reaction mixture was filtered through Celite, washed with DCM and evaporated to dryness. The residue was suspended in DCM and neutralized carefully with saturated sodium hydrogencarbonate. The aqueous phase was extracted with DCM and the combined organic phases were dried over sodium sulfate and evaporated to yield 4-amino-3-bromo-2,5-difluorobenzaldehyde (3.4 g, 14.3 mmol, 83%). 1H NMR (d6-DMSO) δ 9.91 (d, J=3.0 Hz, 1H), 7.45 (dd, J=11.0, 6.0 Hz, 1H), 6.96 (br s, 2H).

Workup

  1. filtrationthe reaction mixture was filtered through Celite
  2. washwashed with DCM
  3. customevaporated to dryness
  4. extractionThe aqueous phase was extracted with DCM
  5. dry with materialthe combined organic phases were dried over sodium sulfate
  6. customevaporated

Sources & evidence

ORD record
ord-c2b821d083ec4d0d8472be6ae05764ba
Source dataset
uspto-grants-2016_01
Patent number
US09242987B2

Reaction notes

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