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

HRID 1607180Notes

Reaction equation

HRID 1607180 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 66%

Reagents, catalysts & solvents 1

HCID 935NickelCatalyst

Procedure

A stirred mixture of 30 g of 4-amino-3-bromo-2,5-difluorobenzonitrile, 40 g of Raney nickel and 450 mL of 95-97% HCOOH is heated at 75°-85° C. for 1 hour. The hot solution is filtered through diatomaceous earth filter and the cake washed with 2×200 ml of CH2Cl2. The total filtrate is stripped in vacuo and the residue treated with excess saturated NaHCO3 and 500 mL of CH2Cl2. Further extraction with 2×200 mL of CH2Cl2 is followed by washing the CH2Cl2 extracts with saturated NaHCO3, 2×H2O (200 mL each), drying with Na2SO4 and evaporating in vacuo to furnish 28.25 g of crude 4-amino-3-bromo-2,5-difluorobenzaldehyde. The crude product is purified by dry-column chromatography on silica gel using CH2Cl2 as eluent to give 20.15 g (66% yield), m.p. 132°-133° C., of the title compound.

Workup

  1. temperatureis heated at 75°-85° C. for 1 hour
  2. filtrationThe hot solution is filtered through diatomaceous earth
  3. filtrationfilter
  4. washthe cake washed with 2×200 ml of CH2Cl2
  5. additionthe residue treated with excess saturated NaHCO3 and 500 mL of CH2Cl2
  6. extractionFurther extraction with 2×200 mL of CH2Cl2
  7. washby washing the CH2Cl2
  8. dry with materialdrying with Na2SO4
  9. customevaporating in vacuo

Sources & evidence

ORD record
ord-e0f0877b142f4acc86abb687e2a46449
Source dataset
uspto-grants-1989_09
Patent number
US04863959

Reaction notes

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