6-Bromo-3-pyridinecarboxaldehyde → 5-Formylpyridine-2-carbonitrile

HRID 930456Notes

Reaction equation

HRID 930456 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH:8]=[O:9])=[CH:4][N:3]=1.[Cu][C:11]#[N:12]>CN(C=O)C>[CH:8]([C:5]1[CH:6]=[CH:7][C:2]([C:11]#[N:12])=[N:3][CH:4]=1)=[O:9]

Participants

4

Reactant 2

HCID 117692346-Bromo-3-pyridinecarboxaldehydeHCID 178418546HCID 178418546, compound

Product 1

HCID 109862635-Formylpyridine-2-carbonitrileYield 35.4%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
120 °C

Procedure

A suspension of 2-bromo-5-formylpyridine (940 mg, 5.05 mmol) and copper (I) cyanide (233 μL, 7.58 mmol) in DMF (8.4 mL) was stirred at 120° C. for 1.5 hours, cooled to RT, and partitioned between water and EtOAc. The solids were removed from the aqueous layer by filtration, and the filtrate was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous magnesium sulfate, filtered and concentrated. The crude product was purified by silica-gel chromatography, eluting with a gradient of 40%-60% (40% ethyl acetate in heptane) in heptane, to provide the title compound (236 mg, 1.786 mmol) as white solid. LC/MS (ESI+) m/z=133 (M+H).

Workup

  1. temperaturecooled to RT
  2. custompartitioned between water and EtOAc
  3. customThe solids were removed from the aqueous layer by filtration
  4. extractionthe filtrate was extracted with ethyl acetate
  5. washThe combined organic layers were washed with brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude product was purified by silica-gel chromatography
  10. washeluting with a gradient of 40%-60% (40% ethyl acetate in heptane) in heptane

Sources & evidence

ORD record
ord-9cece4c307d54497bd0605e93604a1f0
Source dataset
uspto-grants-2016_03
Patent number
US09296734B2

Reaction notes

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