Hydrochloric Acid → 5-Bromo-3-chloropyridine-2-carbonitrile

HRID 872528Notes

Reaction equation

HRID 872528 reaction equation
N([O-])=O.[Na+].N[C:6]1[C:7]([C:13]#[N:14])=[N:8][CH:9]=[C:10]([Br:12])[CH:11]=1.[ClH:15]>O.[Cu]>[Br:12][C:10]1[CH:11]=[C:6]([Cl:15])[C:7]([C:13]#[N:14])=[N:8][CH:9]=1

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 220301763-Amino-5-bromopyridine-2-carbonitrileHCID 23668193Sodium Nitrite

Product 1

HCID 453821485-Bromo-3-chloropyridine-2-carbonitrileYield 66%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 962WaterSolvent

Conditions

Temperature
2.5 °C

Procedure

Sodium nitrite (0.7 g, 10.15 mmol) was added to a cooled suspension of 3-amino-5-bromopicolinonitrile (1.67 g, 8.43 g) in 37% hydrochloric acid (14 ml, 169 mmol) and water (4.5 ml) and stirred for 1 h at 0-5° C. Copper powder (0.134 g, 2.11 mmol) was added and the mixture refluxed for 1 h. The mixture was cooled, quenched with ice water and basified with 48% NaOH. The mixture was extracted with EtOAc. The organic phase was washed with water and brine, dried over anhydrous Na2SO4, filtered and evaporated to give 1.21 g of the product. 1H-NMR (400 MHz; d6-DMSO): δ 8.75 (d, 1H, J=1.9 Hz), 8.90 (d, 1H, J=1.9 Hz).

Workup

  1. temperaturethe mixture refluxed for 1 h
  2. temperatureThe mixture was cooled
  3. customquenched with ice water and basified with 48% NaOH
  4. extractionThe mixture was extracted with EtOAc
  5. washThe organic phase was washed with water and brine
  6. dry with materialdried over anhydrous Na2SO4
  7. filtrationfiltered
  8. customevaporated

Sources & evidence

ORD record
ord-285c3a916e2441acb581c557612fe345
Source dataset
uspto-grants-2015_03
Patent number
US08975254B2

Reaction notes

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