Dimethylformamide → 5-Bromopyridine-2-carbonitrile

HRID 887640Notes

Reaction equation

HRID 887640 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([Br:8])=[CH:4][N:3]=1.C(Cl)Cl.[CH3:12][N:13](C=O)C>O.[C-]#N.[Zn+2].[C-]#N.[Zn].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Br:8][C:5]1[CH:6]=[CH:7][C:2]([C:12]#[N:13])=[N:3][CH:4]=1

Participants

8

Reactant 3

HCID 6228DimethylformamideHCID 6344DichloromethaneHCID 693532,5-Dibromopyridine

Product 1

HCID 8171545-Bromopyridine-2-carbonitrile

Reagents, catalysts & solvents 4

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 23994ZincCatalystHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolvent

Procedure

The mixture of 2,5-dibromopyridine (4.74 g, 20.0 mmol), zinc cyanide (1.40 g, 12.0 mmol), zinc dust (0.059 g, 0.90 mmol), and Pd(dppf)Cl2.CH2Cl2 (0.36 g, 0.44 mmol) in 25 ml of DMF was heated at reflux for 5 h, cooled to RT, diluted with H2O, extracted with EtOAc, the organic portion was washed with brine, the solvents were removed, the crude compound was purified by flash column chromatography (5 to 15% of EtOAc in hexanes), the titled compound was obtained as an off-white solid.

Workup

  1. temperatureat reflux for 5 h
  2. extractionextracted with EtOAc
  3. washthe organic portion was washed with brine
  4. customthe solvents were removed
  5. customthe crude compound was purified by flash column chromatography (5 to 15% of EtOAc in hexanes)

Sources & evidence

ORD record
ord-bb23be7ebbff415a934070b69dcca029
Source dataset
uspto-grants-2012_08
Patent number
US08247430B2

Reaction notes

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