Dimethylformamide → 5-Methylpicolinonitrile

HRID 431844

Reaction equation

HRID 431844 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][N:3]=1.ClCCl.[CH3:12][N:13](C)C=O>C(OCC)(=O)C.[C-]#N.[Zn+2].[C-]#N.[Zn].Cl[Pd]Cl.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[CH3:8][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 5642162-Bromo-5-methylpyridine

Product 1

HCID 741835-MethylpicolinonitrileYield 56%

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 8857Ethyl AcetateSolvent

Procedure

A mixture of 2-bromo-5-methylpyridine (2.001 g, 11.63 mmol), zinc cyanide (830 mg, 7 mmol), zinc (dust, 35 mg, 0.53 mmol), [1,1′-bis(diphenylphosphino)ferrocene] dichloropalladium(II), complex with dichloromethane (1:1) (192.5 mg, 0.24 mmol) in N,N-dimethylformamide (10 mL) was heated at reflux for 16 hours. After cooling, the reaction was diluted with ethyl acetate and extracted with water and brine. The organic solution was filtered through a plug of silica gel, washing dichloromethane. Removal of the solvent in vacuo, afforded 770 mg (56%) of 5-methyl-2-cyano-pyridine.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 16 hours
  3. temperatureAfter cooling
  4. extractionextracted with water and brine
  5. filtrationThe organic solution was filtered through a plug of silica gel
  6. washwashing dichloromethane
  7. customRemoval of the solvent in vacuo

Sources & evidence

ORD record
ord-2e27af0b4bbc4ccf8085e124a9ccd2b1
Source dataset
uspto-grants-2003_12
Patent number
US06660753B2

Linked notes

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