Dimethylformamide → 5-Methylpicolinonitrile

HRID 2216740Notes

Reaction equation

HRID 2216740 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].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]>[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-fec0df1fa3854b5aafa7091e0aa6fee8
Source dataset
uspto-grants-2006_09
Patent number
US07112595B2

Reaction notes

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