Dimethylformamide → 2-Methylpentane

HRID 1693384Notes

Reaction equation

HRID 1693384 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[NH:15][C:9]2=[CH:10][N:11]=[C:12](Br)[CH:13]=[C:8]2[CH:7]=1)=[O:5])[CH3:2].[CH3:16][N:17](C=O)C>[C-]#N.[Zn+2].[C-]#N>[CH3:4][CH2:6][CH2:7][CH:8]([CH3:9])[CH3:13].[CH2:1]([O:3][C:4]([C:6]1[NH:15][C:9]2=[CH:10][N:11]=[C:12]([C:16]#[N:17])[CH:13]=[C:8]2[CH:7]=1)=[O:5])[CH3:2]

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 50998338Ethyl 5-bromo-1H-pyrrolo[2,3-c]pyridine-2-carboxylate

Product 2

HCID 78922-MethylpentaneHCID 59753720HCID 59753720, compound

Reagents, catalysts & solvents 1

HCID 11186Zinc cyanide (Zn(CN)2)Catalyst

Procedure

To a solution of 5-bromo-1H-pyrrolo[2,3-c]pyridine-2-carboxylic acid ethyl ester (Preparation 26, 0.160 g, 0.590 mmol) in DMF (anhydrous, 5 mL) was added zinc (II) cyanide (0.041 g, 0.35 mmol) then tetrakis-triphenylphosphine palladium (0). The reaction mixture was degassed by bubbling argon through it for 10 min. The reaction mixture was heated to reflux temperature for 4.5 h then allowed to cool to rt. Water (30 mL) was added and the mixture extracted with ethyl acetate (2×50 mL). The combined organics were washed with brine (30 mL), dried (MgSO4), filtered and concentrated in vacuo. The residue was dissolved in ethyl acetate then adsorbed onto silica gel. Purification via flash column chromatography (SiO2, ethyl acetate: isohexane, 1:3, v/v) gave the title compound as a white solid. δH (CDCl3): 1.45 (3H, t), 4.49 (2H, quartet), 7.31 (1H, s), 8.09 (1H, s), 8.97 (1H, s), 9.60 (1H, br s); m/z (ES+)=216 [M+H]+; RT=3.03 min.

Workup

  1. customThe reaction mixture was degassed
  2. customby bubbling argon through it for 10 min
  3. temperatureThe reaction mixture was heated
  4. temperatureto reflux temperature for 4.5 h
  5. additionWater (30 mL) was added
  6. extractionthe mixture extracted with ethyl acetate (2×50 mL)
  7. washThe combined organics were washed with brine (30 mL)
  8. dry with materialdried (MgSO4)
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. dissolutionThe residue was dissolved in ethyl acetate
  12. customPurification via flash column chromatography (SiO2, ethyl acetate

Sources & evidence

ORD record
ord-add311b8546449c2b2040916cbe17a33
Source dataset
uspto-grants-2012_04
Patent number
US08158622B2

Reaction notes

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