Dimethylformamide → Methyl (3-cyanophenyl)acetate

HRID 2117602Notes

Reaction equation

HRID 2117602 reaction equation
[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[C:7](Br)[CH:6]=1.[NH4+].[OH-].[CH3:15][N:16](C=O)C>[C-]#N.[C-]#N.[Zn+2]>[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([C:15]#[N:16])[CH:6]=1

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 14923Ammonium HydroxideHCID 11746402Methyl 2-(3-bromophenyl)acetate

Product 1

HCID 1514291Methyl (3-cyanophenyl)acetate

Reagents, catalysts & solvents 1

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

Conditions

Temperature
80 °C

Procedure

Nitrogen was bubbled through a mixture of (3-bromo-phenyl)-acetic acid methyl ester (22.85 g, 99.78 mmol), Zn(CN)2 (7.25 g, 61.75 mmol), and DMF (100 mL) for about 5 minutes followed by addition of tetrakistriphenylphosphine(0) palladium (4.60 g, 3.98 mmol). The mixture was heated for 3 h at 80° C. and was cooled to room temperature. Aqueous 2N NH4OH was added and the product was extracted into EtOAc (3×). The organic solution was washed with 2N NH4OH (2×) followed by brine (2×). The organic solution was dried (MgSO4), filtered, and concentrated in vacuo. Purification by flash chromatography (6:1 hexanes:EtOAc) provided the title compound of Step A as an oil (15.19 g). 1H NMR (400 MHz, CDCl3) δ 7.57-7.41 (m, 4H), 3.70 (s, 3H), 3.70 (s, 2H).

Workup

  1. temperaturewas cooled to room temperature
  2. extractionthe product was extracted into EtOAc (3×)
  3. washThe organic solution was washed with 2N NH4OH (2×)
  4. dry with materialThe organic solution was dried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customPurification by flash chromatography (6:1 hexanes:EtOAc)

Sources & evidence

ORD record
ord-d76f38899ae34dd7a477532cc1e1ee89
Source dataset
uspto-grants-2008_10
Patent number
US07442702B2

Reaction notes

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