Dimethylformamide → Ethyl 2-(3-cyanophenyl)acetate

HRID 1699059Notes

Reaction equation

HRID 1699059 reaction equation
[CH2:1]([O:3][C:4](=[O:13])[CH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[C:8](Br)[CH:7]=1)[CH3:2].[NH4+].[OH-].[CH3:16][N:17](C=O)C>[C-]#N.[Zn+2].[C-]#N.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:1]([O:3][C:4](=[O:13])[CH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[C:8]([C:16]#[N:17])[CH:7]=1)[CH3:2]

Participants

6

Reactant 3

HCID 6228DimethylformamideHCID 14923Ammonium HydroxideHCID 11470552Ethyl 3-(bromophenyl)acetate

Product 1

HCID 11194802Ethyl 2-(3-cyanophenyl)acetate

Reagents, catalysts & solvents 2

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
90 °C

Procedure

A mixture of (3-bromo-phenyl)-acetic acid ethyl ester (12.38 g, 54.05 mmol), zinc cyanide (4.33 g, 36.9 mmol), and DMF (150 mL) was deoxygenated with nitrogen and Pd(PPh3)4 (3.10 g, 2.68 mmol) was added. The mixture was heated in a 90° C. oil bath for 2.5 h and was cooled to room temperature. Aqueous NH4OH (5%) was added and the product was extracted into Et2O (3×). The combined organic extracts were washed with 5% NH4OH followed by brine. The organic solution was dried over MgSO4, filtered and concentrated. Flash chromatography (9:1 hexanes:EtOAc) provided (3-cyano-phenyl)-acetic acid ethyl ester (9.08 g) as a pale yellow liquid which was identical spectroscopically to that obtained using Method A above.

Workup

  1. additionwas added
  2. temperaturewas cooled to room temperature
  3. extractionthe product was extracted into Et2O (3×)
  4. washThe combined organic extracts were washed with 5% NH4OH
  5. dry with materialThe organic solution was dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-4a3b64ea7cfd40a3a878d743a27c0ab6
Source dataset
uspto-grants-2002_02
Patent number
US06344485B1

Reaction notes

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