Dimethylacetamide → Methyl (3-cyanophenyl)acetate

HRID 1162524Notes

Reaction equation

HRID 1162524 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.C[C:14]([N:16](C)C)=O>CCOC(C)=O.O.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([C:14]#[N:16])[CH:6]=1

Participants

6

Reactant 2

HCID 31374DimethylacetamideHCID 11746402Methyl 2-(3-bromophenyl)acetate

Product 1

HCID 1514291Methyl (3-cyanophenyl)acetate

Reagents, catalysts & solvents 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of (3-bromophenyl)-acetic acid methyl ester 46 (1.20 g, 5.28 mmol) in dry dimethyl-acetamide (5 mL) is added under argon zinc cyanide (0.78 g, 6.64 mmol) and tetrakis(triphenylphosphine) palladium (0.63 g, 0.55 mmol). The mixture is stirred for 24 hours at 80° C. After cooling to room temperature, the mixture is diluted with EtOAc (15 mL) and water (20 mL). The resulting precipitate is removed by vacuum filtration. The organic layer of the filtrate is separated and washed with H2O, then dried over MgSO4, filtered and concentrated. Purification by silica gel chromatography (0 to 20% EtOAc/hexane) to give (3-cyano-phenyl)acetic acid methyl ester 47 as an oil: 1H-NMR (400 MHz, CDCl3) δ=7.63 (d, J=8.0 Hz, 1H), 7.47 (d, J=1.2 Hz, 1H), 7.30 (dd, J=1.2 Hz, J=8.0 Hz, 1H), 3.72 (s, 3H), 3.69 (s, 2H). MS calculated for C10H9O2ClN (M+H+) 210.0, found 210.0.

Workup

  1. temperatureAfter cooling to room temperature
  2. customThe resulting precipitate is removed by vacuum filtration
  3. customThe organic layer of the filtrate is separated
  4. washwashed with H2O
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customPurification by silica gel chromatography (0 to 20% EtOAc/hexane)

Sources & evidence

ORD record
ord-6d400afe9d6640adafb91e879de9e29c
Source dataset
uspto-grants-2010_10
Patent number
US07820705B2

Reaction notes

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