Methyl 3-bromo-4-methylbenzoate → Methyl 3-cyano-4-methylbenzoate

HRID 1839445

Reaction equation

HRID 1839445 reaction equation
[Cu][C:2]#[N:3].Br[C:5]1[CH:6]=[C:7]([CH:12]=[CH:13][C:14]=1[CH3:15])[C:8]([O:10][CH3:11])=[O:9]>CN(C=O)C.CCOC(C)=O>[C:2]([C:5]1[CH:6]=[C:7]([CH:12]=[CH:13][C:14]=1[CH3:15])[C:8]([O:10][CH3:11])=[O:9])#[N:3]

Participants

5

Reactant 2

HCID 7015747Methyl 3-bromo-4-methylbenzoateHCID 178418546HCID 178418546, compound

Product 1

HCID 11819538Methyl 3-cyano-4-methylbenzoateYield 61.2%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
140 °C

Procedure

A mixture of copper (I) cyanide (510 mg, 5.69 mmol) and DMF (16 mL) was heated to 140° C. The reaction was added methyl 3-bromo-4-methylbenzoate (505 mg, 2.2 mmol) in DMF (10 mL) and heating was continued for 12 h. The reaction was cooled, diluted with EtOAc (125 mL) and washed with H2O (5×25 mL). The EtOAc layer was dried over MgSO4 and concentrated. The residue was chromatographed (40 g silica, 10% EtOAc/hexanes) to give the title compound as a solid (236 mg, 61%); IR(CHCl3): 1128, 1269, 1300, 1725, 2231, 3024 cm−1; NMR(300 MHz, CDCl3): 2.63 (s, 3H); 3.95 (s, 3H); 7.43 (d, 1H, J=8.1 Hz); 8.14 (d, 1H, J=8.1 Hz); 8.28 (s, 1H); MS(FD): 175.1.

Workup

  1. temperatureheating
  2. temperatureThe reaction was cooled
  3. washwashed with H2O (5×25 mL)
  4. dry with materialThe EtOAc layer was dried over MgSO4
  5. concentrationconcentrated
  6. customThe residue was chromatographed (40 g silica, 10% EtOAc/hexanes)

Sources & evidence

ORD record
ord-007ed27e61c3471f80a8dce3617778d6
Source dataset
uspto-grants-2004_01
Patent number
US06677369B2

Linked notes

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