Dimethylformamide → Methyl 4-cyano-3-methylbenzoate

HRID 607052Notes

Reaction equation

HRID 607052 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[CH3:12].[CH3:13][N:14](C=O)C>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.[C-]#N.[C-]#N.[Zn+2]>[C:13]([C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[CH3:12])#[N:14]

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 3294148Methyl 4-bromo-3-methylbenzoate

Product 1

HCID 19969932Methyl 4-cyano-3-methylbenzoate

Reagents, catalysts & solvents 2

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

Procedure

To a microwave tube, was added methyl 4-bromo-3-methylbenzoate (100 mg, 0.437 mmol), Pd(Ph3P)4 (25.2 mg, 0.022 mmol), Zn(CN)2 (51.3 mg, 0.437 mmol) and DMF (2 mL). The mixture was flushed with N2 and capped tightly. The reaction mixture was exposed to microwave irradiation at 150° C. for 5 min. The mixture was diluted with EtOAc and washed with water. The organic layer was dried (Na2SO4), filtered and the solvent was evaporated in vacuo. The residue was purified by flash chromatography on silica gel to give methyl 4-cyano-3-methylbenzoate. LCMS calc.=176.1; found=176.1 (M+1)+. 1H NMR (500 MHz, CDCl3) δ 8.02 (s, 1H); 7.95 (d, J=8.1 Hz, 1H); 7.71 (d, J=8.0 Hz, 1H); 7.29 (s, 1H); 3.98 (s, 3H); 2.64 (s, 3H).

Workup

  1. customThe mixture was flushed with N2
  2. customcapped tightly
  3. customirradiation at 150° C. for 5 min
  4. additionThe mixture was diluted with EtOAc
  5. washwashed with water
  6. dry with materialThe organic layer was dried (Na2SO4)
  7. filtrationfiltered
  8. customthe solvent was evaporated in vacuo
  9. customThe residue was purified by flash chromatography on silica gel

Sources & evidence

ORD record
ord-f733182763f84bc092259a724991666d
Source dataset
uspto-grants-2011_03
Patent number
US07915271B2

Reaction notes

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