Sodium Carbonate → Methyl 3-cyano-2-methylbenzoate

HRID 1642341Notes

Reaction equation

HRID 1642341 reaction equation
Br[C:2]1[C:3]([CH3:12])=[C:4]([CH:9]=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].C([O-])([O-])=O.[Na+].[Na+].[CH3:19][N:20](C)C(=O)C>[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.O.O.O.[K+].[K+].[K+].[K+].[Fe+2].CC([O-])=O.CC([O-])=O.[Pd+2]>[C:19]([C:2]1[C:3]([CH3:12])=[C:4]([CH:9]=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6])#[N:20]

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 31374DimethylacetamideHCID 12929135Methyl 3-Bromo-2-methylbenzoate

Product 1

HCID 13170186Methyl 3-cyano-2-methylbenzoateYield 70%

Reagents, catalysts & solvents 2

HCID 161067Potassium ferrocyanide trihydrateCatalystHCID 167845palladium(II) acetateCatalyst

Conditions

Temperature
120 °C

Procedure

To a flask was added methyl 3-bromo-2-methylbenzoate (21 g, 91.7 mmol), potassium hexacyanoferrate (II) trihydrate (9.7 g, 22.9 mmol), Na2CO3 (9.7 g, 91.7 mmol) and Pd(OAc)2 (102 mg) in N,N-dimethylacetamide (100 mL). The flask's atmosphere was evacuated and replaced with nitrogen, and the reaction mixture heated at 120° C. for 10 hours. The reaction mixture was cooled to room temperature and diluted with ethyl acetate (150 mL). The resultant slurry was filtered and washed thoroughly with ethyl acetate (2×50 mL). The combined filtrate was washed with brine and water, dried over Na2SO4 and evaporated under reduced pressure. The residue obtained after the concentration was purified using flash chromatography (ethyl acetate-hexanes (1:9) as the eluent) to provide methyl 3-cyano-2-methylbenzoate (11.2 g, 70% yield). 1H NMR spectrum (in DMSO-d6): δ 8.03 (d, J=8.1 Hz, 1H); 7.98 (d, J=7.9 Hz, 1H); 7.49 (t, 1H); 3.84 (s, 3H); 2.65 (s, 3H).

Workup

  1. customThe flask's atmosphere was evacuated
  2. temperatureThe reaction mixture was cooled to room temperature
  3. additiondiluted with ethyl acetate (150 mL)
  4. filtrationThe resultant slurry was filtered
  5. washwashed thoroughly with ethyl acetate (2×50 mL)
  6. washThe combined filtrate was washed with brine and water
  7. dry with materialdried over Na2SO4
  8. customevaporated under reduced pressure
  9. customThe residue obtained
  10. concentrationafter the concentration
  11. customwas purified

Sources & evidence

ORD record
ord-65e2a0a881614dc1b5007dcb67d5d725
Source dataset
uspto-grants-2012_02
Patent number
US08119654B2

Reaction notes

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