Dimethylformamide → 4-Formyl-2-methoxy-5-methylbenzonitrile

HRID 1187007Notes

Reaction equation

HRID 1187007 reaction equation
FC(F)(F)S(O[C:7]1[CH:12]=[C:11]([CH3:13])[C:10]([CH:14]=[O:15])=[CH:9][C:8]=1[O:16][CH3:17])(=O)=O.CCOC(C)=O.[CH3:26][N:27](C=O)C>[C-]#N.[Zn+2].[C-]#N>[CH:14]([C:10]1[C:11]([CH3:13])=[CH:12][C:7]([C:26]#[N:27])=[C:8]([O:16][CH3:17])[CH:9]=1)=[O:15]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 8857Ethyl AcetateHCID 866473084-Formyl-2-methoxy-5-methylphenyl trifluoromethanesulfonate

Product 1

HCID 772312524-Formyl-2-methoxy-5-methylbenzonitrile

Reagents, catalysts & solvents 1

HCID 11186Zinc cyanide (Zn(CN)2)Catalyst

Conditions

Temperature
110 °C

Procedure

A mixture of 4-formyl-2-methoxy-5-methylphenyl trifluoromethanesulfonate (35.0 g, 117 mmol), zinc cyanide (55.1 g, 469 mmol) and tetrakis triphenylphosphine palladium (0) (20.34 g, 17.60 mmol) in DMF (300 mL) were stirred at 110° C. under nitrogen atmosphere for 8 hr. EtOAc was added to the reaction mixture and the organic layer was washed two times with water, dried, filtered and concentrated. The crude product was then purified by column chromatography (silica gel, ethylacetate/hexanes 3:7) which afforded 4-formyl-2-methoxy-5-methylbenzonitrile. 1H NMR (CDCl3, 500 MHz) δ 10.39 (s, 1H), 7.47 (s, 1H), 7.44 (s, 1H), 4.02 (s, 3H), 2.66 (s, 3H); LC/MS: (IE, m/z) [M+1]+=176.06; tR=2.71 min.

Workup

  1. washthe organic layer was washed two times with water
  2. customdried
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe crude product was then purified by column chromatography (silica gel, ethylacetate/hexanes 3:7) which

Sources & evidence

ORD record
ord-9f278389221643be972373a1e187239e
Source dataset
uspto-grants-2014_03
Patent number
US08673920B2

Reaction notes

Loading…