Dimethylformamide → Methyl 4-cyano-2-methylbenzoate

HRID 906150Notes

Reaction equation

HRID 906150 reaction equation
Br[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([CH3:12])[CH:3]=1.[CH3:13][N:14](C=O)C>[C-]#N.[Zn+2].[C-]#N.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:13]([C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[C:4]([CH3:12])[CH:3]=1)#[N:14]

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 22031226Methyl 4-bromo-2-methylbenzoate

Product 1

HCID 18766060Methyl 4-cyano-2-methylbenzoateYield 89%

Reagents, catalysts & solvents 2

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

Procedure

To a solution of methyl 4-bromo-2-methylbenzoate (26.6 g, 0.116 mol) in DMF (300 mL) was added zinc cyanide (8.1 g, 0.07 mol) followed by tetrakis(triphenylphosphine)palladium(0) (6.7 g, 0.0058 mol). The reaction mixture was placed in a 100° C. oil bath and stirred for 2 h, at which time it was filtered through a bed of celite and the filter cake rinsed with ethyl acetate. The filtrate was concentrated in vacuo and the residue was purified by flash chromatography (10% ethyl acetate in hexanes) to afford methyl 4-cyano-2-methylbenzoate (18.1 g, 89%) as a white powder. 1H NMR (400 MHz, CDCl3): 7.97 (d, 1H), 7.55 (s, 1H), 7.53 (br m, 1H), 3.93 (s, 3H), 2.62 (s, 3H).

Workup

  1. customwas placed in a 100° C.
  2. filtrationwas filtered through a bed of celite
  3. washthe filter cake rinsed with ethyl acetate
  4. concentrationThe filtrate was concentrated in vacuo
  5. customthe residue was purified by flash chromatography (10% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-8a99fc28c13b4f58badc7ddc8607a926
Source dataset
uspto-grants-2011_09
Patent number
US08012956B2

Reaction notes

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