Dimethylformamide → Methyl 4-cyano-3-nitrobenzoate

HRID 1943111Notes

Reaction equation

HRID 1943111 reaction equation
[CH3:1][O:2][C:3](=[O:21])[C:4]1[CH:9]=[CH:8][C:7](OS(C(F)(F)F)(=O)=O)=[C:6]([N+:18]([O-:20])=[O:19])[CH:5]=1.[CH3:22][N:23](C)C=O>[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>[CH3:1][O:2][C:3](=[O:21])[C:4]1[CH:9]=[CH:8][C:7]([C:22]#[N:23])=[C:6]([N+:18]([O-:20])=[O:19])[CH:5]=1

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 10925511Methyl 3-nitro-4-[[(trifluoromethyl)sulfonyl]oxy]benzoate

Product 1

HCID 53419688Methyl 4-cyano-3-nitrobenzoateYield 60.7%

Reagents, catalysts & solvents 2

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

Conditions

Temperature
100 °C

Procedure

3-Nitro-4-trifluoromethanesulfonyloxy-benzoic acid methyl ester (89.7 g, 272 mmol), zinc cyanide (19.2 g, 163 mmol) and tetrakis(triphenylphosphine)palladium(0) (15 g) were suspended in N,N-dimethylformamide (2500 ml). The reaction mixture was stirred for 3 hours at 100° C. under an inert atmosphere. The solvent was evaporated and the residue was purified by column chromatography on silica gel (eluent: cyclohexane/ethyl acetate 3:1) to give 4-cyano-3-nitro-benzoic acid methyl ester (34.0 g, 60.7% yield). 1H-NMR (400 MHz, CDCl3): 8.92 (s, 1H), 8.48 (d, 1H), 8.04 (d, 1H), 4.03 (s, 3H) ppm.

Workup

  1. customThe solvent was evaporated
  2. customthe residue was purified by column chromatography on silica gel (eluent: cyclohexane/ethyl acetate 3:1)

Sources & evidence

ORD record
ord-4cca7ba35e2140b094d770e83f2d9273
Source dataset
uspto-grants-2013_03
Patent number
US08389766B2

Reaction notes

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