Dimethylformamide → 3-Amino-4-nitrobenzonitrile

HRID 272704Notes

Reaction equation

HRID 272704 reaction equation
Cl[C:2]1[CH:3]=[CH:4][C:5]([N+:9]([O-:11])=[O:10])=[C:6]([CH:8]=1)[NH2:7].[CH3:12][N:13](C=O)C>[C-]#N.[C-]#N.[Zn+2].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>[NH2:7][C:6]1[CH:8]=[C:2]([CH:3]=[CH:4][C:5]=1[N+:9]([O-:11])=[O:10])[C:12]#[N:13]

Participants

5

Reactant 2

HCID 6228DimethylformamideHCID 742185-Chloro-2-nitroaniline

Product 1

HCID 114919823-Amino-4-nitrobenzonitrileYield 23%

Reagents, catalysts & solvents 2

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

Procedure

A solution of 5-chloro-2-nitro-aniline (6.902 g, 40 mmol), Zn(CN)2 (2.818 g, 24 mmol), and Pd(PPh3)4 (2.311 g, 2 mmol) in DMF (40 mL) was heated to 120° C. for 4 days. Cooled to room temperature. Partitioned between ethyl acetate and water. The organic layer was washed with brine, dried (MgSO4), filtered, and concentrated under vacuum. The residue was purified by flash column chromatography on silica gel with 4:1 hexanes/ethyl acetate to provide 1.49 g (23%) of 3-amino-4-nitro-benzonitrile.

Workup

  1. customPartitioned between ethyl acetate and water
  2. washThe organic layer was washed with brine
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated under vacuum
  6. customThe residue was purified by flash column chromatography on silica gel with 4:1 hexanes/ethyl acetate

Sources & evidence

ORD record
ord-73e6eac9766a429487758639eac28f18
Source dataset
uspto-grants-2008_11
Patent number
US07456169B2

Reaction notes

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