Pyridine → 2-Amino-4-nitrobenzonitrile

HRID 1688132Notes

Reaction equation

HRID 1688132 reaction equation
Br[C:2]1[CH:8]=[CH:7][C:6]([N+:9]([O-:11])=[O:10])=[CH:5][C:3]=1[NH2:4].[N:12]1C=CC=C[CH:13]=1.[Cu]C#N>CN(C=O)C>[NH2:4][C:3]1[CH:5]=[C:6]([N+:9]([O-:11])=[O:10])[CH:7]=[CH:8][C:2]=1[C:13]#[N:12]

Participants

5

Reactant 3

HCID 1049PyridineHCID 826072-Bromo-5-nitroanilineHCID 178418546HCID 178418546, compound

Product 1

HCID 111478972-Amino-4-nitrobenzonitrileYield 74.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
160 °C

Procedure

A solution of 2-bromo-5-nitroaniline (10 g, 46 mmol) in DMF (100 mL) and pyridine (40 mL, 490 mmol) was treated with copper(I) cyanide (11.5 g, 128 mmol). The mixture was heated at 160° C. for 2 days under a reflux condenser. After the mixture had cooled to room temperature, it was filtered through celite and washed with ethyl acetate. Concentration and silica gel chromatography using methylene chloride gave 5.57 g of 2-amino-4-nitro-benzonitrile (74%): 1H NMR (300 MHz, CDCl3) δ 7.72 (d, 1H), 7.67 (m, 2H), 4.9 (br, 2H); MS (m/e): 164.1 (M+1).

Workup

  1. temperatureAfter the mixture had cooled to room temperature
  2. filtrationit was filtered through celite
  3. washwashed with ethyl acetate
  4. concentrationConcentration and silica gel chromatography

Sources & evidence

ORD record
ord-707e6208ffd240f5919fdb24a6a9e7f6
Source dataset
uspto-grants-2012_04
Patent number
US08148391B2

Reaction notes

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