Aniline → 4-Nitro-3-phenylaminobenzonitrile

HRID 242800Notes

Reaction equation

HRID 242800 reaction equation
F[C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][C:9]=1[N+:10]([O-:12])=[O:11])[C:5]#[N:6].[C:13]1([NH2:19])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1>CS(C)=O>[N+:10]([C:9]1[CH:8]=[CH:7][C:4]([C:5]#[N:6])=[CH:3][C:2]=1[NH:19][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)([O-:12])=[O:11]

Participants

4

Reactant 2

HCID 6115AnilineHCID 27833993-Fluoro-4-nitrobenzonitrile

Product 1

HCID 681579814-Nitro-3-phenylaminobenzonitrileYield 98.2%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
120 °C

Procedure

A suspension of 3-fluoro-4-nitrobenzonitrile (1.66 g, 10.0 mmol) in DMSO (5 mL) was purged with a stream of argon prior to addition of phenylamine (1.82 mL, 20.0 mmol) and then the mixture was stirred at 120° C. for 1 h under an argon atmosphere. After cooling to RT, the reaction mixture was partitioned between EtOAc (75 mL) and an aqueous solution of KHSO4 (100 mL). The organic layer was then washed with brine, dried (Na2SO4) and concentrated in vacuo. The resulting residue was triturated with diethyl ether affording 4-Nitro-3-phenylaminobenzonitrile as red crystals (2.35 g, 98%). 1H NMR (CDCl3, 400 MHz): δ 9.48 (1H, bs), 8.29 (1H, d, J=8.76 Hz), 7.53-7.40 (3H, m), 7.35 (1H, t, J=7.52 Hz), 7.29-7.22 (2H, m), 6.97 (1H, d, J=8.79 Hz).

Workup

  1. customwas purged with a stream of argon
  2. temperatureAfter cooling to RT
  3. customthe reaction mixture was partitioned between EtOAc (75 mL)
  4. washThe organic layer was then washed with brine
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated in vacuo
  7. customThe resulting residue was triturated with diethyl ether

Sources & evidence

ORD record
ord-9d8f1c53e2a64e629f2c33cfb962b937
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

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