Aniline → 5-Chloro-2-nitrodiphenylamine

HRID 242909Notes

Reaction equation

HRID 242909 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4](F)[CH:3]=1.[NH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1>CS(C)=O>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]([NH:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH:3]=1

Participants

4

Reactant 2

HCID 6115AnilineHCID 696914-Chloro-2-fluoro-1-nitrobenzene

Product 1

HCID 1176355-Chloro-2-nitrodiphenylamineYield 98.4%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
110 °C

Procedure

A mixture of 4-chloro-2-fluoro-1-nitrobenzene (983 mg, 5.60 mmol) and aniline (1.0 mL, 11.20 mmol) in DMSO (3 mL) was heated at 110° C. for 4 h. After cooling to RT, the reaction mixture was partitioned between EtOAc and water. The organic layer was washed with a saturated aqueous solution of KHSO4 (×3), followed by brine, then dried (Na2SO4) and concentrated in vacuo to afford the title compound as an orange solid (1.37 g, 98%). 1H NMR (CDCl3, 400 MHz): δ 9.54 (1H, s), 8.16 (1H, d, J=9.13 Hz), 7.46 (2H, t, J=7.61 Hz), 7.32-7.22 (3H, m), 7.14 (1H, d, J=2.14 Hz), 6.72 (1H, dd, J=9.12, 2.15 Hz)

Workup

  1. temperatureAfter cooling to RT
  2. customthe reaction mixture was partitioned between EtOAc and water
  3. washThe organic layer was washed with a saturated aqueous solution of KHSO4 (×3)
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-2fa5016b2dfe43bea5927cfa06bd6d13
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

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