Aniline → (2-Fluoro-6-nitrophenyl)phenylamine

HRID 242783Notes

Reaction equation

HRID 242783 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[C:3]=1F.[C:12]1([NH2:18])[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(=O)([O-])[O-].[K+].[K+]>CS(C)=O>[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-:10])=[O:9])[C:3]=1[NH:18][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

5

Reactant 3

HCID 6115AnilineHCID 11430Potassium CarbonateHCID 813351,2-Difluoro-3-nitrobenzene

Product 1

HCID 69251985(2-Fluoro-6-nitrophenyl)phenylamineYield 39%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

A mixture of 1,2-difluoro-3-nitrobenzene (690 μL, 6.29 mmol), phenylamine (600 μL, 6.60 mmol) and potassium carbonate (1.74 g, 12.57 mmol) in DMSO (3 mL) was stirred at RT for 3 h and then heated to 90° C. for 4 h. After cooling to RT, the reaction mixture was partitioned between EtOAc and water. The organic layer was then washed with brine, dried (Na2SO4) and concentrated in vacuo and the resulting residue was purified by column chromatography (Si—PCC, gradient 0-20% EtOAc in cyclohexane) followed by (Si—PCC, gradient 0-50% DCM in cyclohexane) affording (2-Fluoro-6-nitrophenyl)phenylamine as a orange/red oil (563 mg, 39%). 1H NMR (CDCl3, 400 MHz): δ 8.70 (1H, s), 8.00 (1H, d, J=8.66 Hz), 7.36-7.23 (3H, m), 7.09 (1H, t, J=7.41 Hz), 7.03-6.89 (3H, m).

Workup

  1. temperatureheated to 90° C. for 4 h
  2. temperatureAfter cooling to RT
  3. customthe reaction mixture was partitioned between EtOAc and water
  4. washThe organic layer was then washed with brine
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated in vacuo
  7. customthe resulting residue was purified by column chromatography (Si—PCC, gradient 0-20% EtOAc in cyclohexane)

Sources & evidence

ORD record
ord-66b6ffd0d57a40dbb5418f8a8927b3a6
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

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