Aniline → 3-Fluoro-2-nitro-N-phenylaniline

HRID 242815Notes

Reaction equation

HRID 242815 reaction equation
CC(C)([O-])C.[Na+].F[C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([F:14])[C:9]=1[N+:15]([O-:17])=[O:16].[C:18]1([NH2:24])[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.[NH4+].[Cl-]>CN(C=O)C>[F:14][C:10]1[C:9]([N+:15]([O-:17])=[O:16])=[C:8]([NH:24][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH:13]=[CH:12][CH:11]=1

Participants

6

Reactant 4

HCID 6115AnilineHCID 25517Ammonium ChlorideHCID 879221,3-Difluoro-2-nitrobenzeneHCID 23676156Sodium t-butoxide

Product 1

HCID 442552223-Fluoro-2-nitro-N-phenylanilineYield 73%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Sodium tertbutoxide (1.2 g, 12.58 mmol) was added portionwise to a stirred solution of 1,3-difluoro-2-nitrobenzene (1 g, 6.29 mmol) and phenylamine (1.15 mL, 12.58 mmol) in a hydrous DMF (5 mL) under a nitrogen atmosphere at RT and stirring was continued for 20 h. The mixture was poured into an aqueous solution of NH4Cl and extracted with EtOAc (150 mL). The organic layer was washed with brine, then dried and concentrated in vacuo and the resulting residue was purified by column chromatography (Si—PCC, gradient 0-15% EtOAc in cyclohexane) affording (3-Fluoro-2-nitrophenyl)phenylamine as a red solid (1.06 g, 73%). LCMS: RT 3.80 min.

Workup

  1. extractionextracted with EtOAc (150 mL)
  2. washThe organic layer was washed with brine
  3. customdried
  4. concentrationconcentrated in vacuo
  5. customthe resulting residue was purified by column chromatography (Si—PCC, gradient 0-15% EtOAc in cyclohexane)

Sources & evidence

ORD record
ord-a0a9db8cbc444e43ad119e6de6cf1b12
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

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