Aniline → (3-Chloro-2-nitrophenyl)phenylamine

HRID 242791Notes

Reaction equation

HRID 242791 reaction equation
[Li+].C[Si]([N-][Si](C)(C)C)(C)C.[C:11]1([NH2:17])[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[Cl:18][C:19]1[CH:24]=[CH:23][CH:22]=[C:21](F)[C:20]=1[N+:26]([O-:28])=[O:27].[NH4+].[Cl-]>C1COCC1>[Cl:18][C:19]1[C:20]([N+:26]([O-:28])=[O:27])=[C:21]([NH:17][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH:22]=[CH:23][CH:24]=1

Participants

6

Reactant 4

HCID 6115AnilineHCID 25517Ammonium ChlorideHCID 2733832Lithium HexamethyldisilazideHCID 30175001-Chloro-3-fluoro-2-nitrobenzene

Product 1

HCID 44126964(3-Chloro-2-nitrophenyl)phenylamine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

LiHMDS (1.0M in THF, 23 mL) was added to a stirred solution of phenylamine (1.12 g, 12.0 mmol) in THF (15 mL) at −78° C. under a nitrogen atmosphere. Stirring was continued for 30 min then 1-chloro-3-fluoro-2-nitrobenzene (1.92 g, 10.9 mmol) in THF (15 mL) was added. The reaction mixture was stirred at −78° C. for 30 min, then slowly warmed to RT and stirred at RT for 2 h. The reaction mixture was poured into a saturated solution of NH4Cl and then extracted with EtOAc (×2). The combined organic layers were washed with brine, then dried (Na2SO4) and concentrated in vacuo affording (3-Chloro-2-nitrophenyl)phenylamine as a dark brown oil (2.85 g, quantitative). 1H NMR (CDCl3, 400 MHz): δ 7.41-7.25 (3H, m), 7.23-7.12 (5H, m), 6.96-6.91 (1H, m).

Workup

  1. stirringThe reaction mixture was stirred at −78° C. for 30 min
  2. stirringstirred at RT for 2 h
  3. extractionextracted with EtOAc (×2)
  4. washThe combined organic layers were washed with brine
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-39ee6b664bdf4b3caeb23fb3568869f4
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

Loading…