Ammonium Chloride → 3-Chloro-N2-phenylbenzene-1,2-diamine

HRID 242835Notes

Reaction equation

HRID 242835 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([N+:8]([O-])=O)[C:3]=1[NH:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.[NH4+].[Cl-]>CO.O.[Fe]>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([NH2:8])[C:3]=1[NH:11][C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 30158142-Chloro-6-nitro-N-phenylaniline

Product 1

HCID 431486273-Chloro-N2-phenylbenzene-1,2-diamineYield 84.1%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 887MethanolSolventHCID 962WaterSolvent

Procedure

To a mixture of (2-chloro-6-nitrophenyl)phenylamine (676 mg, 2.72 mmol) in MeOH (45 mL) and water (15 mL) were added NH4Cl (872 mg, 16.31 mol) and iron powder (607 mg, 10.87 mmol) and the reaction mixture was heated to reflux temperature for 4 h. After cooling to RT, the solid was filtered through a pad of Celite® and washed with additional MeOH. The filtrate was concentrated in vacuo and then partitioned between EtOAc and water. The aqueous phase was further extracted with EtOAc and the combined organic layers were washed with brine, then dried (Na2SO4) and concentrated in vacuo. The resulting residue was purified by column chromatography (Si—PCC, gradient 50-100% DCM in cyclohexane). The product containing fractions were concentrated in vacuo affording 3-Chloro-N2-phenylbenzene-1,2-diamine as a pale orange solid (500 mg, 84%). LCMS: RT 3.45 min [M+H]+ 219.1.

Workup

  1. temperaturethe reaction mixture was heated
  2. temperatureto reflux temperature for 4 h
  3. filtrationthe solid was filtered through a pad of Celite®
  4. washwashed with additional MeOH
  5. concentrationThe filtrate was concentrated in vacuo
  6. custompartitioned between EtOAc and water
  7. extractionThe aqueous phase was further extracted with EtOAc
  8. washthe combined organic layers were washed with brine
  9. dry with materialdried (Na2SO4)
  10. concentrationconcentrated in vacuo
  11. customThe resulting residue was purified by column chromatography (Si—PCC, gradient 50-100% DCM in cyclohexane)
  12. additionThe product containing fractions
  13. concentrationwere concentrated in vacuo

Sources & evidence

ORD record
ord-2c850d2f7d234f33946dc28afdb27830
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

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