Ammonium Chloride → 2-(2,4-Dichlorophenoxy)aniline

HRID 1642225Notes

Reaction equation

HRID 1642225 reaction equation
[Cl-].[NH4+].[Cl:3][C:4]1[CH:19]=[C:18]([Cl:20])[CH:17]=[CH:16][C:5]=1[O:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[N+:13]([O-])=O>C(O)C.O.[Fe]>[Cl:3][C:4]1[CH:19]=[C:18]([Cl:20])[CH:17]=[CH:16][C:5]=1[O:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=1[NH2:13]

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 7759752,4-Dichloro-1-(2-nitrophenoxy)benzene

Product 1

HCID 968292-(2,4-Dichlorophenoxy)anilineYield 90%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

To a refluxing mixture of iron powder (2.68 g, 48.4 mmol) and ammonium chloride (323 mg, 6.05 mmol) in ethanol (45 mL) and water (8 mL) was added 1-(2,4-dichlorophenoxy)-2-nitrobenzene (AMR01025, 2.5 g, 8.8 mmol) and the resulting mixture was stirred at reflux for 2 h. After removal of the solvent, the residue was diluted in aqueous sodium hydrogen carbonate (40 mL) and extracted with DCM (3×20 mL). The organic layer was dried (MgSO4), filtered and evaporated to give 2-(2,4-dichlorophenoxy)phenylamine (2.01 g, 90%) as a colorless oil which was used in the next step without further purification. Rf: 0.56 (DCM) 1H NMR (400 MHz, CDCl3) δ 3.85 (2H, br s, NH2), 6.75 (1H, m, ArH), 6.84 (1H, d, J=8.8 Hz, ArH), 6.84 (1H, dd, ArH), 6.87 (1H, dd, J=7.6, 1.6 Hz, ArH), 7.04 (1H, m, ArH), 7.17 (1H, dd, J=8.8, 2.4 Hz, ArH) and 7.49 (1H, d, J=2.4 Hz, ArH).

Workup

  1. temperatureat reflux for 2 h
  2. customAfter removal of the solvent
  3. additionthe residue was diluted in aqueous sodium hydrogen carbonate (40 mL)
  4. extractionextracted with DCM (3×20 mL)
  5. dry with materialThe organic layer was dried (MgSO4)
  6. filtrationfiltered
  7. customevaporated

Sources & evidence

ORD record
ord-3ef9be441b964731ae75ace98cbe767b
Source dataset
uspto-grants-2012_02
Patent number
US08119627B2

Reaction notes

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