Ammonium Chloride → 4-(3-Chlorophenoxy)-2-methylaniline

HRID 246357Notes

Reaction equation

HRID 246357 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:16]=[CH:17][CH:18]=1)[O:5][C:6]1[CH:11]=[CH:10][C:9]([N+:12]([O-])=O)=[C:8]([CH3:15])[CH:7]=1.[Cl-].[NH4+]>C(O)C.O.[Fe]>[Cl:1][C:2]1[CH:3]=[C:4]([CH:16]=[CH:17][CH:18]=1)[O:5][C:6]1[CH:11]=[CH:10][C:9]([NH2:12])=[C:8]([CH3:15])[CH:7]=1

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 712795964-(3-Chlorophenoxy)-2-methyl-1-nitrobenzene

Product 1

HCID 261903124-(3-Chlorophenoxy)-2-methylanilineYield 87%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

To a stirred solution of 4-(3-chloro-phenoxy)-2-methyl-1-nitro-benzene (0.56 g, 2.12 mmol) in ethanol and water, iron (594 mg, 10.6 mmol) and saturated ammonium chloride (569 mg, 10.6 mmol) were added. This reaction mixture was then heated to reflux for 12 h. This was then filtered through celite and then extracted with EtOAc (3×15 mL). The EtOAc layer was washed with brine, dried over sodium sulfate and concentrated. This was then purified by chromatography (11% EtOAc in hexanes) to afford 4-(3-chloro-phenoxy)-2-methyl-phenylamine (0.43 g, 87%). MS (M+H)+=234.1; 1H NMR (CDCl3) δ: 7.17 (t, J=6.0 Hz, 1H), 6.95 (d, J=2.8 Hz, 1H), 6.88-6.86 (m, 1H), 6.82-6.71 (m, 2H), 6.65 (d, J=6.27 Hz, 1H).

Workup

  1. temperatureThis reaction mixture was then heated
  2. temperatureto reflux for 12 h
  3. filtrationThis was then filtered through celite
  4. extractionextracted with EtOAc (3×15 mL)
  5. washThe EtOAc layer was washed with brine
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated
  8. customThis was then purified by chromatography (11% EtOAc in hexanes)

Sources & evidence

ORD record
ord-cf4aef7b09164c2cb449254ec0013787
Source dataset
uspto-grants-2014_02
Patent number
US08658646B2

Reaction notes

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