Ammonium Chloride → 4-(Benzyloxy)-2-fluoroaniline

HRID 388020

Reaction equation

HRID 388020 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([N+:15]([O-])=O)=[C:11]([F:18])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Cl-].[NH4+]>C(O)C.O.[Fe]>[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([NH2:15])=[C:11]([F:18])[CH:10]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 221807044-Benzyloxy-2-fluoro-1-nitrobenzene

Product 1

HCID 114998094-(Benzyloxy)-2-fluoroanilineYield 81.35%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

After dissolving the 4-benzyloxy-2-fluoronitrobenzene crude crystals (16.06 g, 63.65 mmol) in ethanol (1000 ml) and water (200 ml), electrolytic iron powder (14.0 g, 254.60 mmol) and ammonium chloride (27.2 g, 509.20 mmol) were added and the mixture was heated to reflux for 4.5 hours. The reaction solution was cooled to near room temperature, the insoluble portion was filtered off, washing was performed with ethanol and the solvent of the filtrate was distilled off under reduced pressure. The residue was dissolved in ethyl acetate, washed with saturated saline and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was adsorbed onto silica gel and purified by silica gel column chromatography (hexane-ethyl acetate system) to obtain the title compound (11.25 g, 51.78 mmol, 81.35%) as a brown oil.

Workup

  1. additionwere added
  2. temperaturethe mixture was heated
  3. temperatureto reflux for 4.5 hours
  4. filtrationthe insoluble portion was filtered off
  5. washwashing
  6. distillationthe solvent of the filtrate was distilled off under reduced pressure
  7. dissolutionThe residue was dissolved in ethyl acetate
  8. washwashed with saturated saline
  9. dry with materialdried over anhydrous magnesium sulfate
  10. distillationthe solvent was distilled off under reduced pressure
  11. custompurified by silica gel column chromatography (hexane-ethyl acetate system)

Sources & evidence

ORD record
ord-4d1e4b4af20942f88e0b8630084c9314
Source dataset
uspto-grants-2013_02
Patent number
US08372981B2

Linked notes

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