Ammonium Chloride → 3-Bromo-5-(difluoromethyl)aniline

HRID 1040031Notes

Reaction equation

HRID 1040031 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([N+:8]([O-])=O)[CH:5]=[C:4]([CH:11]([F:13])[F:12])[CH:3]=1.[NH4+].[Cl-]>C(O)C.O.C(OCC)(=O)C.[Fe]>[Br:1][C:2]1[CH:7]=[C:6]([CH:5]=[C:4]([CH:11]([F:12])[F:13])[CH:3]=1)[NH2:8]

Participants

7

Reactant 2

HCID 25517Ammonium ChlorideHCID 672481711-Bromo-3-(difluoromethyl)-5-nitrobenzene

Product 1

HCID 584563863-Bromo-5-(difluoromethyl)anilineYield 82.1%

Reagents, catalysts & solvents 4

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
95 °C

Procedure

Iron (1.99 g, 35.7 mmol) was added to a vigorously stirred mixture of 1-bromo-3-(difluoromethyl)-5-nitrobenzene (1.80 g, 7.14 mmol) and NH4Cl (0.191 g, 3.57 mmol) in ethanol (30 mL) and water (15 mL). The mixture was heated to 95° C. for 2 h. It was then diluted with ethyl acetate while still hot and filtered over Celite. The filtrate was washed with dilute aqueous NaHCO3 and brine. After solvent evaporation the residue was purified through a silica plug, eluting with 1:5 ethyl acetate:hexanes to yield 3-bromo-5-(difluoromethyl)aniline (1.3 g, 5.86 mmol, 82%).

Workup

  1. filtrationfiltered over Celite
  2. washThe filtrate was washed with dilute aqueous NaHCO3 and brine
  3. customAfter solvent evaporation the residue
  4. customwas purified through a silica plug
  5. washeluting with 1:5 ethyl acetate

Sources & evidence

ORD record
ord-42645d21227d45138c896c2aef8ff410
Source dataset
uspto-grants-2013_10
Patent number
US08551984B2

Reaction notes

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