Ammonium Chloride → 6-Bromo-5-fluoro-1-N-methylbenzene-1,2-diamine

HRID 243186Notes

Reaction equation

HRID 243186 reaction equation
[Cl-].[NH4+:2].[Br:3][C:4]1[C:9]([F:10])=[CH:8][CH:7]=[C:6]([N+:11]([O-])=O)[C:5]=1CN.[CH3:16]O.O>[Fe]>[Br:3][C:4]1[C:9]([F:10])=[CH:8][CH:7]=[C:6]([NH2:11])[C:5]=1[NH:2][CH3:16]

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 22242641Methanol--water (1/1)HCID 68157229(2-Bromo-3-fluoro-6-nitrophenyl)methylamine

Product 1

HCID 681576336-Bromo-5-fluoro-1-N-methylbenzene-1,2-diamineYield 47%

Reagents, catalysts & solvents 1

HCID 23925IronCatalyst

Procedure

Ammonium chloride (6.24 g, 117 mmol) and iron powder (4.34 g, 77.7 mmol) were added to a stirred mixture of (2-bromo-3-fluoro-6-nitrophenyl)methylamine (4.84 g, 19.4 mmol) in 3:1 methanol/water (320 mL) and the resultant mixture heated at reflux for 24 h. The solid material was removed by filtration and the filtrate concentrated to approximately ⅓ volume. This mixture was partitioned between DCM (3×) and water then the combined DCM extracts were dried (Na2SO4) and concentrated in vacuo. The resulting residue was purified by chromatography (SiO2, eluting with 0-5% methanol in DCM) to give title compound as an oil (1.99 g, 47%). LCMS (Method C): RT 2.37 min [M+H]+ 219.0, 221.0

Workup

  1. temperatureat reflux for 24 h
  2. customThe solid material was removed by filtration
  3. concentrationthe filtrate concentrated to approximately ⅓ volume
  4. customThis mixture was partitioned between DCM (3×) and water
  5. dry with materialthe combined DCM extracts were dried (Na2SO4)
  6. concentrationconcentrated in vacuo
  7. customThe resulting residue was purified by chromatography (SiO2, eluting with 0-5% methanol in DCM)

Sources & evidence

ORD record
ord-2e22d1031c464714a8dc7005bfdf5c9e
Source dataset
uspto-grants-2014_02
Patent number
US08653089B2

Reaction notes

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