Acetic Acid → 4-Bromo-5-(2,4-difluorophenoxy)benzene-1,2-diamine

HRID 629294Notes

Reaction equation

HRID 629294 reaction equation
[Br:1][C:2]1[C:8]([O:9][C:10]2[CH:15]=[CH:14][C:13]([F:16])=[CH:12][C:11]=2[F:17])=[CH:7][C:5]([NH2:6])=[C:4]([N+:18]([O-])=O)[CH:3]=1.C(O)(=O)C>O1CCCC1.C(OCC)(=O)C.[Fe]>[Br:1][C:2]1[CH:3]=[C:4]([NH2:18])[C:5]([NH2:6])=[CH:7][C:8]=1[O:9][C:10]1[CH:15]=[CH:14][C:13]([F:16])=[CH:12][C:11]=1[F:17]

Participants

6

Reactant 2

HCID 176Acetic AcidHCID 1180936684-Bromo-5-(2,4-difluorophenoxy)-2-nitroaniline

Product 1

HCID 1180936764-Bromo-5-(2,4-difluorophenoxy)benzene-1,2-diamineYield 99.8%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
60 °C

Procedure

A suspension of 4-bromo-5-(2,4-difluorophenoxy)-2-nitroaniline (0.406 g, 1.18 mmol) in tetrahydrofuran (5.0 mL) was treated with iron (0.657 g, 11.8 mmol), followed by acetic acid (4.9 mL, 87 mmol) and stirred at 60° C. for 1 h. The reaction mixture was diluted with ethyl acetate and quenched carefully with saturated sodium bicarbonate. The organic layer was separated and washed again with saturated sodium bicarbonate and brine, dried with magnesium sulfate, filtered, and concentrated to give the desired product (371 mg, quantitative) that was used immediately without further purification. LCMS calculated for C12H10BrF2N2O (M+H)+: m/z=315.0, 317.0. found: 315.0, 316.9.

Workup

  1. customquenched carefully with saturated sodium bicarbonate
  2. customThe organic layer was separated
  3. washwashed again with saturated sodium bicarbonate and brine
  4. dry with materialdried with magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-26b489fef1bc4ac395a040371148d955
Source dataset
uspto-grants-2016_04
Patent number
US09315501B2

Reaction notes

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