Water → 3-Bromo-5-(2,4-difluoro-phenoxy)-2-methyl-phenylamine

HRID 1818741Notes

Reaction equation

[Br:1][C:2]1[CH:7]=[C:6]([O:8][C:9]2[CH:14]=[CH:13][C:12]([F:15])=[CH:11][C:10]=2[F:16])[CH:5]=[C:4]([N+:17]([O-])=O)[C:3]=1[CH3:20].O.[Cl-].[NH4+]>CCO.[Fe]>[Br:1][C:2]1[C:3]([CH3:20])=[C:4]([NH2:17])[CH:5]=[C:6]([O:8][C:9]2[CH:14]=[CH:13][C:12]([F:15])=[CH:11][C:10]=2[F:16])[CH:7]=1

Participants

Conditions

Temperature: 85 °C

Procedure

1-Bromo-5-(2,4-difluoro-phenoxy)-2-methyl-3-nitro-benzene (7.31 g, 21.2 mmol) was dissolved in 145 mL EtOH and 35 mL water was added, followed by addition of ammonium chloride (3.63 g, 67.9 mmol) and powdered iron (3.56 g, 63.8 mmol). The reaction mixture was placed under nitrogen atmosphere and heated to 85° C. for 2.5 hours. The reaction mixture was cooled, filtered through celite, and the filtrate was concentrated under reduced pressure. The residue was partitioned between water and EtOAc and the organic phase was separated, washed with brine, dried (MgSO4), filtered and concentrated under reduced pressure. The residue was chromatographed through silica (0%-25% EtOAc in hexanes) to give 7.583 g of 3-bromo-5-(2,4-difluoro-phenoxy)-2-methyl-phenylamine, MS(M+H)=314.

Workup

temperatureThe reaction mixture was cooled
filtrationfiltered through celite
concentrationthe filtrate was concentrated under reduced pressure
customThe residue was partitioned between water and EtOAc
customthe organic phase was separated
washwashed with brine
dry with materialdried (MgSO4)
filtrationfiltered
concentrationconcentrated under reduced pressure
customThe residue was chromatographed through silica (0%-25% EtOAc in hexanes)

Sources & evidence

ORD record: ord-9e4c1b14d8fb4cbfb72e48c977869ac7
Source dataset: uspto-grants-2009_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07601726B2

Reaction notes

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