Ammonium Chloride → 3-Chloro-4-fluoro-N2-phenylbenzene-1,2-diamine

HRID 242931Notes

Reaction equation

[Cl:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[C:4]([N+:9]([O-])=O)[C:3]=1[NH:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[NH4+].[Cl-]>CO.O.[Fe]>[Cl:1][C:2]1[C:7]([F:8])=[CH:6][CH:5]=[C:4]([NH2:9])[C:3]=1[NH:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

Conditions

Temperature: 90 °C

Procedure

To a mixture of (2-chloro-3-fluoro-6-nitrophenyl)phenylamine (1.28 g, 4.8 mmol) in MeOH (45 mL) and water (15 mL) were added NH4Cl (1.48 g, 28.8 mmol) and iron powder (1.07 g, 19.2 mmol) and the reaction mixture heated at 90° C. for 2 h. After cooling to RT, the crude mixture was filtered through a pad of Celite® and the filtrate concentrated in vacuo. The resulting residue was partitioned between EtOAc and water. The aqueous phase was extracted with EtOAc (×3) and the combined organic fractions washed with brine, dried (MgSO4) and concentrated in vacuo. The resulting residue was purified by column chromatography (Si—PCC, gradient 0-100% DCM in cyclohexane) to afford the title compound (918 mg, 81%). LCMS (Method C): RT 3.46 min [M+H]+ 237.1/239.1.

Workup

temperatureAfter cooling to RT
filtrationthe crude mixture was filtered through a pad of Celite®
concentrationthe filtrate concentrated in vacuo
customThe resulting residue was partitioned between EtOAc and water
extractionThe aqueous phase was extracted with EtOAc (×3)
washthe combined organic fractions washed with brine
dry with materialdried (MgSO4)
concentrationconcentrated in vacuo
customThe resulting residue was purified by column chromatography (Si—PCC, gradient 0-100% DCM in cyclohexane)

Sources & evidence

ORD record: ord-af610b4edd2d4582b26a0f6716d4d887
Source dataset: uspto-grants-2014_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08653089B2

Reaction notes

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