Methanol → 4-Fluoro-3-methyl-N2-phenylbenzene-1,2-diamine

HRID 242982Notes

Reaction equation

[F:1][C:2]1[C:3]([CH3:18])=[C:4]([NH:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:5]([N+:8]([O-])=O)=[CH:6][CH:7]=1.CO.[NH4+].[Cl-]>[Fe].O>[F:1][C:2]1[C:3]([CH3:18])=[C:4]([NH:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[C:5]([NH2:8])=[CH:6][CH:7]=1

Participants

Conditions

Temperature: 90 °C

Procedure

To a mixture of (3-fluoro-2-methyl-6-nitrophenyl)phenylamine (1.5 g, 6.1 mmol) in a 3:1 mixture of MeOH:water (40 mL) were added NH4Cl (1.88 g, 36.5 mmol) and iron powder (1.36 g, 24.4 mmol) and the reaction mixture heated at 90° C. for 1 h. After cooling to RT, the solid was filtered through a pad of Celite® and washed with additional MeOH. The filtrate was concentrated in vacuo and the resulting residue partitioned between EtOAc and water. The aqueous phase was further extracted with EtOAc (×3) and the combined organic fractions were washed with brine, dried (MgSO4) and concentrated in vacuo to afford the title compound as a pink solid (1.16 g, 88%). 1H NMR (CDCl3, 400 MHz): δ 7.22-7.15 (2H, m), 6.88-6.77 (2H, m), 6.64-6.55 (3H, m), 5.03 (1H, br s), 3.68 (2H, br s), 2.11 (3H, d, J=2.24 Hz).

Workup

temperatureAfter cooling to RT
filtrationthe solid was filtered through a pad of Celite®
washwashed with additional MeOH
concentrationThe filtrate was concentrated in vacuo
customthe resulting residue partitioned between EtOAc and water
extractionThe aqueous phase was further extracted with EtOAc (×3)
washthe combined organic fractions were washed with brine
dry with materialdried (MgSO4)
concentrationconcentrated in vacuo

Sources & evidence

ORD record: ord-91f9fdd64f144e30aa058b205e24b833
Source dataset: uspto-grants-2014_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08653089B2

Reaction notes

Loading…