N-Methyl-4-nitroaniline → (2-Bromo-4-nitro-phenyl)-methyl-amine (2-bromo-4-nitro-phenyl)-methyl-amine

HRID 1908409Notes

Reaction equation

[CH3:1][NH:2][C:3]1[CH:8]=[CH:7][C:6]([N+:9]([O-:11])=[O:10])=[CH:5][CH:4]=1.[Br:12]Br.C([O-])(O)=O.[Na+]>CC(O)=O.C(Cl)(Cl)Cl>[Br:12][C:4]1[CH:5]=[C:6]([N+:9]([O-:11])=[O:10])[CH:7]=[CH:8][C:3]=1[NH:2][CH3:1].[Br:12][C:4]1[CH:5]=[C:6]([N+:9]([O-:11])=[O:10])[CH:7]=[CH:8][C:3]=1[NH:2][CH3:1]

Participants

Conditions

Temperature: 10 °C

Procedure

To a solution of methyl-(4-nitro-phenyl)-amine (15.2 g, 0.1 mol) in AcOH (150 mL) and CHCl3 (50 mL) was added Br2 (16.0 g, 0.1 mol) dropwise at 5° C. The mixture was stirred at 10° C. for 1 h and then basified with sat. aq. NaHCO3. The resulting mixture was extracted with EtOAc (100 mL×3), and the combined organics were dried over anhydrous Na2SO4 and evaporated under vacuum to give (2-bromo-4-nitro-phenyl)-methyl-amine (2-bromo-4-nitro-phenyl)-methyl-amine (23.0 g, 99%), which was used in the next step without further purification. 1H NMR (300 MHz, CDCl3) δ 8.37 (d, J=2.4 Hz, 1H), 8.13 (dd, J=2.4, 9.0 Hz, 1H), 6.58 (d, J=9.0 Hz, 1H), 5.17 (brs, 1H), 3.01 (d, J=5.4 Hz, 3H).

Workup

extractionThe resulting mixture was extracted with EtOAc (100 mL×3)
dry with materialthe combined organics were dried over anhydrous Na2SO4
customevaporated under vacuum

Sources & evidence

ORD record: ord-f597af17f1fa497da4db6e4b034cd62b
Source dataset: uspto-grants-2013_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08598181B2

Reaction notes

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