Methylamine → 5-bromo-N-methyl-2-nitroaniline

HRID 882190Notes

Reaction equation

HRID 882190 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4](F)[CH:3]=1.[CH3:12][NH2:13]>CCO>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]([CH:3]=1)[NH:13][CH3:12]

Participants

4

Reactant 2

HCID 6329MethylamineHCID 27833624-Bromo-2-fluoro-1-nitrobenzene

Product 1

HCID 106095305-bromo-N-methyl-2-nitroaniline

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A solution of 4-Bromo-2-fluoronitrobenzene (1-1, 10.5 g, 47.7 mmol) in EtOH (100 ml) was treated with Methylamine (2M in MeOH, 28.6 ml, 57.3 mmol, 1.2 eq) and the resulting dark maroon solution was stirred at 23 deg C. for 13 h. The reaction was then concentrated in vacuo, and the residual yellow-orange solid was partitioned between EtOAc (2×250 ml) and water (300 ml). The combined organic layers were dried over Na2SO4 and concentrated, leaving the title compound, 5-bromo-N-methyl-2-nitroaniline (1-2), as a bright orange solid. 1H NMR (300 MHz, CDCl3) δ 8.03 (d, 1H, J=9.15 Hz), 7.01 (sd, 1H, J=1.83 Hz), 6.77 (dd, 1H, J=7.02 Hz), 3.02 (d, 3H, J=4.88 Hz). LRMS m/z: Calc'd for C7H7BrN2O2 (M+H) 232.1, found 232.8.

Workup

  1. concentrationThe reaction was then concentrated in vacuo
  2. customthe residual yellow-orange solid was partitioned between EtOAc (2×250 ml) and water (300 ml)
  3. dry with materialThe combined organic layers were dried over Na2SO4
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-749c6a97ec2d4b6a914e7f26857b9aa0
Source dataset
uspto-grants-2015_03
Patent number
US08993779B2

Reaction notes

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