Methylamine → 2-fluoro-3-methoxy-N-methyl-6-nitroaniline

HRID 882203Notes

Reaction equation

HRID 882203 reaction equation
[F:1][C:2]1[C:7](F)=[C:6]([N+:9]([O-:11])=[O:10])[CH:5]=[CH:4][C:3]=1[O:12][CH3:13].[CH3:14][NH2:15]>CCO>[F:1][C:2]1[C:3]([O:12][CH3:13])=[CH:4][CH:5]=[C:6]([N+:9]([O-:11])=[O:10])[C:7]=1[NH:15][CH3:14]

Participants

4

Reactant 2

HCID 6329MethylamineHCID 101039612,3-Difluoro-4-nitroanisole

Product 1

HCID 667492842-fluoro-3-methoxy-N-methyl-6-nitroaniline

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A solution of 2,3-Difluoro-4-nitroanisole (7-1, 1.0 g, 5.29 mmol) in EtOH (20 ml) was treated with Methylamine (2M in THF, 3.17 ml, 6.35 mmol, 1.2 eq) and the resulting yellow solution was stirred at 23 deg C. for 1 h. The reaction was complete by LC/MS, but allowed to stir at 23 deg C. for an additional 17 h. The residual bright orange-yellow solution was concentrated in vacuo, then partitioned between EtOAc (2×80 ml) and water (90 ml). The combined organic layers were dried over Na2SO4 and concentrated, leaving the title compound, 2-fluoro-3-methoxy-N-methyl-6-nitroaniline (7-2), as an orange solid with >90% purity. 1H NMR (500 MHz, CDCl3) δ 8.01 (d, 1H, J=1.9 Hz), 7.84 (bs, 1H), 6.81-6.83 (m, 1H), 3.95 (s, 3H), 3.24 (m, 3H). LRMS m/z: Calc'd for C8H9FN2O3 (M+H) 201.2, found 200.9.

Workup

  1. stirringto stir at 23 deg C
  2. waitfor an additional 17 h
  3. concentrationThe residual bright orange-yellow solution was concentrated in vacuo
  4. custompartitioned between EtOAc (2×80 ml) and water (90 ml)
  5. dry with materialThe combined organic layers were dried over Na2SO4
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-4406944a99e44fe18320186f07d59e8f
Source dataset
uspto-grants-2015_03
Patent number
US08993779B2

Reaction notes

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