Methylamine → 1-N-methyl-4-nitrobenzene-1,2-diamine

HRID 1640706Notes

Reaction equation

HRID 1640706 reaction equation
F[C:2]1[CH:8]=[CH:7][C:6]([N+:9]([O-:11])=[O:10])=[CH:5][C:3]=1[NH2:4].[CH3:12][NH2:13].C1COCC1.C(=O)([O-])[O-].[K+].[K+]>CN1CCCC1=O>[CH3:12][NH:13][C:2]1[C:3]([NH2:4])=[CH:5][C:6]([N+:9]([O-:11])=[O:10])=[CH:7][CH:8]=1

Participants

6

Reactant 4

HCID 6329MethylamineHCID 8028TetrahydrofuranHCID 11430Potassium CarbonateHCID 677852-Fluoro-5-nitroaniline

Product 1

HCID 34200251-N-methyl-4-nitrobenzene-1,2-diamine

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
120 °C

Procedure

In a 350 mL pressure flask, 2-fluoro-5-nitroaniline (10 g, 0.064 mol), methylamine as a 2M solution in THF (65 mL, 0.13 mol) and potassium carbonate (18 g, 0.13 mol) in 1-Methyl-2-pyrrolidinone (80 mL) were combined. The flask was sealed and heated to 120 degrees C. overnight. The reaction was monitored by TLC. When reaction was judged to be complete based upon consumption of 2-fluoro-5-nitroaniline, it was cooled to room temperature and poured into 2-3 times the total reaction volume of water. When a precipitate was formed, it was filtered and dried. The product was carried on without purification. 1H NMR (300 MHz, d6DMSO) δ 7.54 (dd, J=8.79, 2.64 Hz, 1H), 7.39 (d, J=2.64 Hz, 1H), 6.41 (d, J=8.79 Hz, 1H), 6.11 (d, J=4.39 Hz, 1H), 5.07 (s, 2H), 2.83 (d, J=4.83 Hz, 3H).

Workup

  1. customThe flask was sealed
  2. customovernight
  3. customWhen reaction
  4. customto be complete based upon consumption of 2-fluoro-5-nitroaniline, it
  5. temperaturewas cooled to room temperature
  6. additionpoured into 2-3 times the total reaction volume of water
  7. customWhen a precipitate was formed
  8. filtrationit was filtered
  9. customdried
  10. customThe product was carried on without purification

Sources & evidence

ORD record
ord-04cbb9f6e8d04a38b4813ffc47ffd625
Source dataset
uspto-grants-2012_02
Patent number
US08114885B2

Reaction notes

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