Potassium Carbonate → 2-(2,4-Dimethoxybenzylamino)-4-methylaniline

HRID 857873Notes

Reaction equation

HRID 857873 reaction equation
[CH3:1][O:2][C:3]1[C:10](OC)=[CH:9][CH:8]=[CH:7][C:4]=1[CH2:5][NH2:6].[C:13](=[O:16])([O-])[O-].[K+].[K+].F[C:20]1[CH:21]=[C:22]([CH3:29])[CH:23]=[CH:24][C:25]=1[N+:26]([O-])=O.[Cl-].[NH4+]>CN1CCCC1=O.C(O)C.[Fe].O.CCOCC>[CH3:1][O:2][C:3]1[CH:10]=[C:9]([O:16][CH3:13])[CH:8]=[CH:7][C:4]=1[CH2:5][NH:6][C:20]1[CH:21]=[C:22]([CH3:29])[CH:23]=[CH:24][C:25]=1[NH2:26]

Participants

10

Reactant 4

HCID 11430Potassium CarbonateHCID 25517Ammonium ChlorideHCID 67966Benzene, 2-fluoro-4-methyl-1-nitro-HCID 781062,3-Dimethoxybenzylamine

Product 1

HCID 223857232-(2,4-Dimethoxybenzylamino)-4-methylanilineYield 67.1%

Reagents, catalysts & solvents 5

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
120 °C

Procedure

2,3-Dimethoxybenzylamine (1.05 g) and potassium-carbonate (1.52 g) were added to a solution of 3-fluoro-4-nitrotoluene (0.832 g) in 1-methyl-2-pyrrolidinone (5.0 ml), and the mixture was stirred at 120° C. for 4 hours. Then, ether was added to the reaction mixture. The organic layer was washed with water and brine, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated in vacuo to give a yellow oil. The yellow oil was dissolved in ethanol (100 ml), and to the solution were added water (50 ml), saturated aqueous ammonium chloride (50 ml) and iron dust (352 g). The mixture was heated under reflux for 3 hours while vigorous stirring. Then insolubles were removed by filtration, and the filtrate was concentrated in vacuo. The residue was dissolved in chloroform, and the organic layer was washed with water and brine and dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated in vacuo, and the residue was purified by silica gel column chromatography (hexane:ethyl acetate, 3:1 to 2:1) and then recrystallized by ethyl acetate-hexane to give the title compound (0.980 g).

Workup

  1. washThe organic layer was washed with water and brine
  2. dry with materialdried over anhydrous magnesium sulfate
  3. filtrationfiltered
  4. concentrationThe filtrate was concentrated in vacuo
  5. customto give a yellow oil
  6. temperatureThe mixture was heated
  7. temperatureunder reflux for 3 hours while vigorous stirring
  8. customThen insolubles were removed by filtration
  9. concentrationthe filtrate was concentrated in vacuo
  10. dissolutionThe residue was dissolved in chloroform
  11. washthe organic layer was washed with water and brine
  12. dry with materialdried over anhydrous magnesium sulfate
  13. filtrationfiltered
  14. concentrationThe filtrate was concentrated in vacuo
  15. customthe residue was purified by silica gel column chromatography (hexane:ethyl acetate, 3:1 to 2:1)
  16. customrecrystallized by ethyl acetate-hexane

Sources & evidence

ORD record
ord-3e441a221e094f7184f773fbdac704c8
Source dataset
uspto-grants-2006_12
Patent number
US07148224B2

Reaction notes

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