3,4-Dimethoxyaniline → 2-Bromo-4,5-dimethoxyaniline

HRID 539636Notes

Reaction equation

HRID 539636 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]([O:10][CH3:11])[C:5]([O:8][CH3:9])=[CH:6][CH:7]=1.[Br-:12].[Br-].[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C([N+](CCCC)(CCCC)CCCC)CCC.C([N+](CCCC)(CCCC)CCCC)CCC>ClCCl.CO>[Br:12][C:7]1[CH:6]=[C:5]([O:8][CH3:9])[C:4]([O:10][CH3:11])=[CH:3][C:2]=1[NH2:1]

Participants

5

Reactant 2

HCID 227703,4-DimethoxyanilineHCID 23500184Tetra-n-butylammonium tribromide

Product 1

HCID 4140762-Bromo-4,5-dimethoxyanilineYield 52.7%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

Following the procedure reported in JACS 1996, 118, 1028-1030, 4-aminoveratrole (3.06 g, 20.0 mmol) was dissolved in a mixture of dichloromethane (80 ml) and methanol (40 ml) at room temperature. Tetrabutylammonium tribromide (1.15 eq, 11.09 g) was added and the mixture was allowed to stir for 20 minutes. The mixture was extracted with saturated aqueous sodium sulfite solution. The organic layer was washed with water, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified by flash chromatography (gradient 10:1 to 7:3 hexanes/ethyl acetate) to give 2-bromo-4,5-dimethoxy-aniline 1.403 g (30%) of a yellow oil.

Workup

  1. extractionThe mixture was extracted with saturated aqueous sodium sulfite solution
  2. washThe organic layer was washed with water
  3. dry with materialdried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by flash chromatography (gradient 10:1 to 7:3 hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-ae1e8f9458de4fd48af66ccc1414429a
Source dataset
uspto-grants-2014_10
Patent number
US08871760B2

Reaction notes

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