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

HRID 1060483Notes

Reaction equation

HRID 1060483 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:7]=[C:8]([O:10][CH3:11])[CH:9]=1)[NH2:6].[Br-:12].[Br-].[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C([N+](CCCC)(CCCC)CCCC)CCC.C([N+](CCCC)(CCCC)CCCC)CCC>C(Cl)Cl>[Br:12][C:9]1[C:8]([O:10][CH3:11])=[CH:7][C:5]([NH2:6])=[CH:4][C:3]=1[O:2][CH3:1]

Participants

4

Reactant 2

HCID 663013,5-DimethoxyanilineHCID 23500184Tetra-n-butylammonium tribromide

Product 1

HCID 225717984-Bromo-3,5-dimethoxyanilineYield 62.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

3,5-Dimethoxyaniline (7.55 g) was dissolved in CH2Cl2 (100 mL) under N2 and the solution was cooled to −78° C. A solution of tetrabutylammonium tribromide (25 g) in CH2Cl2 (100 mL) was added and the mixture was stirred at that temperature for 45 min. The mixture was allowed to warm up to room temperature, stirred for 1.5 h and extracted with 1N HCl. The extract was neutralized with 3 N NaOH and extracted with AcOEt. The extract was dried (MgSO4), filtered and evaporated. The residue was purified by column chromatography (silica gel; eluent: hexane/AcOEt 4:1 to 2:3) to give 4-bromo-3,5-dimethoxyaniline (3.76 g).

Workup

  1. temperatureto warm up to room temperature
  2. stirringstirred for 1.5 h
  3. extractionextracted with 1N HCl
  4. extractionextracted with AcOEt
  5. dry with materialThe extract was dried (MgSO4)
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue was purified by column chromatography (silica gel; eluent: hexane/AcOEt 4:1 to 2:3)

Sources & evidence

ORD record
ord-99cd628700dc46fabba5f9b4f4b89e5d
Source dataset
uspto-grants-2003_02
Patent number
US06521666B1

Reaction notes

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