Acetic Acid → 2-Bromo-3-methoxyaniline

HRID 1632019Notes

Reaction equation

HRID 1632019 reaction equation
[Br:1][C:2]1[C:7]([N+:8]([O-])=O)=[CH:6][CH:5]=[CH:4][C:3]=1[O:11][CH3:12].C(O)(=O)C.ClCCl>C(O)C.O.C(=O)([O-])[O-].[Na+].[Na+].[Fe]>[Br:1][C:2]1[C:3]([O:11][CH3:12])=[CH:4][CH:5]=[CH:6][C:7]=1[NH2:8]

Participants

8

Reactant 3

HCID 176Acetic AcidHCID 6344DichloromethaneHCID 177502992-Bromo-3-nitroanisole

Product 1

HCID 109105752-Bromo-3-methoxyanilineYield 90%

Reagents, catalysts & solvents 4

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 10340Sodium CarbonateSolvent

Procedure

(Prepared by a modification of reported procedure WO Patent: WO2006/7700). To a solution of 2-bromo-3-nitro-anisole synthesized above (10.3 mmol, 1.0 eq.) in absolute ethanol and glacial acetic acid at room temperature was added iron powder (42.1 mmol, 4.1 eq). The resultant mixture was heated to reflux for 1.5 hours, and then cooled to room temperature. The reaction mixture was diluted with water, and solid sodium carbonate was added until the pH was 6-7. Dichloromethane was added, and the mixture was filtered through celite. The dried (sodium sulfate) organics were concentrated to afford 2-bromo-3-methoxy-aniline (I-10, X═Br, R1═CH3) as an oil. Yield: 90%; 1H NMR (400 MHz; CDCl3): 3.87 (s, 3H), 4.16 (br s, 2H), 6.31 (dd, J=8.0, 1.2 Hz, 1H), 6.42 (dt, J=8.0, 0.8, 0.4 Hz, 1H), 7.05 (t, J=8.0 Hz, 1H) ppm.

Workup

  1. custom(Prepared by a modification of reported procedure WO Patent
  2. temperatureto reflux for 1.5 hours
  3. additionwas added until the pH was 6-7
  4. filtrationthe mixture was filtered through celite
  5. dry with materialThe dried (sodium sulfate)
  6. concentrationorganics were concentrated

Sources & evidence

ORD record
ord-cd145f4e64c44f529b4a262b5be96fae
Source dataset
uspto-grants-2014_07
Patent number
US08791267B2

Reaction notes

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