N-bromobutanimide → 4-Bromo-3-(trifluoromethoxy)aniline

HRID 2042674Notes

Reaction equation

HRID 2042674 reaction equation
[F:1][C:2]([F:12])([F:11])[O:3][C:4]1[CH:5]=[C:6]([CH:8]=[CH:9][CH:10]=1)[NH2:7].[Br:13]N1C(=O)CCC1=O>C1(C)C=CC=CC=1>[Br:13][C:10]1[CH:9]=[CH:8][C:6]([NH2:7])=[CH:5][C:4]=1[O:3][C:2]([F:11])([F:12])[F:1].[Br:13][C:8]1[CH:9]=[CH:10][C:4]([O:3][C:2]([F:11])([F:12])[F:1])=[CH:5][C:6]=1[NH2:7]

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 737533-(Trifluoromethoxy)aniline

Product 2

HCID 141291984-Bromo-3-(trifluoromethoxy)anilineHCID 269851112-Bromo-5-(trifluoromethoxy)aniline

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of 3-trifluoromethoxy-aniline (1.77 g) in toluene (20 ml) was treated with N-bromosuccinimide (1.87 g) at ambient temperature and the reaction mixture was stirred for 2 hours at ambient temperature, quenched by addition of water and the mixture extracted with ethyl acetate (3×50 ml). The combined organic extracts were washed with aqueous sodium hydrogen carbonate (saturated), dried over sodium sulfate and then concentrated in vacuo. The residue was purified by chromatography on silica gel (eluent: cyclohexane/ethyl acetate 95:5) to afford 4-bromo-3-trifluoromethoxy-aniline (270 mg) and 2-bromo-5-trifluoromethoxy-aniline (1.45 g), which were both characterized by mass and NMR spectra. 4-bromo-3-trifluoromethoxy-aniline: MS (ES+) 256/258 (MH+); 1H NMR (400 MHz, CDCl3) 3.5 (brs, 2H), 6.5 (d, 1H), 6.7 (s, 1H), 7.3 (d, 1H). 2-bromo-5-trifluoromethoxy-aniline: MS (ES+) 256/258 (MH+); 1H NMR (400 MHz, CDCl3) 4.2 (brs, 2H), 6.5 (d, 1H), 6.6 (s, 1H), 7.4 (d, 1H).

Workup

  1. customquenched by addition of water
  2. extractionthe mixture extracted with ethyl acetate (3×50 ml)
  3. washThe combined organic extracts were washed with aqueous sodium hydrogen carbonate (saturated)
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by chromatography on silica gel (eluent: cyclohexane/ethyl acetate 95:5)

Sources & evidence

ORD record
ord-1c6f0aac75cc4614af8f219ed9f7e3b7
Source dataset
uspto-grants-2013_11
Patent number
US08586593B2

Reaction notes

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