p-Aminoacetophenone → 1-(4-Amino-3-bromo-phenyl)-ethanone

HRID 2367853Notes

Reaction equation

HRID 2367853 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:10])[CH3:9])=[CH:4][CH:3]=1.C1C(=O)N([Br:18])C(=O)C1>C1(C)C=CC=CC=1>[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:10])[CH3:9])=[CH:4][C:3]=1[Br:18]

Participants

4

Reactant 2

HCID 7468p-AminoacetophenoneHCID 67184N-bromobutanimide

Product 1

HCID 15152811-(4-Amino-3-bromo-phenyl)-ethanoneYield 42.9%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

1-(4-aminophenyl)ethanone (2.50 g; 18.5 mmol) was dissolved in 100 mL toluene. NBS (3.30 g; 18.8 mmol) was added portionwise. After 15 min stirring at RT, the organic phase was washed with water twice, and dried over Na2SO4. The solvent was removed by rotavap to get oil, which was purified by silica gel chromatography, to afford 1.7 g of a white solid, 1-(4-amino-3-bromophenyl)ethanone (1.7 g; 7.94 mmol). The intermediate was dissolved in CH2Cl2. The reaction mixture was cooled to 0° C. Trifluoroacetic anhydride (2.0 g; 9.52 mmol) and NEt3 (1.0 g; 9.90 mmol) were added sequentially. The reaction mixture was stirred at RT for another hour. The organic phase was washed twice with water, dried over MgSO4. The solvent was removed, to afford 2.4 g (yield 42%) of product as white solid. 1H NMR (400 MHz, CDCl3) δ 8.61 (s, 1H, N—H), 8.46, (d, 3JHH=8.6 Hz, 1H, Ar—H), 8.21 (d, 4JHH=2.0 Hz, 1H, Ar—H), 7.95 (dd, 3JHH=8.6 Hz, 4JHH=1.9 Hz, 1H, Ar—H), 2.58 (s, 3H, CH3).

Workup

  1. washthe organic phase was washed with water twice
  2. dry with materialdried over Na2SO4
  3. customThe solvent was removed by rotavap
  4. customto get oil, which
  5. customwas purified by silica gel chromatography

Sources & evidence

ORD record
ord-25d5a7b81bd1460293cedf993997d5c8
Source dataset
uspto-grants-2014_04
Patent number
US08703096B2

Reaction notes

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