N-bromobutanimide → 1-Bromo-2-methoxy-4-methyl-5-nitrobenzene

HRID 2403692Notes

Reaction equation

HRID 2403692 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([N+:9]([O-:11])=[O:10])=[C:5]([CH3:12])[CH:4]=1.[Br:13]N1C(=O)CCC1=O>CN(C)C=O.S([O-])([O-])(=O)=S.[Na+].[Na+]>[Br:13][C:8]1[CH:7]=[C:6]([N+:9]([O-:11])=[O:10])[C:5]([CH3:12])=[CH:4][C:3]=1[O:2][CH3:1]

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 793303-Methyl-4-nitroanisole

Product 1

HCID 445513181-Bromo-2-methoxy-4-methyl-5-nitrobenzeneYield 88.1%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 24477Sodium ThiosulfateSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of 4-methoxy-2-methyl-1-nitrobenzene (2.0 g, 12 mmol) in N,N-dimethylformamide (5 mL) was added N-bromosuccinimide (8.52 g, 47.9 mmol). The reaction was heated to 100° C. for 1.5 hours. The reaction was cooled to room temperature and diluted with saturated aqueous sodium thiosulfate. The mixture was extracted with ethyl acetate (3×). The combined organics were washed with water, saturated sodium thiosulfate, and brine, dried over sodium sulfate, filtered, and concentrated. The residue was purified via flash column chromatography (0-30% ethyl aceate/heptanes) to provide the title compound (2.6 g, ˜43% pure) as a pale yellow solid. 1H NMR (400 MHz, CDCl3, δ): 8.32 (s, 1 H), 6.74 (s, 1 H), 3.97 (s, 3 H), 2.63 (s, 3 H).

Workup

  1. temperatureThe reaction was cooled to room temperature
  2. extractionThe mixture was extracted with ethyl acetate (3×)
  3. washThe combined organics were washed with water, saturated sodium thiosulfate, and brine
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified via flash column chromatography (0-30% ethyl aceate/heptanes)

Sources & evidence

ORD record
ord-3689605b9f9f4e8c97d139037ca6da87
Source dataset
uspto-grants-2014_08
Patent number
US08802688B2

Reaction notes

Loading…