N-bromobutanimide → 7-Bromo-1,3,4,5-tetrahydro-2H-1-benzazepin-2-one

HRID 1521574Notes

Reaction equation

HRID 1521574 reaction equation
[NH:1]1[C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][C:6]=2[CH2:5][CH2:4][CH2:3][C:2]1=[O:12].[Br:13]N1C(=O)CCC1=O>CN(C)C=O.C(OCC)(=O)C>[Br:13][C:10]1[CH:9]=[CH:8][C:7]2[NH:1][C:2](=[O:12])[CH2:3][CH2:4][CH2:5][C:6]=2[CH:11]=1

Participants

5

Reactant 2

HCID 67184N-bromobutanimideHCID 2485801,3,4,5-Tetrahydro-2H-1-benzazepin-2-one

Product 1

HCID 149781117-Bromo-1,3,4,5-tetrahydro-2H-1-benzazepin-2-one

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of the title compound from Example 2 Step B (17.0 g, 106 mmol) in N,N-dimethylformamide (500 mL) was added N-bromosuccinimide (25.2 g, 141 mmol) at room temperature, and then the mixture was refluxed for 16 hours. The reaction mixture was diluted with ethyl acetate (1 L), and the separated organic layer was washed with 0.1 M aqueous sodium hydroxide solution and saturated aqueous sodium chloride solution, dried over Na2SO4, filtered and concentrated. Purification by flash chromatography on silica gel (petroleum ether:ethyl acetate=12:1 to 3:1) provided a crude product that was recrystallized from ethyl acetate and petroleum ether (v:v=1:10) to give the title compound: LCMS m/z=241 [M+2+H]+. 1H NMR (400 MHz, d6-DMSO): δ 9.56 (s, 1H), 7.46 (s, 1H), 7.37 (d, J=8.4 Hz, 1H), 6.87 (d, J=8.4 Hz, 1H), 2.65 (m, 2H), 2.12-2.07 (m, 4H).

Workup

  1. temperaturethe mixture was refluxed for 16 hours
  2. washthe separated organic layer was washed with 0.1 M aqueous sodium hydroxide solution and saturated aqueous sodium chloride solution
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customPurification by flash chromatography on silica gel (petroleum ether:ethyl acetate=12:1 to 3:1)
  7. customprovided a crude product that
  8. customwas recrystallized from ethyl acetate and petroleum ether (v:v=1:10)

Sources & evidence

ORD record
ord-d381ec2eff0d467891f37d4bd14e601f
Source dataset
uspto-grants-2015_07
Patent number
US09073929B2

Reaction notes

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