N-bromobutanimide → HCID 57722777, compound

HRID 222295Notes

Reaction equation

HRID 222295 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]2[C:12](=[O:13])[C:11]3[CH:14]=[C:15]([CH:18]=[CH2:19])[CH:16]=[CH:17][C:10]=3[CH:9]=[CH:8][C:5]2=[N:6][CH:7]=1.BrN1C(=[O:26])CCC1=O.CC([O-])(C)C.[K+]>CS(C)=O.O>[Cl:1][C:2]1[CH:3]=[C:4]2[C:12](=[O:13])[C:11]3[CH:14]=[C:15]([CH:18]4[CH2:19][O:26]4)[CH:16]=[CH:17][C:10]=3[CH:9]=[CH:8][C:5]2=[N:6][CH:7]=1

Participants

6

Reactant 3

HCID 67184N-bromobutanimide2×HCID 23665647Potassium tert-butoxideHCID 57722897HCID 57722897, compound

Product 1

HCID 57722777HCID 57722777, compound

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent3×

Conditions

Temperature
60 °C

Procedure

3-chloro-7-vinyl-5H-benzo[4,5]cyclohepta[1,2-b]pyridin-5-one (0.30 g, 1.12 mmol) was dissolved in 17 mL DMSO and 3.0 mL water. N-Bromosuccinimide (0.20 g, 1.12 mmol) was added and the reaction was heated in an oil bath at 60° C. for 1 hour at which time an additional 0.1 g N-Bromosuccinimide (0.56 mmol) was added and the mixture was stirred an additional 45 min at 60° C. The resulting mixture was diluted with water and extracted with ethyl acetate three times. The combined organics were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The resulting crude residue was dissolved in 30 mL tetrahydrofuran and 6 mL t-BuOH. t-BuOK (2.24 mL of 1.0 M in THF, 2.24 mmol) was added dropwise and the resulting orange slurry was stirred at room temperature for 45 min. The reaction was diluted with water and extracted with ethyl acetate three times. The combined organics were washed with brine, dried over magnesium sulfate, concentrated in vacuo, and purified via flash chromatography (silica, 0-25% ethyl acetate/hexanes) to afford the title compound. 1H NMR (600 MHz, CDCl3) δ 8.79 (d, 1H); 8.49 (d, 1H); 8.20 (d, 1H); 7.57 (d, 1H); 7.55 (dd, 1H); 7.27 (d, 1H); 7.23 (d, 1H); 3.99 (dd, 1H); 3.21 (dd, 1H); 2.84 (dd, 1H).

Workup

  1. additionwas added
  2. extractionextracted with ethyl acetate three times
  3. washThe combined organics were washed with brine
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. dissolutionThe resulting crude residue was dissolved in 30 mL tetrahydrofuran
  8. stirringthe resulting orange slurry was stirred at room temperature for 45 min
  9. extractionextracted with ethyl acetate three times
  10. washThe combined organics were washed with brine
  11. dry with materialdried over magnesium sulfate
  12. concentrationconcentrated in vacuo
  13. custompurified via flash chromatography (silica, 0-25% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-f59e936a8adb4503b12c909dcf286af8
Source dataset
uspto-grants-2012_06
Patent number
US08207186B2

Reaction notes

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