Water → 1-(Benzenesulfonyl)-5-bromo-1H-pyrrolo[2,3-b]pyridine

HRID 1926633Notes

Reaction equation

HRID 1926633 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[CH:10]=[CH:9][NH:8][C:5]2=[N:6][CH:7]=1.[H-].[Na+].[C:13]1([S:19](Cl)(=[O:21])=[O:20])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.O>CN(C=O)C>[Br:1][C:2]1[CH:3]=[C:4]2[CH:10]=[CH:9][N:8]([S:19]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)(=[O:21])=[O:20])[C:5]2=[N:6][CH:7]=1

Participants

6

Reactant 4

HCID 962WaterHCID 7369Benzenesulfonyl chlorideHCID 24758Sodium hydrideHCID 103079325-bromo-1H-pyrrolo[2,3-b]pyridine

Product 1

HCID 242292461-(Benzenesulfonyl)-5-bromo-1H-pyrrolo[2,3-b]pyridine

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred solution of 5-bromo-1H-pyrrolo[2,3-b]pyridine (20.0 g, 102 mmol) in DMF (400 ml) at 0° C. was added NaH (60% mineral oil dispersion; 4.87 g, 122 mmol) slowly (CAUTION: GAS EVOLUTION). The reaction mixture was stirred at 0° C. for 2 h. Benzenesulfonyl chloride (17.0 ml, 132 mmol) was added dropwise, and the reaction mixture was allowed to warm to ambient. After 1 hour the reaction mixture was cooled in an ice bath, and 100 mL of water was added slowly (CAUTION: GAS EVOLUTION, EXOTHERM). The reaction mixture was partitioned between ethyl acetate (500 mL) and brine (600 mL). The organic layer was washed with additional brine (500 mL), followed by saturated aqueous ammonium chloride (250 mL). The first and 3rd aqueous layers were combined and back-extracted with ethyl acetate (500 mL). The combined organics were dried over sodium sulfate, filtered and concentrated to a thick slurry. EtOAc (100 mL) was added, followed by hexanes (100 mL). The mixture was filtered, and the filter cake was rinsed with 1:1 EtOAc/Hexanes (50 mL) to afford 5-bromo-1-(phenylsulfonyl)-1H-pyrrolo[2,3-b]pyridine as a grey solid. The filtrate can be concentrated and purified by silica gel chromatography (EtOAc/Hexanes gradient) to afford additional product. LRMS (ESI) calculated for C13H9BrN2O2S [M+H]+, 337.0; found 336.9.

Workup

  1. temperatureto warm to ambient
  2. temperatureAfter 1 hour the reaction mixture was cooled in an ice bath
  3. customThe reaction mixture was partitioned between ethyl acetate (500 mL) and brine (600 mL)
  4. washThe organic layer was washed with additional brine (500 mL)
  5. extractionback-extracted with ethyl acetate (500 mL)
  6. dry with materialThe combined organics were dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated to a thick slurry
  9. additionEtOAc (100 mL) was added
  10. filtrationThe mixture was filtered
  11. washthe filter cake was rinsed with 1:1 EtOAc/Hexanes (50 mL)

Sources & evidence

ORD record
ord-e6d3675f7c6e4178909006ad4d078c60
Source dataset
uspto-grants-2012_05
Patent number
US08183245B2

Reaction notes

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