Benzenesulfonyl chloride → 4-Bromo-1-(phenylsulfonyl)-1H-pyrrolo[2,3-B]pyridine

HRID 1174550Notes

Reaction equation

HRID 1174550 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[NH:8][CH:9]=[CH:10][C:3]=12.[H-].[Na+].[C:13]1([S:19](Cl)(=[O:21])=[O:20])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1>C1COCC1.CCCCC>[C:13]1([S:19]([N:8]2[C:4]3=[N:5][CH:6]=[CH:7][C:2]([Br:1])=[C:3]3[CH:10]=[CH:9]2)(=[O:21])=[O:20])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

6

Reactant 3

HCID 7369Benzenesulfonyl chlorideHCID 24758Sodium hydrideHCID 222736434-Bromo-1H-pyrrolo[2,3-b]pyridine

Product 1

HCID 450745614-Bromo-1-(phenylsulfonyl)-1H-pyrrolo[2,3-B]pyridineYield 73%

Reagents, catalysts & solvents 2

HCID 8003PentaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

4-bromo-1H-pyrrolo[2,3-b]pyridine (1 g, 1 Eq.) was dissolved in dry THF and cooled in an ice-bath. NaH (60% dispersion in mineral oil, 305 mg, 1.2 Eq.) was added portionwise. The resultant mixture was stirred at 0° C. for 45 minutes and benzene sulfonyl chloride (1.076 g, 1.2 Eq.) was added slowly dropwise. The resultant mixture was stirred at 0° C. for a further 75 minutes and then the solvent was removed in vacuo. The residue was partitioned in EtOAc/sat. NH4Cl and extracted with EtOAc (3×50 mL). The combined organics were washed with sat. aq. Na2CO3 (1×20 mL), brine (1×20 mL), dried over Na2SO4, filtered and concentrated under reduced pressure. Purification was achieved using column chromatography (20% EtOAc/80% hexanes), followed by recrystallization from EtOAc/hexanes. The product was filtered and then washed with pentane obtaining the title compound as a white powder (1.24 g, 73% yield); 1H NMR (DMSO D6) 6.8 (1H, d), 7.6-7.66 (3H, m), 7.72-7.76 (1H, m), 8.0 (1H, d), 8.1 (2H, m), 8.24-8.26 (1H, m); LC/MS M+1; (obs.) 339.1; LC/MS M−1 (obs.) 337.1.

Workup

  1. temperaturecooled in an ice-bath
  2. customthe solvent was removed in vacuo
  3. customThe residue was partitioned in EtOAc/
  4. extractionNH4Cl and extracted with EtOAc (3×50 mL)
  5. washThe combined organics were washed with sat. aq. Na2CO3 (1×20 mL), brine (1×20 mL)
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customPurification
  10. customfollowed by recrystallization from EtOAc/hexanes
  11. filtrationThe product was filtered

Sources & evidence

ORD record
ord-bd1c9c3b32f7486a8334660acd443cda
Source dataset
uspto-grants-2010_11
Patent number
US07838517B2

Reaction notes

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