Benzenesulfonyl chloride → 1H-Pyrrolo[2,3-b]pyridine-3-carboxaldehyde, 5-bromo-1-(phenylsulfonyl)-

HRID 1432323Notes

Reaction equation

HRID 1432323 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:10]([CH:11]=[O:12])=[CH:9][NH:8][C:5]2=[N:6][CH:7]=1.[C:13]1([S:19](Cl)(=[O:21])=[O:20])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[OH-].[Na+]>ClCCl.S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC>[C:13]1([S:19]([N:8]2[C:5]3=[N:6][CH:7]=[C:2]([Br:1])[CH:3]=[C:4]3[C:10]([CH:11]=[O:12])=[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 14798Sodium HydroxideHCID 247296055-bromo-1H-pyrrolo(2,3-b)pyridine-3-carbaldehyde

Product 1

HCID 592397531H-Pyrrolo[2,3-b]pyridine-3-carboxaldehyde, 5-bromo-1-(phenylsulfonyl)-Yield 91%

Reagents, catalysts & solvents 2

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 6344DichloromethaneSolvent

Procedure

To a suspension of 6 (5.0 g, 22.2 mmol) in dichloromethane (130 mL) was added benzenesulfonyl chloride (4.25 mL, 33.3 mmol), tetra-n-butylammonium hydrogen sulphate (0.98 g, 2.98 mmol) and 50% aqueous NaOH (4.2 mL). The reaction mixture was stirred for 2 h then poured onto water (500 mL), extracted with dichloromethane (3×200 mL). The combined organic extracts were washed with saturated aqueous NaHCO3 (2×150 mL) and dried (MgSO4). Concentration produced a white solid which was washed with ether (3×150 mL) to give product 7 as a light orange solid (7.34 g, 91%); 1H NMR (400 MHz, CDCl3+4 drops d4-MeOH) δ 9.95 (s, 1H), 8.61 (d, J=2.3 Hz, 1H), 8.46 (d, J=2.1 Hz, 1H), 8.38 (s, 1H), 8.19 (m, 2H), 7.62 (tt, J=7.5, 1.3 Hz, 1H), 7.51 (t, J=7.1 Hz, 2H).

Workup

  1. additionthen poured onto water (500 mL)
  2. extractionextracted with dichloromethane (3×200 mL)
  3. washThe combined organic extracts were washed with saturated aqueous NaHCO3 (2×150 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationConcentration
  6. customproduced a white solid which
  7. washwas washed with ether (3×150 mL)

Sources & evidence

ORD record
ord-55428cb5735041df95aaa21994f65b4f
Source dataset
uspto-grants-2009_11
Patent number
US07612086B2

Reaction notes

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