Iodine → 3-Iodo-1-tosyl-1H-pyrrolo[2,3-b]pyridine-4-carbaldehyde

HRID 1627185Notes

Reaction equation

HRID 1627185 reaction equation
[NH:1]1[C:5]2[N:6]=[CH:7][CH:8]=[C:9]([CH:10]=[O:11])[C:4]=2[CH:3]=[CH:2]1.[I:12]I.[I-].[Na+].[OH-].[Na+].[H-].[Na+].[S:20](Cl)([C:23]1[CH:29]=[CH:28][C:26]([CH3:27])=[CH:25][CH:24]=1)(=[O:22])=[O:21]>CCO.O.CCOC(C)=O>[I:12][C:3]1[C:4]2[C:9]([CH:10]=[O:11])=[CH:8][CH:7]=[N:6][C:5]=2[N:1]([S:20]([C:23]2[CH:29]=[CH:28][C:26]([CH3:27])=[CH:25][CH:24]=2)(=[O:22])=[O:21])[CH:2]=1

Participants

10

Reactant 6

HCID 807IodineHCID 5238Sodium IodideHCID 73974-Toluenesulfonyl chlorideHCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 219638871H-Pyrrolo[2,3-b]pyridine-4-carbaldehyde

Product 1

HCID 582934163-Iodo-1-tosyl-1H-pyrrolo[2,3-b]pyridine-4-carbaldehydeYield 60%

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 1H-pyrrolo[2,3-b]pyridine-4-carbaldehyde (2.0 g, 13.7 mmol) in EtOH (40 mL) was added iodine (4.17 g, 16.4 mmol), sodium iodide (2.46 g, 16.4 mmol), and aqueous NaOH (1N, 16 mL). After stirring for 4 h at room temperature, the reaction mixture was diluted with water (200 mL), and the orange precipitate was collected by filtration and dried under vacuum. The solid was dissolved in DMF (20 mL); sodium hydride (60%, 660 mg, 16.4 mmol) was slowly added, and after stirring the deep red solution at room temperature for 30 min, tosyl chloride (2.87 g, 15.1 mmol) was added. The reaction mixture was stirred for an additional 2 h at room temperature, and was then diluted with EtOAc and quenched with water. The organics were separated, washed with aqueous NaHSO3 (0.1 N) and brine, dried over MgSO4, and concentrated in vacuo. Purification by silica gel chromatography (3:1:1 hexane/DCM/EtOAc) gave the title compound as a yellow solid (3.48 g, 60%). 1H NMR (500 MHz, DMSO-d6) δ 2.33 (s, 3H), 7.43 (d, J=8.5 Hz, 2H), 7.63 (d, J=5.0 Hz, 1H), 8.03 (d, J=8.5 Hz, 2H), 8.39 (s, 1H), 8.60 (d, J=5.0 Hz, 1H), 11.31 (s, 1H). [M+H] calc'd for C15H11N2O3S, 427; found, 427.

Workup

  1. filtrationthe orange precipitate was collected by filtration
  2. customdried under vacuum
  3. dissolutionThe solid was dissolved in DMF (20 mL)
  4. stirringafter stirring the deep red solution at room temperature for 30 min
  5. stirringThe reaction mixture was stirred for an additional 2 h at room temperature
  6. customquenched with water
  7. customThe organics were separated
  8. washwashed with aqueous NaHSO3 (0.1 N) and brine
  9. dry with materialdried over MgSO4
  10. concentrationconcentrated in vacuo
  11. customPurification by silica gel chromatography (3:1:1 hexane/DCM/EtOAc)

Sources & evidence

ORD record
ord-0c7ecc9c448640c98f669589a0f9d2bd
Source dataset
uspto-grants-2014_07
Patent number
US08785429B2

Reaction notes

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