4-Toluenesulfonyl chloride → HCID 67088968, compound

HRID 1943865Notes

Reaction equation

HRID 1943865 reaction equation
[H-].[Na+].[Br:3][C:4]1[C:12]2[C:7](=[N:8][CH:9]=[CH:10][CH:11]=2)[NH:6][N:5]=1.[CH3:13][C:14]1[CH:19]=[CH:18][C:17]([S:20](Cl)(=[O:22])=[O:21])=[CH:16][CH:15]=1>C1COCC1>[Br:3][C:4]1[C:12]2[C:7](=[N:8][CH:9]=[CH:10][CH:11]=2)[N:6]([S:20]([C:17]2[CH:18]=[CH:19][C:14]([CH3:13])=[CH:15][CH:16]=2)(=[O:22])=[O:21])[N:5]=1

Participants

5

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 24758Sodium hydrideHCID 178419491HCID 178419491, compound

Product 1

HCID 67088968HCID 67088968, compoundYield 70%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

NaH (1.8 g, 44.9 mmol, 60% suspension in mineral oil) was added portionwise to a cold (0° C.) solution of 3-bromo-1H-pyrazolo[3,4-b]pyridine (3.7 g, 18.7 mmol) in dry THF (50 mL). After 10 minutes, 4-methylbenzene-1-sulfonyl chloride (5.3 g, 28.0 mmol) was added. The cold bath was removed, and the reaction mixture was left at room temperature overnight. The reaction mixture was placed in an ice bath, diluted with ethyl acetate (200 mL) and carefully quenched with water (20 mL). The aqueous layer was extracted with ethyl acetate (3×50 mL). The combined organic layers were dried, filtered and concentrated. The crude product was purified by column chromatography, eluting with hexanes/ethyl acetate (7:3) to give 3-bromo-1-tosyl-1H-pyrazolo[3,4-b]pyridine (4.6 g, 70%) as a solid.

Workup

  1. customThe cold bath was removed
  2. waitthe reaction mixture was left at room temperature overnight
  3. customThe reaction mixture was placed in an ice bath
  4. additiondiluted with ethyl acetate (200 mL)
  5. customcarefully quenched with water (20 mL)
  6. extractionThe aqueous layer was extracted with ethyl acetate (3×50 mL)
  7. customThe combined organic layers were dried
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe crude product was purified by column chromatography
  11. washeluting with hexanes/ethyl acetate (7:3)

Sources & evidence

ORD record
ord-4359f6cc11f14c19b19c3f70b4b06216
Source dataset
uspto-grants-2013_03
Patent number
US08394795B2

Reaction notes

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