Sodium hydride → 4-Bromo-1-methyl-1H-pyrazolo(3,4-c)pyridine

HRID 931340Notes

Reaction equation

HRID 931340 reaction equation
[H-].[Na+].[Br:3][C:4]1[CH:5]=[N:6][CH:7]=[C:8](Br)[C:9]=1[CH:10]=[N:11][NH:12][CH3:13]>O1CCCC1>[Br:3][C:4]1[CH:5]=[N:6][CH:7]=[C:8]2[N:12]([CH3:13])[N:11]=[CH:10][C:9]=12

Participants

4

Reactant 2

HCID 24758Sodium hydride2×HCID 76624368HCID 76624368, compound

Product 1

HCID 576069364-Bromo-1-methyl-1H-pyrazolo(3,4-c)pyridine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Sodium hydride (60% in mineral oil, 0.524 g, 13.1 mmol) was added to a solution of C7 (3.20 g, 10.9 mmol) in tetrahydrofuran (20 mL), and the reaction mixture was heated at reflux for 1.5 hours, then allowed to sit at room temperature for 90 hours. Additional sodium hydride (1 equivalent) was added, and the reaction mixture was heated at reflux for 3 hours. After cooling to room temperature, the mixture was quenched with water, diluted with saturated aqueous sodium chloride solution, and extracted with ethyl acetate. The combined organic layers were dried over magnesium sulfate, filtered, and concentrated in vacuo. Purification via silica gel chromatography (Gradient: 0% to 100% ethyl acetate in heptane) afforded the product as a solid. Yield: 1.51 g, 7.12 mmol, 65%. 1H NMR (400 MHz, CDCl3) δ 8.87 (s, 1H), 8.38 (s, 1H), 8.03 (s, 1H), 4.19 (s, 3H).

Workup

  1. temperaturethe reaction mixture was heated
  2. temperatureat reflux for 1.5 hours
  3. temperaturethe reaction mixture was heated
  4. temperatureat reflux for 3 hours
  5. customthe mixture was quenched with water
  6. additiondiluted with saturated aqueous sodium chloride solution
  7. extractionextracted with ethyl acetate
  8. dry with materialThe combined organic layers were dried over magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customPurification via silica gel chromatography (Gradient: 0% to 100% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-43a33cd6905f4943a05e478a0c6069a4
Source dataset
uspto-grants-2016_03
Patent number
US09296761B2

Reaction notes

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