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

HRID 1427350Notes

Reaction equation

HRID 1427350 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-ad28a7d56ae048b9880ea4f09f5d0ab6
Source dataset
uspto-grants-2015_01
Patent number
US08933224B2

Reaction notes

Loading…