Azobisisobutyronitrile → tert-Butyl 5-bromo-3-(bromomethyl)-1H-pyrazolo[3,4-b]pyridine-1-carboxylate

HRID 2043655Notes

Reaction equation

[Br:1][C:2]1[CH:3]=[C:4]2[C:10]([CH3:11])=[N:9][N:8]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[C:5]2=[N:6][CH:7]=1.[Br:19]N1C(=O)CCC1=O.N(C(C)(C)C#N)=NC(C)(C)C#N>C(Cl)(Cl)(Cl)Cl>[Br:1][C:2]1[CH:3]=[C:4]2[C:10]([CH2:11][Br:19])=[N:9][N:8]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[C:5]2=[N:6][CH:7]=1

Participants

Conditions

Temperature: 80 °C

Procedure

A mixture of tert-butyl 5-bromo-3-methyl-1H-pyrazolo[3,4-b]pyridine-1-carboxylate x154 (10.8 mmol, 1 eq, 3.37 g), N-bromosuccinimide (1.92 g, 1 eq, 10.8 mmol) and azo-bisiso-butyronitrile (AIBN) (10.8 mmol, 1 eq, 1.77 g) in CCl4 (50 ml) is heated for 2 hours at 80° C. The solvent is removed under reduce pressure, water is added and the resulting mixture is extracted with dichloromethane. The combined organic phases are dried over MgSO4, filtered and volatiles removed under reduced pressure. The product is purified by chromatography on silicagel (hexane/AcOEt 8/2) and recristallized in AcOEt to afford 0.28 g of pure tert-butyl 5-bromo-3-(bromomethyl)-1H-pyrazolo[3,4-b]pyridine-1-carboxylate x155.

Workup

customThe solvent is removed
additionis added
extractionthe resulting mixture is extracted with dichloromethane
dry with materialThe combined organic phases are dried over MgSO4
filtrationfiltered
customvolatiles removed under reduced pressure
customThe product is purified by chromatography on silicagel (hexane/AcOEt 8/2)

Sources & evidence

ORD record: ord-05e7e3847bac4e78bb0c8b5319b84c2f
Source dataset: uspto-grants-2013_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08586623B2

Reaction notes

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