Benzoyl Peroxide → tert-butyl 3-(bromomethyl)-6-fluoro-1H-pyrazolo[3,4-b]pyridine-1-carboxylate

HRID 1157411Notes

Reaction equation

HRID 1157411 reaction equation
[F:1][C:2]1[N:7]=[C:6]2[N:8]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[N:9]=[C:10]([CH3:11])[C:5]2=[CH:4][CH:3]=1.C1C(=O)N([Br:26])C(=O)C1.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C(Cl)(Cl)(Cl)Cl>[Br:26][CH2:11][C:10]1[C:5]2[C:6](=[N:7][C:2]([F:1])=[CH:3][CH:4]=2)[N:8]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[N:9]=1

Participants

5

Reactant 3

HCID 7187Benzoyl PeroxideHCID 67184N-bromobutanimideHCID 251322461-Boc-3-methyl-6-fluoro-1H-pyrazolo[3,4-B]pyridine

Product 1

HCID 25132591tert-butyl 3-(bromomethyl)-6-fluoro-1H-pyrazolo[3,4-b]pyridine-1-carboxylate

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

A stirring solution of 8.88 g (35.2 mmol) of 37-4, 6.88 g (38.7 mmol) of NBS and 851 mg (3.52 mmol) of benzoyl peroxide in 250 mL of CCl4 was heated to reflux for 6 hours. The reaction was stopped after a 66% conversion of starting material as determined by LC/MS. The reaction mixture was cooled to room temperature, filtered through a pad of Celite to remove precipitated succinimide, and the filtrate concentrated in vacuo. The crude residue was purified by silica gel chromatography (0-70% ethyl acetate/hexanes) to afford the title product as a solid. 1H NMR (CDCl3): 1.75 (s, 9H), 4.75 (s, 2H), 7.00 (d, 1H), 8.30 (t, 1H).

Workup

  1. temperatureto reflux for 6 hours
  2. filtrationfiltered through a pad of Celite
  3. customto remove
  4. customprecipitated succinimide
  5. concentrationthe filtrate concentrated in vacuo
  6. customThe crude residue was purified by silica gel chromatography (0-70% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-22b73d4888844f029f33a815440409e4
Source dataset
uspto-grants-2010_10
Patent number
US07807684B2

Reaction notes

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