Ethyl Acetate → Ethyl [3-(bromomethyl)-1H-pyrazolo[3,4-b]pyridin-1-yl]acetate

HRID 930569Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 930569
C(OCC[N:7]1[C:11]2=[N:12][CH:13]=[CH:14][CH:15]=[C:10]2[C:9]([CH3:16])=[N:8]1)(=O)C.C1C(=O)N([Br:24])C(=O)C1.[CH3:25][CH2:26][O:27][C:28]([CH3:30])=[O:29]>C(Cl)(Cl)(Cl)Cl>[CH2:26]([O:27][C:28](=[O:29])[CH2:30][N:7]1[C:11]2=[N:12][CH:13]=[CH:14][CH:15]=[C:10]2[C:9]([CH2:16][Br:24])=[N:8]1)[CH3:25]

Komponenten

5

Edukt 3

HCID 8857Ethyl AcetateHCID 67184N-bromobutanimideHCID 67103879HCID 67103879, Verbindung

Produkt 1

HCID 57642772Ethyl [3-(bromomethyl)-1H-pyrazolo[3,4-b]pyridin-1-yl]acetate

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 5943Carbon TetrachlorideLösungsmittel

Versuchsvorschrift

A mixture of (3-methyl-pyrazolo[3,4-b]pyridine-1-yl)ethyl acetate (2.5 mmol, 1 eq.), NBS (3.0 mmol, 1.2 eq.), and benzoly peroxide (0.05 mmol, 0.02 eq.) in 10 mL of CCl4 was refluxed for 1.5 h. The resultant mixture was cooled to rt, and diluted with 500 mL of EtOAc. The resultant solution was then washed with 100 mL of sat. sodium bicarbonate aqueous solution, brine solution, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude residue was purified by silica gel chromatography (20% EtOAc in hexane to 35% EtOAc in hexane) to provide 450.2 mg of the desired product: HPLC retention time=2.50 minutes (Agilent Zorbax SB-C18, 2.1×50 mm, 5μ, 35° C.) using 1 ml/min flow rate, a 2.5 minute gradient of 0% to 100% B with a 1.1 minute wash at 100% B (A=0.1% formic acid/5% acetonitrile/94.9% water, B=0.1% formic acid/5% water/94.9% acetonitrile); MS (ES) M+H expect=298.0. found=298.3.

Aufarbeitung

  1. temperaturewas refluxed for 1.5 h
  2. washThe resultant solution was then washed with 100 mL of sat. sodium bicarbonate aqueous solution, brine solution
  3. dry with materialdried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe crude residue was purified by silica gel chromatography (20% EtOAc in hexane to 35% EtOAc in hexane)

Quellen und Nachweise

ORD-Eintrag
ord-41d9fd7bf61942b3bcf91cf092a73efd
Quelldatensatz
uspto-grants-2016_03
Patentnummer
US09296740B2

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