5-Bromo-4,6-dimethylpyridin-3-amine → 4-bromo-5-methyl-1H-pyrazolo[3,4-c]pyridine

HRID 1502352Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1502352
[Br:1][C:2]1[C:3]([CH3:10])=[C:4]([NH2:9])[CH:5]=[N:6][C:7]=1[CH3:8].[N:11]([O-])=O.[Na+]>C(O)(=O)C>[Br:1][C:2]1[C:7]([CH3:8])=[N:6][CH:5]=[C:4]2[NH:9][N:11]=[CH:10][C:3]=12

Komponenten

4

Edukt 2

HCID 70606665-Bromo-4,6-dimethylpyridin-3-amineHCID 23668193Sodium Nitrite

Produkt 1

HCID 679764014-bromo-5-methyl-1H-pyrazolo[3,4-c]pyridineAusbeute 53 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 176Acetic AcidLösungsmittel

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

To a solution of 5-bromo-4,6-dimethylpyridin-3-amine (1.00 g, 4.98 mmol) in acetic acid (12 mL) at ambient temperature was added sodium nitrite (364 mg, 5.28 mmol) and the mixture heated to 60° C. for 1.5 hr. The cooled reaction mixture was concentrated in vacuo, the residue partitioned between ethyl acetate and saturated aqueous sodium bicarbonate and the biphasic mixture filtered through a celite pad. The separated aqueous phase was extracted with ethyl acetate, and the combined organic phases washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by flash chromatography (silica, ISCO, 10-100% ethyl acetate in heptane) to afford the title compound as a pale brown solid (554 mg, 53%). 1H NMR (300 MHz, DMSO) δ 13.91 (s, 1H), 8.95 (s, 1H), 8.14 (s, 1H), 2.67 (s, 3H). LCMS: M+H+=212 & 214.

Aufarbeitung

  1. customThe cooled reaction mixture
  2. concentrationwas concentrated in vacuo
  3. customthe residue partitioned between ethyl acetate and saturated aqueous sodium bicarbonate
  4. filtrationthe biphasic mixture filtered through a celite pad
  5. extractionThe separated aqueous phase was extracted with ethyl acetate
  6. washthe combined organic phases washed with brine
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe residue was purified by flash chromatography (silica, ISCO, 10-100% ethyl acetate in heptane)

Quellen und Nachweise

ORD-Eintrag
ord-b862ed3e55e84604b5e6a22148427850
Quelldatensatz
uspto-grants-2015_12
Patentnummer
US09206175B2

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