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

HRID 1502352ノート

反応式

HRID 1502352 の反応式
[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

参加物

4

反応物 2

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 176Acetic Acid溶媒

反応条件

温度
60 °C

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-b862ed3e55e84604b5e6a22148427850
出典データセット
uspto-grants-2015_12
特許番号
US09206175B2

反応ノート

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