Acetic Acid → HCID 178418886、化合物

HRID 7777

反応式

HRID 7777 の反応式
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([NH:7][C:8](=[O:13])[C:9]([CH3:12])([CH3:11])[CH3:10])[CH:2]=1.C([Li])CCC.B(OC)(OC)[O:20]C.CC(O)=O.OO>C1COCC1.O>[OH:20][C:4]1[CH:5]=[CH:6][N:1]=[CH:2][C:3]=1[NH:7][C:8](=[O:13])[C:9]([CH3:10])([CH3:12])[CH3:11]

参加物

8

反応物 5

HCID 176Acetic AcidHCID 784Hydrogen PeroxideHCID 8470Trimethyl borateHCID 46550442,2-dimethyl-N-(pyridin-3-yl)propanamideHCID 178418339Butyllithium

生成物 1

HCID 178418886HCID 178418886、化合物

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

To a stirred solution of N-(pyridin-3-yl)-2,2-dimethylpropanamide (8.90 g, 50.0 mmol) in THF (200 mL) at −78° C. was added n-Butyllithium (50 mL, 125 mmol) dropwise over 30 min. After addition, the reaction mixture was warmed to 0° C. and stirred an additional 3 h. The reaction was then cooled back to −78° C. and trimethyl borate (14.2 mL, 125 mmol) in THF was added dropwise over 15 min. After addition, the reaction mixture was warmed to 0° C. and stirred an additional 2 h. Glacial AcOH (10.8 mL, 188 mmol) was added to the reaction, followed by dropwise addition of 30% H2O2 (14.3 mL, 138 mmol). The reaction mixture was warmed to rt and stirred overnight. The mixture was diluted with H2O and concentrated in vacuo. The residue was extracted three times with 10% iPrOH/CHCl3, the combined extracts treated with activated charcoal, and the slurry filtered through Celite. The organic layer was washed three times with H2O, once with brine, dried over MgSO4, filtered, and concentrated in vacuo. The residue was purified by column chromatography (3–10% MeOH/CHCl3) to give N-(4-hydroxypyridin-3-yl)-2,2-dimethylpropanamide as a light yellow solid. 1H NMR (DMSO-d6, 300 MHz) δ 11.58 (br s, 1H), 8.76 (br s, 1H), 8.67 (s, 1H), 7.68 (d, 1H), 6.26 (d, 1H), 1.22 (s, 9H).

後処理

  1. additionAfter addition
  2. temperatureThe reaction was then cooled back to −78° C.
  3. additionAfter addition
  4. temperaturethe reaction mixture was warmed to 0° C.
  5. stirringstirred an additional 2 h
  6. temperatureThe reaction mixture was warmed to rt
  7. stirringstirred overnight
  8. concentrationconcentrated in vacuo
  9. extractionThe residue was extracted three times with 10% iPrOH/CHCl3
  10. additionthe combined extracts treated with activated charcoal
  11. filtrationthe slurry filtered through Celite
  12. washThe organic layer was washed three times with H2O
  13. dry with materialonce with brine, dried over MgSO4
  14. filtrationfiltered
  15. concentrationconcentrated in vacuo
  16. customThe residue was purified by column chromatography (3–10% MeOH/CHCl3)

出典と根拠

ORDレコード
ord-41a9e16aa1e4461f9bed0abe910ce2eb
出典データセット
uspto-grants-2006_08
特許番号
US07087601B2

関連ノート

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