Hydrochloric Acid → N-(3-formyl-4-methylpyridin-2-yl)-2,2-dimethylpropanamide

HRID 987901ノート

反応式

HRID 987901 の反応式
[CH3:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]([NH:8][C:9](=[O:14])[C:10]([CH3:13])([CH3:12])[CH3:11])[CH:3]=1.[Li]C(C)(C)C.CN([CH:23]=[O:24])C.Cl.C([O-])([O-])=O.[K+].[K+]>C(OCC)C>[CH:23]([C:3]1[C:4]([NH:8][C:9](=[O:14])[C:10]([CH3:11])([CH3:13])[CH3:12])=[N:5][CH:6]=[CH:7][C:2]=1[CH3:1])=[O:24]

参加物

7

反応物 5

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 11430Potassium CarbonateHCID 35314852,2-Dimethyl-N-(4-Methyl-2-pyridyl)propionamideHCID 178418306HCID 178418306、化合物

生成物 1

HCID 22987126N-(3-formyl-4-methylpyridin-2-yl)-2,2-dimethylpropanamide収率 59%

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒

反応条件

温度
-78 °C

実験手順

To a precooled (−78° C.) solution of 4-methyl-2-(pivaloylamino)pyridine (6.87 g, 36.0 mmol) in diethyl ether (100 mL, dried over molecular seives) was slowly added tert-BuLi (50.0 mL, 75.0 mmol). The resulting solution was stirred at −78° C. for 3.5 h prior to the addition of DMF (5.19 g, 71.0 mmol) and was stirred for additionally 30 min at −78° C. and then allowed to warm to rt, and poored into 2 M HCl (aqueous, 100 mL). After stirring this mixture for 15 min. the pH was adjusted to 7.0 by addition of K2CO3. The aqueous phase washed with diethyl ether (3×75 mL, dried over molecular seives), and the combined organic fractions was washed with brine (100 mL), dried (MgSO4) and evaporated in vacuo. The crude product was recrystallised from ethyl acetate/hexane to give the desired product (4.66 g, 59%) as a slightly tan crystals (mp 117-20° C.). 1H NMR(DMSO-d6): δ 11.19 (s br, 1H), 10.41 (s, 1H), 8.49 (d, 5.0 Hz, 1H), 6.92 (d, 5.0 Hz), 2.69 (s, 3H), 1.37 (s, 9H). 13C NMR (DMSO-d6): δ 192.02, 176.97, 154.15, 152.82, 152.69, 121.70, 116.09, 40.69, 27.46, 18.77. FAB+ MS (m/z): 221.1300 (M+H+, calc. for C12H16N2O2+H+ 221.1290).

後処理

  1. stirringwas stirred for additionally 30 min at −78° C.
  2. temperatureto warm to rt
  3. stirringAfter stirring this mixture for 15 min. the pH
  4. washThe aqueous phase washed with diethyl ether (3×75 mL, dried over molecular seives)
  5. washthe combined organic fractions was washed with brine (100 mL)
  6. dry with materialdried (MgSO4)
  7. customevaporated in vacuo
  8. customThe crude product was recrystallised from ethyl acetate/hexane

出典と根拠

ORDレコード
ord-2546935636d54aac91a0d8a490446b0e
出典データセット
uspto-grants-2003_10
特許番号
US06632919B1

反応ノート

読み込み中…