Methyl iodide → N-(6-ethyl-3-methyl-pyridin-2-yl)-2,2-dimethyl-propionamide

HRID 900962ノート

反応式

HRID 900962 の反応式
[CH2:1]([C:3]1[N:8]=[C:7]([NH:9][C:10](=[O:15])[C:11]([CH3:14])([CH3:13])[CH3:12])[CH:6]=[CH:5][CH:4]=1)[CH3:2].[C:16]([Li])(C)(C)C.CI>C(OCC)C.O>[CH2:1]([C:3]1[N:8]=[C:7]([NH:9][C:10](=[O:15])[C:11]([CH3:14])([CH3:13])[CH3:12])[C:6]([CH3:16])=[CH:5][CH:4]=1)[CH3:2]

参加物

6

反応物 3

HCID 6328Methyl iodideHCID 45094816N-(6-ethyl-pyridin-2-yl)-2,2-dimethyl-propionamideHCID 178418306HCID 178418306、化合物

生成物 1

HCID 45095400N-(6-ethyl-3-methyl-pyridin-2-yl)-2,2-dimethyl-propionamide収率 69%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 3283Diethyl Ether溶媒2 回

反応条件

温度
-20 °C

実験手順

A solution of N-(6-ethyl-pyridin-2-yl)-2,2-dimethyl-propionamide (24.0 g, 0.116 mol) in diethyl ether (600 mL, 0.2 M) is cooled to −78° C. and treated with tert-butyllithium (144 mL 1.7 M in pentane). After the addition is complete the solution is warmed to −20° C. for 2 h, treated with a solution of methyliodide (23 mL, 0.372 mol) in diethylether (10 mL) and warmed to room temperature. After stirring overnight the reaction is diluted with water, extracted with diethyl ether and dried over MgSO4. The resulting solution is filtered through a short pad of silica gel, concentrated and recrystallized from heptane to give N-(6-ethyl-3-methyl-pyridin-2-yl)-2,2-dimethyl-propionamide (17.6 g, 69%) as an off-white crystalline solid. mp 72-75° C.; Rf 0.43 (50% ethyl acetate in hexanes); 1H NMR (DMSO-d6, 300 MHz) δ 9.48 (s, 1H), 7.53 (d, J=7.8 Hz, 1 H), 7.48 (d, J=7.5 Hz, 1 H), 2.65 (q, J=7.5 Hz, 2 H), 2.02 (s, 3 H), 1.20 (s, 9 H), 1.18 (t, J=7.5 Hz, 3 H); LRMS calcd for C13H20N2O: 220.3; found 220.0 (M)+. Anal. Calcd for C13H20N2O : C, 70.87; H, 9.15; N, 12.72. Found C, 70.70; H, 9.18; N, 12.74.

後処理

  1. additionAfter the addition
  2. temperaturewarmed to room temperature
  3. extractionextracted with diethyl ether
  4. dry with materialdried over MgSO4
  5. filtrationThe resulting solution is filtered through a short pad of silica gel
  6. concentrationconcentrated
  7. customrecrystallized from heptane

出典と根拠

ORDレコード
ord-73aea3d4fa2c457dbd6fe1958143f382
出典データセット
uspto-grants-2008_04
特許番号
US07361671B2

反応ノート

読み込み中…