Toluene → Ethyl 3-(6-methylpyridin-2-yl)-3-oxopropanoate

HRID 751254

反応式

HRID 751254 の反応式
[O-]CC.[Na+].C1(C)C=CC=CC=1.[C:12]([O:15][CH2:16][CH3:17])(=[O:14])[CH3:13].C[O:19][C:20]([C:22]1[CH:27]=[CH:26][CH:25]=[C:24]([CH3:28])[N:23]=1)=O>C(O)(=O)C>[CH2:16]([O:15][C:12](=[O:14])[CH2:13][C:20]([C:22]1[CH:27]=[CH:26][CH:25]=[C:24]([CH3:28])[N:23]=1)=[O:19])[CH3:17]

参加物

6

反応物 4

HCID 1140TolueneHCID 8857Ethyl AcetateHCID 73022Methyl 6-methylpyridine-2-carboxylateHCID 2723922Sodium ethoxide

生成物 1

HCID 59710028Ethyl 3-(6-methylpyridin-2-yl)-3-oxopropanoate収率 112.6%

試薬・触媒・溶媒 1

HCID 176Acetic Acid溶媒

反応条件

温度
92 °C

実験手順

Stir a mixture of sodium ethoxide (90 g, 1.32 mol, 2 eq), toluene (0.5 L, 5 vol), and ethyl acetate (0.2 L, 1.98 mol, 3 eq) in a 2 L flask equipped with reflux condenser, mechanical stirrer, and nitrogen inlet. After 1 h, add 6-methyl-pyridine-2-carboxylic acid methyl ester (Cheung, Y, Tetrahedron Lett. 1979, 40, 3809-10; 100 g, 0.66 mol). Heat the mixture at reflux (92° C.) for 20 h. Cool the mixture to room temperature and acidify with glacial acetic acid to pH 6. Wash the resulting gel with water (0.5 L). Separate the layers and extract the aqueous layer with toluene (1×0.5 L) Dry the combined organic layers (sodium sulfate), filter, and concentrate in vacuo to yield the subtitled product (154 g) as a dark oil in 86% purity by HPLC analysis. MS ES+ m/e 208 (M+1).

後処理

  1. customequipped
  2. temperaturewith reflux condenser, mechanical stirrer, and nitrogen inlet
  3. temperatureHeat the mixture
  4. temperatureCool the mixture to room temperature
  5. washWash the resulting gel with water (0.5 L)
  6. customSeparate the layers
  7. extractionextract the aqueous layer with toluene (1×0.5 L)
  8. dry with materialDry the combined organic layers (sodium sulfate)
  9. filtrationfilter
  10. concentrationconcentrate in vacuo

出典と根拠

ORDレコード
ord-9e7952648ad74ddc88db4efa9ed90fb9
出典データセット
uspto-grants-2008_07
特許番号
US07405299B2

関連ノート

読み込み中…