Acetic Acid → Ethyl 3-(4-methyl-1,3-thiazol-2-yl)-3-oxopropanoate

HRID 254171ノート

反応式

HRID 254171 の反応式
[H-].[Na+].[C:3](=[O:10])([O:7][CH2:8][CH3:9])OCC.[C:11]([C:14]1[S:15][CH:16]=[C:17]([CH3:19])[N:18]=1)(=[O:13])[CH3:12].CC(O)=O>CCCC(C)C.C1(C)C=CC=CC=1.O>[CH3:19][C:17]1[N:18]=[C:14]([C:11](=[O:13])[CH2:12][C:3]([O:7][CH2:8][CH3:9])=[O:10])[S:15][CH:16]=1

参加物

8

反応物 4

HCID 176Acetic AcidHCID 7766Diethyl CarbonateHCID 24758Sodium hydrideHCID 53247972-Acetyl-4-methylthiazole

生成物 1

HCID 66846879Ethyl 3-(4-methyl-1,3-thiazol-2-yl)-3-oxopropanoate収率 74%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 1140Toluene溶媒2 回HCID 78922-Methylpentane溶媒

反応条件

温度
80 °C

実験手順

NaH (60% in oil, 1.34 g, 33.5 mmol) was washed with isohexane (2×14 mL), suspended in toluene (25 mL), treated with diethyl carbonate (4.7 mL, 4.6 g, 38.8 mmol), heated to 80° C., treated dropwise over 20 min with a solution of 2-acetyl-4-methylthiazole (2.72 g, 19.2 mmol) in toluene (5 mL) and stirred at 80° C. for 2 h. The mixture was cooled to 0° C., treated dropwise with HOAc (4.65 mL, 4.9 g, 81 mmol) followed by ice (25 g) and water (50 mL) and stirred for 30 min. The aqueous phase was extracted with toluene (50 mL), the combined organic phase was washed with water (50 mL), dried (MgSO4) and concentrated in vacuo to give the crude product (3 g, 74%) as a dark red oil, used in the next step without further purification; NMR δH (400 MHz, CDCl3) 1.26 (3H, t, J 7.2 Hz), 2.92 (3H, s), 4.14 (2H, s), 4.18-4.25 (2H, m) and 7.31 (1H, s).

後処理

  1. temperatureThe mixture was cooled to 0° C.
  2. stirringstirred for 30 min
  3. extractionThe aqueous phase was extracted with toluene (50 mL)
  4. washthe combined organic phase was washed with water (50 mL)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-f39492cb4dc843edad1063bf49cffa23
出典データセット
uspto-grants-2011_01
特許番号
US07875600B2

反応ノート

読み込み中…