Diazomethane → Ethyl 2-(1-(4-methoxybenzyl)-2-oxo-1,2-dihydroquinolin-6-yl)cyclopropanecarboxylate

HRID 1023168ノート

反応式

HRID 1023168 の反応式
[CH3:1][O:2][C:3]1[CH:27]=[CH:26][C:6]([CH2:7][N:8]2[C:17]3[C:12](=[CH:13][C:14](/[CH:18]=[CH:19]/[C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:15][CH:16]=3)[CH:11]=[CH:10][C:9]2=[O:25])=[CH:5][CH:4]=1.[N+](=[CH2:30])=[N-]>C(OCC)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:1][O:2][C:3]1[CH:27]=[CH:26][C:6]([CH2:7][N:8]2[C:17]3[C:12](=[CH:13][C:14]([CH:18]4[CH2:30][CH:19]4[C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:15][CH:16]=3)[CH:11]=[CH:10][C:9]2=[O:25])=[CH:5][CH:4]=1

参加物

5

反応物 2

HCID 9550DiazomethaneHCID 86680408(E)-ethyl 3-(1-(4-methoxybenzyl)-2-oxo-1,2-dihydroquinolin-6-yl)acrylate

生成物 1

HCID 86680409Ethyl 2-(1-(4-methoxybenzyl)-2-oxo-1,2-dihydroquinolin-6-yl)cyclopropanecarboxylate収率 57%

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 3283Diethyl Ether溶媒2 回

反応条件

温度
-10 °C

実験手順

To a stirred solution of (E)-ethyl 3-(1-(4-methoxybenzyl)-2-oxo-1,2-dihydroquinolin-6-yl)acrylate (1.2 g, 3.21 mmol) in diethyl ether (50 mL) was added palladium (II) acetate (0.031 g, 0.138 mmol). The reaction mixture was cooled to −10° C., and a cold solution of diazomethane (1.351 g, 32.1 mmol) in ether (generated from aqueous KOH (8 g, 143 mmol) and 1-methyl-1-nitrosourea (4 g, 38.8 mmol) at −15° C.) was added. The reaction mixture was stirred at room temperature for 12 h. The reaction mixture was filtered through celite, diluted with diethyl ether, and washed with water and saturated NaCl solution. The organic layer was dried over sodium sulfate, concentrated, and purified by flash chromatography on silica gel column using 15% ethyl acetate in hexane to give ethyl 2-(1-(4-methoxybenzyl)-2-oxo-1,2-dihydroquinolin-6-yl)cyclopropanecarboxylate as a yellow gum (510 mg, 57%). 1H NMR 400 MHz, CDCl3: δ 1.29 (t, J=4.80 Hz, 3H), 1.31 (d, J=4.80 Hz, 1H), 1.62 (d, J=4.80 Hz, 1H), 1.84-1.89 (m, 1H), 2.51-2.56 (m, 1H), 3.76 (d, J=2.80 Hz, 3H), 3.98 (q, J=174.00 Hz, 2H), 5.47 (s, 2H), 6.77-6.83 (m, 3H), 7.13-7.28 (m, 5H), 7.66 (d, J=9.60 Hz, 1H).

後処理

  1. filtrationThe reaction mixture was filtered through celite
  2. additiondiluted with diethyl ether
  3. washwashed with water and saturated NaCl solution
  4. dry with materialThe organic layer was dried over sodium sulfate
  5. concentrationconcentrated
  6. custompurified by flash chromatography on silica gel column

出典と根拠

ORDレコード
ord-5c95e3393ee44943b39a4abd2ddd8299
出典データセット
uspto-grants-2014_05
特許番号
US08722670B2

反応ノート

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