Methanol → 2-(4-Fluoro-benzylidene)-3-methyl-succinic acid 1-methyl ester

HRID 1929565

反応式

HRID 1929565 の反応式
CO.[H-].[Na+].[F:5][C:6]1[CH:13]=[CH:12][C:9]([CH:10]=O)=[CH:8][CH:7]=1.[CH3:14][CH:15]([CH2:20][C:21]([O:23][CH3:24])=[O:22])[C:16]([O:18]C)=[O:17]>C1(C)C=CC=CC=1>[CH3:24][O:23][C:21](=[O:22])[C:20](=[CH:10][C:9]1[CH:12]=[CH:13][C:6]([F:5])=[CH:7][CH:8]=1)[CH:15]([CH3:14])[C:16]([OH:18])=[O:17]

参加物

6

反応物 4

HCID 887MethanolHCID 15350Butanedioic acid, 2-methyl-, 1,4-dimethyl esterHCID 24758Sodium hydrideHCID 680234-Fluorobenzaldehyde

生成物 1

HCID 667755872-(4-Fluoro-benzylidene)-3-methyl-succinic acid 1-methyl ester収率 33%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒2 回

実験手順

After the careful addition of absolute methanol (0.1 mL) to a suspension of sodium hydride (20 g, 0.5 mol, 60% in mineral oil) in anhydrous toluene (200 mL), a solution of 4-fluoro-benzaldehyde (31 g, 0.25 mol) and dimethyl 2-methyl-succinate (60 g, 0.38 mol) in anhydrous toluene (100 mL) was added at room temperature under a stream of nitrogen. The resulting mixture was stirred at room temperature for 30 minutes and then quenched by the slow addition of water (20 mL). The mixture was acidified to pH 3 by the addition of concentrated hydrochloric acid, and extracted with ethyl acetate (200 mL×3). The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by column chromatography (elution with 30% ethyl acetate in petroleum ether) to afford 2-(4-fluoro-benzylidene)-3-methyl-succinic acid 1-methyl ester (20 g, 33%) as a white solid. 1H NMR (400 MHz, acetone-d6) δ ppm 7.77 (s, 1H), 7.54 (d, J=8.8 Hz, 2H), 7.25 (d, J=8.8 Hz, 2H), 3.82 (q, 7.2 Hz, 1H), 1.40 (d, J=6.8 Hz, 3H).

後処理

  1. customquenched by the slow addition of water (20 mL)
  2. additionThe mixture was acidified to pH 3 by the addition of concentrated hydrochloric acid
  3. extractionextracted with ethyl acetate (200 mL×3)
  4. dry with materialThe combined organic layers were dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by column chromatography (elution with 30% ethyl acetate in petroleum ether)

出典と根拠

ORDレコード
ord-eb5a1e77562e43eda648886018130e20
出典データセット
uspto-grants-2012_05
特許番号
US08188090B2

関連ノート

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