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

HRID 238601

반응식

HRID 238601 반응식
CO.[H-].[Na+].[F:5][C:6]1[CH:13]=[CH:12][C:9]([CH:10]=O)=[CH:8][CH:7]=1.C[O:15][C:16](=[O:24])[CH:17]([CH3:23])[CH2:18][C:19]([O:21][CH3:22])=[O:20]>C1(C)C=CC=CC=1>[CH3:22][O:21][C:19](=[O:20])[C:18](=[CH:10][C:9]1[CH:12]=[CH:13][C:6]([F:5])=[CH:7][CH:8]=1)[CH:17]([CH3:23])[C:16]([OH:24])=[O:15]

참가 물질

6

반응물 4

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

생성물 1

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

시약·촉매·용매 1

HCID 1140Toluene용매2회

실험 절차

After careful addition of absolute methanol (0.1 mL) to a suspension of sodium hydride (60% in mineral oil, 20 g, 0.5 mol) in anhydrous toluene (200 mL), a solution of 4-fluoro-benzaldehyde (31 g, 0.25 mol) and 2-methyl-succinic acid dimethyl ester (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 by the addition of concentrated hydrochloric acid, and extracted with ethyl acetate (200 mL×3). The combined organic layers were dried over sodium sulfate, 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).

후처리

  1. customquenched by the slow addition of water (20 mL)
  2. additionThe mixture was acidified 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. concentrationconcentrated in vacuo
  6. customThe residue was purified by column chromatography (elution with 30% ethyl acetate in petroleum ether)

출처 및 근거

ORD 기록
ord-cc74954780564f1fbeb84ad8f3fdcd1d
출처 데이터셋
uspto-grants-2014_02
특허 번호
US08642629B2

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