Diethyl Oxalate → Ethyl (2-fluorophenyl)pyruvate

HRID 1508419ノート

反応式

HRID 1508419 の反応式
[F:1][C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[CH2:4]Cl.[C:10](OCC)(=[O:16])[C:11]([O:13][CH2:14][CH3:15])=[O:12]>C(OCC)C>[F:1][C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[CH2:4][C:10](=[O:16])[C:11]([O:13][CH2:14][CH3:15])=[O:12]

参加物

4

反応物 2

HCID 7268Diethyl OxalateHCID 9580Benzene, 1-(chloromethyl)-2-fluoro-

生成物 1

HCID 18370709Ethyl (2-fluorophenyl)pyruvate収率 70%

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒3 回

実験手順

To a suspension of Mg turnings (0.231 g, 9.51 mmol) in diethyl ether (1.5 mL) was added a solution of 2-fluorobenzyl chloride (1.25 g, 8.65 mmol) in diethyl ether (9 mL) dropwise to the refluxing reaction mixture. The mixture was stirred for 10 min, cooled to room temperature and added dropwise to a solution of diethyl oxalate (2.53 g, 17.29 mmol) in diethyl ether (17 mL) at 0° C. The reaction mixture was stirred at room temperature for 2 hours, quenched with 1M aqueous hydrochloric acid and extracted with diethyl ether. The combined extracts were washed with brine, dried over magnesium sulfate, and concentrated under reduced pressure. The excess of diethyl oxalate was removed by bulb to bulb distillation at room temperature and the residue was purified by flash chromatography (SiO2, 15-20% ethyl acetate in petroleum ether) to give the resulting compound B4 as colorless oil in 70% yield which was used instantly in next step.

後処理

  1. customdropwise to the refluxing reaction mixture
  2. stirringThe reaction mixture was stirred at room temperature for 2 hours
  3. customquenched with 1M aqueous hydrochloric acid
  4. extractionextracted with diethyl ether
  5. washThe combined extracts were washed with brine
  6. dry with materialdried over magnesium sulfate
  7. concentrationconcentrated under reduced pressure
  8. customThe excess of diethyl oxalate was removed by bulb to bulb distillation at room temperature
  9. customthe residue was purified by flash chromatography (SiO2, 15-20% ethyl acetate in petroleum ether)

出典と根拠

ORDレコード
ord-be14719dacbf498eb6220de500d801b4
出典データセット
uspto-grants-2015_12
特許番号
US09221860B2

反応ノート

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