Methyl 3-formylbenzoate → Methyl 3-(4-chloromethyl-5-methyl-1,3-oxazol-2-yl)benzoate

HRID 2221563ノート

反応式

HRID 2221563 の反応式
[CH:1]([C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][CH:12]=1)[C:6]([O:8][CH3:9])=[O:7])=[O:2].[CH3:13][C:14](=[N:18]O)[C:15](=O)[CH3:16].[ClH:20].C(OCC)(=O)C>>[Cl:20][CH2:13][C:14]1[N:18]=[C:1]([C:3]2[CH:4]=[C:5]([CH:10]=[CH:11][CH:12]=2)[C:6]([O:8][CH3:9])=[O:7])[O:2][C:15]=1[CH3:16]

参加物

4

反応物 3

HCID 639145Methyl 3-formylbenzoateHCID 63989692-Oxime 2,3-butanedioneHCID 21866389Hydrogen chloride-ethyl acetate

生成物 1

HCID 23076520Methyl 3-(4-chloromethyl-5-methyl-1,3-oxazol-2-yl)benzoate収率 55%

実験手順

A mixture of methyl 3-formylbenzoate (11.10 g), 2,3-butanedione-2-oxime (6.84 g) and 4N hydrogenchloride-ethyl acetate solution (100 mL) was stirred at room temperature for 4 days. The reaction mixture was concentrated, and the obtained crystals were washed with diethyl ether. Tetrahydrofuran (150 mL) was added to the crystals and thionyl chloride (12.06 g) was further added. The mixture was heated under reflux for 3 hrs. After concentration of the reaction mixture, saturated aqueous sodium hydrogen carbonate was added to the residue, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give methyl 3-(4-chloromethyl-5-methyl-1,3-oxazol-2-yl)benzoate as colorless crystals (9.88 g, 55%) from a fraction eluted with ethyl acetate-hexane (1:4, v/v). Recrystallization from ethyl acetate-hexane gave colorless prism crystals. melting point: 119-120° C.

後処理

  1. concentrationThe reaction mixture was concentrated
  2. washthe obtained crystals were washed with diethyl ether
  3. additionTetrahydrofuran (150 mL) was added to the crystals and thionyl chloride (12.06 g)
  4. additionwas further added
  5. temperatureThe mixture was heated
  6. temperatureunder reflux for 3 hrs
  7. additionAfter concentration of the reaction mixture, saturated aqueous sodium hydrogen carbonate was added to the residue
  8. extractionthe mixture was extracted with ethyl acetate
  9. washThe ethyl acetate layer was washed with saturated brine
  10. dry with materialdried over anhydrous magnesium sulfate
  11. concentrationconcentrated

出典と根拠

ORDレコード
ord-cb65367377314aaba27234903a03de9a
出典データセット
uspto-grants-2008_05
特許番号
US07368578B2

反応ノート

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