Water → Ethyl 4-oxo-3,4-dihydro-2H-pyran-2-carboxylate

HRID 1774167

反応式

HRID 1774167 の反応式
[CH3:1][O:2][CH:3]=[CH:4][C:5]([O:7][Si](C)(C)C)=[CH2:6].[C:12]([O:16][CH2:17][CH3:18])(=[O:15])C=O.O.C(O)(C(F)(F)F)=O>C1COCC1.C1(C)C=CC=CC=1>[CH2:17]([O:16][C:12]([CH:1]1[CH2:6][C:5](=[O:7])[CH:4]=[CH:3][O:2]1)=[O:15])[CH3:18]

参加物

7

反応物 4

HCID 962WaterHCID 6422Trifluoroacetic acidHCID 70211Ethyl oxoacetateHCID 1010511-Methoxy-3-trimethylsilyloxy-1,3-butadiene

生成物 1

HCID 22495097Ethyl 4-oxo-3,4-dihydro-2H-pyran-2-carboxylate収率 102.2%

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

A solution of ZnCl (0.63 g, 4.6 mmol) in anhydrous THF (15 mL) was added to a solution of 1-methoxy-3-(trimethylsilyloxy)-1,3-butadiene (7.94 g, 46.0 mmol) and ethyl glyoxalate (7.05 g, 69.0 mmol) in toluene (30 mL) at room temperature. After stirring for 30 minutes, water (30 mL) and TFA (2 mL) were added, and the mixture was stirred vigorously for 20 minutes. After concentration, the residue was partitioned between EtOAc (200 mL) and water (100 mL). The separated organic layer was washed with brine, dried over sodium sulfate, and concentrated to give 4-oxo-3,4-dihydro-2H-pyran-2-carboxylic acid ethyl ester (8.0 g, 100% yield) as an oil, which was carried to the next step without further purification. 1H NMR (500 MHz, CDCl3) δ 7.40 (d, J=1.0 Hz, 1H), 5.48 (d, J=6.5 Hz, 1H), 5.02 (t, J=8.0 Hz, 1H), 4.26 (q, J=7.0 Hz, 2H), 2.85 (d, J=8.0 Hz, 2H), 1.32 (t, J=7.5 Hz 3H); LCMS (ESI) m/z: 171 [M+H]+.

後処理

  1. stirringthe mixture was stirred vigorously for 20 minutes
  2. concentrationAfter concentration
  3. customthe residue was partitioned between EtOAc (200 mL) and water (100 mL)
  4. washThe separated organic layer was washed with brine
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated

出典と根拠

ORDレコード
ord-3673393cd909473d9398f7d252d597c1
出典データセット
uspto-grants-2016_02
特許番号
US09259470B2

関連ノート

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