Methyl acetoacetate → Methyl 3-oxo-5-(phenylsulfanyl)pentanoate

HRID 366957ノート

反応式

HRID 366957 の反応式
[H-].[Na+].[CH3:3][O:4][C:5](=[O:10])[CH2:6][C:7]([CH3:9])=[O:8].[Li]CCCC.Cl[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[S:23][CH3:24]>C1COCC1.CN(P(N(C)C)(N(C)C)=O)C.C1COCC1>[C:18]1([S:23][CH2:24][CH2:9][C:7](=[O:8])[CH2:6][C:5]([O:4][CH3:3])=[O:10])[CH:19]=[CH:20][CH:21]=[CH:22][CH:17]=1

参加物

7

反応物 4

HCID 7757Methyl acetoacetateHCID 24758Sodium hydrideHCID 27373632-Chlorophenyl methyl sulfideHCID 178418339Butyllithium

生成物 1

HCID 12764772Methyl 3-oxo-5-(phenylsulfanyl)pentanoate収率 22.7%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 86583969tetrahydrofuran HMPA溶媒

反応条件

温度
0 °C

実験手順

To a suspension of NaH (60%) (815 mg, 20.39 mmol) in THF-HMPA (20 ml, 5 ml) was added methylacetoacetate (2.0 g, 18.5 mmol) in THF (5 ml) at 0° C. The mixture was stirred for 10 min. at 0° C. under nitrogen atmosphere. BuLi (12.3 ml, 20.39 mmol) was dropwise added and the red mixture was stirred for 15 min. at 0° C. Then a solution of chlorothioanisole (2.7 ml, 20.39 mmol) in THF (5 ml) was added to the mixture at 0° C. The mixture was stirred for 1 h at -5° C. The mixture was quenched with H2O, then extracted with AcOEt (100 ml×2). AcOEt layer was washed with H2O (10 ml×2) and brine (10 ml), then dried over MgSO4 and evaporated. The residue was purified by a silica gel column chromatography (150 g, hexane :AcOEt=6:1) to give a colorless oil (1.0 g, 22.7%).

後処理

  1. stirringthe red mixture was stirred for 15 min. at 0° C
  2. stirringThe mixture was stirred for 1 h at -5° C
  3. customThe mixture was quenched with H2O
  4. extractionextracted with AcOEt (100 ml×2)
  5. washAcOEt layer was washed with H2O (10 ml×2) and brine (10 ml)
  6. dry with materialdried over MgSO4
  7. customevaporated
  8. customThe residue was purified by a silica gel column chromatography (150 g, hexane :AcOEt=6:1)

出典と根拠

ORDレコード
ord-0662be53814b40eda18d24f9bf08d60d
出典データセット
uspto-grants-2000_10
特許番号
US06131226

反応ノート

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