Sodium hydride → trans-Methyl 2-(3-chloro-2-methylphenyl)cyclopropanecarboxylate

HRID 2175312ノート

反応式

HRID 2175312 の反応式
[I-].[CH3:2][S+](C)(C)=O.[H-].[Na+].[Cl:9][C:10]1[C:11]([CH3:22])=[C:12](/[CH:16]=[CH:17]/[C:18]([O:20][CH3:21])=[O:19])[CH:13]=[CH:14][CH:15]=1>CS(C)=O>[Cl:9][C:10]1[C:11]([CH3:22])=[C:12]([C@@H:16]2[CH2:2][C@H:17]2[C:18]([O:20][CH3:21])=[O:19])[CH:13]=[CH:14][CH:15]=1

参加物

5

反応物 3

HCID 24758Sodium hydrideHCID 74498Sulfoxonium, trimethyl-, iodide (1:1)HCID 86712608(E)-Methyl 3-(3-chloro-2-methylphenyl)acrylate

生成物 1

HCID 70981958trans-Methyl 2-(3-chloro-2-methylphenyl)cyclopropanecarboxylate収率 39.4%

試薬・触媒・溶媒 1

HCID 679Dimethyl Sulfoxide溶媒2 回

実験手順

To a solution of trimethylsulfoxonium iodide (0.157 g, 0.712 mmol) in 1 mL DMSO was added NaH (60% in mineral oil) (0.032 g, 0.807 mmol) portion-wise. The mixture was stirred at room temperature for 30 min, and then a solution (E)-methyl 3-(3-chloro-2-methylphenyl)acrylate (0.1 g, 0.475 mmol) in 1 mL DMSO was added in one portion. The reaction was stirred at room temperature for 16 h. The mixture was partitioned between EtOAc and water. The organic layer was washed with water and brine, dried (MgSO4) and concentrated. The crude material was purified by flash chromatography (0-50% ethyl acetate:hexanes) to afford the title compound (0.042 g, 39% yield) as a clear colorless oil. 1H NMR (500 MHz, CDCl3) δ 7.29-7.24 (d, J=7.8 Hz, 1H), 7.06 (t, J=7.8 Hz, 1H), 6.95 (d, J=7.7 Hz, 1H), 3.79-3.75 (m, 3H), 2.55 (ddd, J=9.1, 6.7, 4.5 Hz, 1H), 2.45 (s, 3H), 1.81 (dt, J=8.4, 4.9 Hz, 1H), 1.64-1.57 (m, 1H), 1.30 (ddd, J=8.4, 6.7, 4.4 Hz, 1H).

後処理

  1. stirringThe reaction was stirred at room temperature for 16 h
  2. customThe mixture was partitioned between EtOAc and water
  3. washThe organic layer was washed with water and brine
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. customThe crude material was purified by flash chromatography (0-50% ethyl acetate:hexanes)

出典と根拠

ORDレコード
ord-37e46d9f8c874032a3f8ad46b99e1574
出典データセット
uspto-grants-2015_06
特許番号
US09062028B2

反応ノート

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