Acetaldehyde → Methyl 2-ethylidenehexanoate

HRID 2119107ノート

反応式

HRID 2119107 の反応式
[CH3:1][O:2][C:3](=[O:17])[CH:4](P(OCC)(OCC)=O)[CH2:5][CH2:6][CH2:7][CH3:8].[H-].[Na+].[H][H].[CH:22](=O)[CH3:23]>O1CCCC1>[CH3:1][O:2][C:3](=[O:17])[C:4]([CH2:5][CH2:6][CH2:7][CH3:8])=[CH:22][CH3:23]

参加物

6

反応物 4

HCID 177AcetaldehydeHCID 24758Sodium hydrideHCID 136533912-(Diethylphosphono)hexanoic acid methyl esterHCID 178418361HCID 178418361、化合物

生成物 1

HCID 54326897Methyl 2-ethylidenehexanoate収率 25%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-30 °C

実験手順

To 2-(diethylphosphono)hexanoic acid methyl ester (53.2 g, 0.2M) in dry tetrahydrofuran (300 ml) was added sodium hydride (5.3 g, 0.22M) under an atmosphere of argon at 0° C. with continuous stirring. The reaction was allowed to warm to room temperature over 1 hour when the evolution of hydrogen had ceased. The reaction was then cooled to -30° C. and acetaldehyde (30 g, 0.66M) added dropwise to the continuously stirred solution over 10 minutes. The reaction was allowed to warm to 20° C. over 16 h and then concentrated in vacuo to a gum which was dissolved in ether. The etherial solution was washed with aqueous saturated sodium hydrogen carbonate, dried over sodium sulphate and concentrated in vacuo. Vacuum distillation of the resulting gum afforded E and Z 2-(butyl)-but-2-enoic acid methyl ester (7.8 g) B.p. 50°-60° C. at 0.8 mm Hg (Found: C, 65.0; H, 10.1 C9H16O 2 +0.5H2O requires: C, 65.4; H, 10.4%); δ(CDCl3) 0.84 (3H, t, J=8 Hz, CH3CH2); 1.34 (4H, m, 2×CH2); 1.8 and 1.96 (3H each d, each J=7 Hz, CH3CH); 2.32 (2H, m, CH2 --C); 3.72 and 3.74 (3H, each s, CH3O); 5.96 and 6.84 (1H, each q, each J=7 Hz, CH).

後処理

  1. temperatureto warm to 20° C. over 16 h
  2. concentrationconcentrated in vacuo to a gum which
  3. dissolutionwas dissolved in ether
  4. washThe etherial solution was washed with aqueous saturated sodium hydrogen carbonate
  5. dry with materialdried over sodium sulphate
  6. concentrationconcentrated in vacuo
  7. distillationVacuum distillation of the resulting gum

出典と根拠

ORDレコード
ord-c9f1e99bc96a435980d14db4fa42f83a
出典データセット
uspto-grants-1987_07
特許番号
US04681966

反応ノート

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