Diethyl Malonate → Diethyl 2-pent-4-enylpropanedioate

HRID 131117

反応式

HRID 131117 の反応式
[H-].[Na+].[C:3]([O:11][CH2:12][CH3:13])(=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].Br[CH2:15][CH2:16][CH2:17][CH:18]=[CH2:19]>CN(C=O)C>[CH2:12]([O:11][C:3](=[O:10])[CH:4]([CH2:19][CH2:18][CH2:17][CH:16]=[CH2:15])[C:5]([O:7][CH2:8][CH3:9])=[O:6])[CH3:13]

参加物

5

反応物 3

HCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 707041-Pentene, 5-bromo-

生成物 1

HCID 361718Diethyl 2-pent-4-enylpropanedioate収率 101.1%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

反応条件

温度
0 °C

実験手順

A mixture of sodium hydride (60% in mineral oil, 2.4 g, 60.5 mmol, 1.1 eq) and diethyl malonate (8.34 mL, 55 mmol, 1 eq) in DMF (200 mL) was cooled to 0° C. and 5-bromo-1-pentene (6.5 mL, 55 mmol, 1 eq) was added dropwise. The reaction mixture was warmed to rt, stirred for 14 hours and then partitioned between ether and water. The layers were separated, the aqueous layer was extracted with ether (2×250 mL) and the combined organic phases were washed with water (2×) and brine, dried over MgSO4 and concentrated to give E1.1 as a colorless oil (12.7 g, 100% yield). 1H NMR (400 MHz, CDCl3): δ 5.71 (m, 1 H), 4.92 (m, 2 H), 4.12 (q, J=7.1 Hz, 4 H), 3.25 (t, J=7.58 Hz, 1 H), 2.01 (m, 2 H), 1.83 (m, 2 H), 1.36 (m, 2 H), 1.20 (t, J=7.1 Hz, 6 H).

後処理

  1. temperatureThe reaction mixture was warmed to rt
  2. custompartitioned between ether and water
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted with ether (2×250 mL)
  5. washthe combined organic phases were washed with water (2×) and brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated

出典と根拠

ORDレコード
ord-f51d1ade8be545a5945de7e438e9c56f
出典データセット
uspto-grants-2008_06
特許番号
US07384937B2

関連ノート

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