Diethyl Malonate → Diethyl (3-methylbut-2-enyl)malonate

HRID 2371852

反応式

HRID 2371852 の反応式
[H-].[Na+].CCCCC.[C:8]([O:16][CH2:17][CH3:18])(=[O:15])[CH2:9][C:10]([O:12][CH2:13][CH3:14])=[O:11].[CH2:19](Br)[CH:20]=[C:21]([CH3:23])[CH3:22]>O1CCCC1.CN(C)C=O>[CH3:22][C:21]([CH3:23])=[CH:20][CH2:19][CH:9]([C:10]([O:12][CH2:13][CH3:14])=[O:11])[C:8]([O:16][CH2:17][CH3:18])=[O:15]

参加物

7

反応物 4

HCID 7761Diethyl MalonateHCID 8003PentaneHCID 24758Sodium hydrideHCID 700922-Butene, 1-bromo-3-methyl-

生成物 1

HCID 89748Diethyl (3-methylbut-2-enyl)malonate収率 89.4%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

422 mg (14.1 mmol, 80% mineral oil dispersion) sodium hydride was washed 3×, each with 5 mL pentane, and suspended in a mixture of 10 mL tetrahydrofuran and 5 mL dimethylformamide. 2.04 g (13.4 mmol) diethyl malonate was added, and the mixture stirred for 40 mins to form a clear light brown solution. Prenyl bromide (2.00 g, 13.4 mmol) was then added, and the solution refluxed for 1 hr. The reaction was quenched with water, acidified to pH 2 with 1N HCl, and extracted 2×, each with 10 mL diethyl ether. The organic phases were dried over MgSO4, filtered, and concentrated. Chromatography on a 2×18 cm column, packed with hexane and eluted with 50 mL each of 2%, 4%, 7%, 10%, and 15% diethyl ether/hexane, furnished 2.734 g of a clear colorless oil in 12 mL fractions 4-16.

後処理

  1. customto form a clear light brown solution
  2. temperaturethe solution refluxed for 1 hr
  3. customThe reaction was quenched with water
  4. extractionextracted 2×
  5. dry with materialThe organic phases were dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. washeluted with 50 mL each of 2%, 4%, 7%, 10%, and 15% diethyl ether/hexane

出典と根拠

ORDレコード
ord-864abe7ff896405a8049bc75e25c37e8
出典データセット
uspto-grants-1992_03
特許番号
US05096838

関連ノート

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