Diethyl cyclopropane-1,1-dicarboxylate → Ethyl 1-(hydroxymethyl)cyclopropane-1-carboxylate

HRID 553636

反応式

HRID 553636 の反応式
[Li+].CC(O[Al-](OC(C)(C)C)OC(C)(C)C)(C)C.[C:18]1([C:26](OCC)=[O:27])([C:21]([O:23][CH2:24][CH3:25])=[O:22])[CH2:20][CH2:19]1>C1COCC1.C(Cl)Cl>[CH2:24]([O:23][C:21]([C:18]1([CH2:26][OH:27])[CH2:20][CH2:19]1)=[O:22])[CH3:25]

参加物

5

反応物 2

HCID 73790Diethyl cyclopropane-1,1-dicarboxylateHCID 16688073Lithium aluminum-tri-tert-butoxyhydride2 回

生成物 1

HCID 12450336Ethyl 1-(hydroxymethyl)cyclopropane-1-carboxylate収率 97.4%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒3 回

実験手順

A solution of lithium aluminum-tri-tert-butoxyhydride 1.0M in THF (28.5 mL, 28.5 mmol) is added to a solution of diethyl 1,1-cyclopropanedicarboxylate (2.0 mL, 11.4 mmol) in anhydrous THF (85.0 mL). After stirring the reaction mixture for 4 h, 10 mL of lithium aluminum-tri-tert-butoxyhydride 1.0M solution in THF is added and the solution is stirred overnight. The reaction mixture is diluted with DCM, washed with 1N HCl, saturated NaHCO3 solution and brine. After drying the organic phase over anhydrous Na2SO4, removal of the solvent under reduced pressure affords 1.60 g of 1-hydroxymethyl-cyclopropanecarboxylic acid ethyl ester that is used in the next step without further purification. Yield: 85%. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 0.88 (2H, q, J=4.1 Hz), 1.21-1.33 (5H, m), 2.59 (1H, t, J=6.9 Hz), 3.63 (2H, d, J=7.2 Hz), 4.17 (2H, q, J=7.1 Hz).

後処理

  1. stirringthe solution is stirred overnight
  2. washwashed with 1N HCl, saturated NaHCO3 solution and brine
  3. customAfter drying the organic phase
  4. customover anhydrous Na2SO4, removal of the solvent under reduced pressure

出典と根拠

ORDレコード
ord-746aa07d22cc4b5ead86c9039548f663
出典データセット
uspto-grants-2011_11
特許番号
US08048899B2

関連ノート

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