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

HRID 386898

반응식

HRID 386898 반응식
[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]

참가 물질

5

반응물 2

HCID 73790Diethyl cyclopropane-1,1-dicarboxylateHCID 16688073Lithium aluminum-tri-tert-butoxyhydride2회

생성물 1

HCID 12450336Ethyl 1-(hydroxymethyl)cyclopropane-1-carboxylate수율 97.4%

시약·촉매·용매 2

HCID 6344Dichloromethane용매HCID 8028Tetrahydrofuran용매3회

실험 절차

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 for 18 h. The reaction mixture is diluted with DCM, washed with 1N aqueous HCl solution, saturated aqueous 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).

후처리

  1. stirringthe solution is stirred for 18 h
  2. washwashed with 1N aqueous HCl solution, saturated aqueous NaHCO3 solution and brine
  3. customAfter drying the organic phase
  4. customover anhydrous Na2SO4, removal of the solvent under reduced pressure

출처 및 근거

ORD 기록
ord-94052ad926a544599a6d4578b1b3906b
출처 데이터셋
uspto-grants-2013_02
특허 번호
US08372874B2

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