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

HRID 1809426Notes

Reaction equation

HRID 1809426 reaction equation
[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]

Participants

5

Reactant 2

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-1c5d484ae09b41348a1b7377f64e7830
Source dataset
uspto-grants-2013_01
Patent number
US08362039B2

Reaction notes

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