Dimethyl malonate → Dimethyl cyclopentane-1,1-dicarboxylate

HRID 217240

Reaction equation

HRID 217240 reaction equation
[CH3:1][O:2][C:3](=[O:9])[CH2:4][C:5]([O:7][CH3:8])=[O:6].Br[CH2:11][CH2:12][CH2:13][CH2:14]Br.C([O-])([O-])=O.[K+].[K+].F[B-](F)(F)F.C([N+]1C=CN(C)C=1)CCC>CN(C=O)C.O>[CH3:1][O:2][C:3]([C:4]1([C:5]([O:7][CH3:8])=[O:6])[CH2:14][CH2:13][CH2:12][CH2:11]1)=[O:9]

Participants

7

Reactant 4

HCID 7943Dimethyl malonateHCID 80561,4-DibromobutaneHCID 11430Potassium CarbonateHCID 27341781-Butyl-3-methylimidazolium tetrafluoroborate

Product 1

HCID 12609605Dimethyl cyclopentane-1,1-dicarboxylateYield 82.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a solution of malonic acid dimethyl ester (5.28 g, 40 mmol) in DMF (100 ml), 1,4-dibromo-butane (5.26 ml, 44 mmol), K2CO3 (13.8 g, 100 mmol), 1-butyl-3-methylimidazolium tetrafluoroborate (0.904 g, 4.0 mmol) are added at room temperature. The mixture is stirred at room temperature for 15 hours. To the mixture, water is added and the solution is extracted with AcOEt. The organic layer is washed with H2O and brine, dried over MgSO4, and concentrated under reduced pressure. The residue is purified by silica gel column chromatography to give cyclopentane-1,1-dicarboxylic acid dimethyl ester (6.13 g, 82%); TLC (hexane/AcOEt, 5:1) Rf 0.48, 1H NMR (400 MHz, chloroform-d) δ ppm 1.67-1.71 (m, 4H), 2.17-2.21 (m, 4H), 3.72 (s, 6H).

Workup

  1. extractionthe solution is extracted with AcOEt
  2. washThe organic layer is washed with H2O and brine
  3. dry with materialdried over MgSO4
  4. concentrationconcentrated under reduced pressure
  5. customThe residue is purified by silica gel column chromatography

Sources & evidence

ORD record
ord-f1910b2b9d6e45aa8fdb51f8d8baf472
Source dataset
uspto-grants-2012_06
Patent number
US08193349B2

Linked notes

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