Dimethyl malonate → 1,1-Dimethyl 2-ethenylcyclopropane-1,1-dicarboxylate

HRID 986489

Reaction equation

HRID 986489 reaction equation
C[O-].[Na+].[C:4]([O:11][CH3:12])(=[O:10])[CH2:5][C:6]([O:8][CH3:9])=[O:7].[CH2:13](Cl)/[CH:14]=[CH:15]/[CH2:16]Cl>CO>[CH:14]([CH:15]1[CH2:16][C:5]1([C:4]([O:11][CH3:12])=[O:10])[C:6]([O:8][CH3:9])=[O:7])=[CH2:13]

Participants

5

Reactant 3

HCID 7943Dimethyl malonateHCID 6421971,4-Dichloro-2-butene, (2E)-HCID 10942334Sodium Methoxide

Product 1

HCID 104649921,1-Dimethyl 2-ethenylcyclopropane-1,1-dicarboxylateYield 105.8%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

Sodium methoxide (108.02 g, 2.0 moles) 25% in MeOH was added in 40 minutes to dimethyl malonate (132.12 g, 1.0 mole), 1,4-dichlorobutene-2 (150 g, 1.2 moles), and 50 mL MeOH and allowed to stir at ambient temperature overnight. The mixture was vacuum filtered, neutralized with concentrated HCl to 3.5-4.0 pH, and filtered a second time. Solvent was then removed under vacuum to give 194.8 g of light yellow crude product. Vacuum distillation (55°/0.25 mm-72°/0.4 mm) with 0.064 g of hydroquinone added gave 142.5 g of product (77.4% yield) and 30.4 g of residue.

Workup

  1. filtrationfiltered
  2. filtrationfiltered a second time
  3. customSolvent was then removed under vacuum

Sources & evidence

ORD record
ord-eedc9610040547acb37c82c9c8752e35
Source dataset
uspto-grants-1987_12
Patent number
US04713478

Linked notes

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