Carbon Dioxide → 1,1-Dimethyl 2-methylcyclopropane-1,1-dicarboxylate

HRID 1721472Notes

Reaction equation

HRID 1721472 reaction equation
[C:1]([O:8][CH3:9])(=[O:7])[CH2:2][C:3]([O:5][CH3:6])=[O:4].C(=O)([O-])[O-].[K+].[K+].Cl[CH2:17][CH:18](Cl)[CH3:19].C(=O)=O>CN(C)C=O>[C:3]([C:2]1([C:1]([O:8][CH3:9])=[O:7])[CH2:17][CH:18]1[CH3:19])([O:5][CH3:6])=[O:4]

Participants

6

Reactant 4

HCID 280Carbon DioxideHCID 65641,2-DichloropropaneHCID 7943Dimethyl malonateHCID 11430Potassium Carbonate

Product 1

HCID 134163111,1-Dimethyl 2-methylcyclopropane-1,1-dicarboxylate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
118 °C

Procedure

The apparatus described in Example 1 was charged successively with 132.1 g dimethyl malonate (1.0 mol), 166 g (1.2 mols) finely comminuted potassium carbonate, 339 g 1,2-dichloropropane (3.0 mols) and 250 ml of dimethylformamide. While stirring vigorously, the reaction mixture was heated to 118° C., and the reaction temperature was increased to 125° C. over a period of 15 hours. While releasing carbon dioxide, the reaction mixture distilled off as an azeotrope which was separated into dichloropropane and water in the phase separator and was then drained. Flash distillation was used to separate the salts and high boiling components, and the distillate was separated by way of a column into the fractions 1,2-dichloropropane, dimethylformamide and 1,1-dicarbomethoxy-2-methylcyclopropane. The target product distilled over at 78° C./14 mbar and was identified by means of H-NMR as the desired target product.

Workup

  1. temperaturethe reaction temperature was increased to 125° C. over a period of 15 hours
  2. distillationthe reaction mixture distilled off as an azeotrope which
  3. customwas separated into dichloropropane and water in the phase separator
  4. distillationFlash distillation
  5. customto separate the salts and high boiling components
  6. customthe distillate was separated by way of a column into the fractions 1,2-dichloropropane, dimethylformamide and 1,1-dicarbomethoxy-2-methylcyclopropane
  7. distillationThe target product distilled over at 78° C./14 mbar

Sources & evidence

ORD record
ord-14eb5445022e4e40b5a75c6b053baa39
Source dataset
uspto-grants-1996_04
Patent number
US05510509

Reaction notes

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