Phosphorus pentachloride → Methyl 3-chloro-2,2-dimethylbut-3-enoate

HRID 1847589Notes

Reaction equation

HRID 1847589 reaction equation
P(Cl)(Cl)(Cl)(Cl)[Cl:2].[CH3:7][C:8]([CH3:16])([C:13](=O)[CH3:14])[C:9]([O:11][CH3:12])=[O:10]>ClCCl.CN(C=O)C>[Cl:2][C:13](=[CH2:14])[C:8]([CH3:16])([CH3:7])[C:9]([O:11][CH3:12])=[O:10]

Participants

5

Reactant 2

HCID 24819Phosphorus pentachlorideHCID 96925Methyl 2,2-dimethylacetoacetate

Product 1

HCID 40423475Methyl 3-chloro-2,2-dimethylbut-3-enoate

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent

Procedure

To a suspension of PCl5 (161 g, 0.772 mol) in dichloromethane (600 mL) was added dropwise methyl 2,2-dimethyl-3-oxobutanoate (52 g, 0.361 mol, crude from last step) at 0° C., followed by the addition of approximately 20 drops of dry DMF. The mixture was heated at reflux overnight. After cooling, the reaction mixture was slowly poured into ice water. The organic layer was separated and the aqueous phase was extracted with dichloromethane (300 mL×3). The combined organic layers were washed with saturated aqueous NaHCO3 solution and dried over anhydrous Na2SO4. The solvent was evaporated to give the product, methyl 3-chloro-2,2-dimethylbut-3-enoate which was used without further purification (47 g, 82%).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux overnight
  3. temperatureAfter cooling
  4. customThe organic layer was separated
  5. extractionthe aqueous phase was extracted with dichloromethane (300 mL×3)
  6. washThe combined organic layers were washed with saturated aqueous NaHCO3 solution
  7. dry with materialdried over anhydrous Na2SO4
  8. customThe solvent was evaporated

Sources & evidence

ORD record
ord-7e92eda1849b408591dac4ce10dace67
Source dataset
uspto-grants-2015_02
Patent number
US08952050B2

Reaction notes

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