Dimethyl malonate → HCID 88466753, compound

HRID 978347Notes

Reaction equation

HRID 978347 reaction equation
[Mg:1].FC(F)(F)OC1C=CC(C(Cl)=O)=CC=1.[C:16]([O:23][CH3:24])(=[O:22])[CH2:17][C:18]([O:20][CH3:21])=[O:19]>C(O)C.C(Cl)(Cl)(Cl)Cl.CCOCC>[C:16]([O:23][CH3:24])(=[O:22])[CH2:17][C:18]([O:20][CH3:21])=[O:19].[Mg:1]

Participants

7

Reactant 3

HCID 7943Dimethyl malonateHCID 1421104-(Trifluoromethoxy)benzoyl ChlorideHCID 5462224Magnesium

Product 1

HCID 88466753HCID 88466753, compound

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 3283Diethyl EtherSolventHCID 5943Carbon TetrachlorideSolvent

Procedure

A solution of magnesium dimethyl malonate is prepared from 4.1 g of magnesium turnings in 25 ml of absolute ethanol and 19.9 ml of dimethyl malonate and 1 ml of carbon tetrachloride. 37.9 g of 4-trifluoromethoxybenzoyl chloride in 85 ml of absolute ether (diethylether) are added dropwise to this solution (while cooling in ice); the cooling bath is then removed, and the reaction mixture is stirred at 20° overnight. Thereafter, while cooling in ice, 25 ml of 25% strength sulfuric acid are added dropwise, the ether layer is removed, and the aqueous phase is extracted twice more with ether. The combined ether extracts are washed with water to neutrality, dried over sodium sulfate and evaporated. The remaining yellow oil is boiled in 300 ml of 6N hydrochloric acid under reflux for 12 hours. After cooling, the oil is removed, the aqueous phase is extracted 6 times with 100 ml of dichloromethane each time. The oil and the dichloromethane extracts are combined, dried over sodium sulfate and evaporated. The remaining oil is distilled at 1.6 kPa. 26.85 g (77.9% of theory) of the title compound (boiling point 94° to 96°). are obtained.

Workup

  1. customthe cooling bath is then removed
  2. temperatureThereafter, while cooling in ice
  3. addition25 ml of 25% strength sulfuric acid are added dropwise
  4. customthe ether layer is removed
  5. extractionthe aqueous phase is extracted twice more with ether
  6. washThe combined ether extracts are washed with water to neutrality
  7. dry with materialdried over sodium sulfate
  8. customevaporated
  9. temperatureunder reflux for 12 hours
  10. temperatureAfter cooling
  11. customthe oil is removed
  12. extractionthe aqueous phase is extracted 6 times with 100 ml of dichloromethane each time
  13. dry with materialdried over sodium sulfate
  14. customevaporated
  15. distillationThe remaining oil is distilled at 1.6 kPa
  16. customare obtained

Sources & evidence

ORD record
ord-9dc122ad68c34fe492134bf17acd4170
Source dataset
uspto-grants-1987_05
Patent number
US04665074

Reaction notes

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