Diethyl Malonate → HCID 11984308, compound

HRID 493465Notes

Reaction equation

HRID 493465 reaction equation
[H-].[Na+].[C:3]([O:11][CH2:12][CH3:13])(=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].[H][H].CS(O[C@@H:21]([CH3:26])[CH2:22][CH2:23][CH2:24][CH3:25])(=O)=O.[Cl-].[NH4+]>COCCOC.CN(C)C=O.CCOCC>[CH3:26][C@@H:21]([CH:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])[C:3]([O:11][CH2:12][CH3:13])=[O:10])[CH2:22][CH2:23][CH2:24][CH3:25]

Participants

9

Reactant 5

HCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 11984307HCID 11984307, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 11984308HCID 11984308, compound

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
25 °C

Procedure

At room temperature, a three-neck flask with internal thermometer, dropping funnel and stirrer was initially charged under protective nitrogen gas with 14.7 g of sodium hydride (95% pure, 0.583 mol) in 290 ml of dry 1,2-dimethoxyethane and 50 ml of dry dimethylformamide. Subsequently, 97.5 g of diethyl malonate (0.609 mol) were added dropwise at from 25 to 30° C. with evolution of hydrogen. The clear mixture was stirred at 25° C. for 30 min and 93 g of (S)-1-methylpentyl methanesulfonate (0.516 mol) were added undiluted. The mixture was heated to 80° C. and stirred for 5 h. After cooling to 25° C., the suspension was admixed with 600 ml of ether and 500 ml of saturated ammonium chloride solution. After phase separation, the organic phase was washed with 250 ml of water and then dried over sodium sulfate. After distillative removal of solvent, diethyl [(R)-1-methylpentyl]malonate was obtained in a yield of 119 g (94% of theory) and a chemical purity of 95% (GC).

Workup

  1. customAt room temperature, a three-neck flask with internal thermometer, dropping
  2. temperatureThe mixture was heated to 80° C.
  3. stirringstirred for 5 h
  4. temperatureAfter cooling to 25° C.
  5. customAfter phase separation
  6. washthe organic phase was washed with 250 ml of water
  7. dry with materialdried over sodium sulfate
  8. customAfter distillative removal of solvent

Sources & evidence

ORD record
ord-ebb48470e8f54188a70d76315342d20d
Source dataset
uspto-grants-2009_05
Patent number
US07534908B2

Reaction notes

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