Acetamidomalonic acid diethyl ester → HCID 86753717, compound

HRID 362153Notes

Reaction equation

HRID 362153 reaction equation
[Na].[C:2]([NH:5][CH:6]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:7]([O:9][CH2:10][CH3:11])=[O:8])(=[O:4])[CH3:3].Br[CH2:18]/[CH:19]=[CH:20]\[CH3:21]>C(O)C>[C:2]([NH:5][C:6]([CH2:18]/[CH:19]=[CH:20]\[CH3:21])([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:7]([O:9][CH2:10][CH3:11])=[O:8])(=[O:4])[CH3:3]

Participants

5

Reactant 3

HCID 14041Acetamidomalonic acid diethyl esterHCID 5354843cis-Crotyl BromideHCID 5360545Sodium

Product 1

HCID 86753717HCID 86753717, compoundYield 98%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

4.37 g (190 mmol) of sodium metal were dissolved in 110 ml of anhydrousethanol. 41.14 g (189.6 mmol) of diethyl acetamidomalonate dissolved in 270ml of anhydrous ethanol were added and the mixture was heated under reflux for 10 minutes. 25.65 g (168 mmol) of (Z)-1-bromo-2-butene were added dropwise at room temperature and the mixture was stirred overnight, then evaporated to dryness under vacuum and the residue was partitioned betweenethyl acetate and 0.1M hydrochloric acid. The organic phase was washed withsaturated sodium hydrogen carbonate solution followed by saturated sodium chloride solution and dried over anhydrous magnesium sulphate. After removal of the solvent by evaporation the crude product was chromatographed on silica gel using 66% ethyl acetate in petroleum ether as eluent to obtain 44.69 g of diethyl (Z)-2-acetamido-2-(2-butenyl)malonate as a colourless oil;1H NMR (250 MHz, CDCl3) δ:1.2 (t, 6 H), 1.6 (d, 3 H), 2.0 (s, 3 H), 3.1 (d, 2 H), 4.2 (q, 4 H), 5.1(m, 1 H), 5.6 (m, 1 H), 6.7 (s, 1 H).

Workup

  1. additionwere added
  2. temperaturethe mixture was heated
  3. temperatureunder reflux for 10 minutes
  4. customevaporated to dryness under vacuum
  5. customthe residue was partitioned betweenethyl acetate and 0.1M hydrochloric acid
  6. washThe organic phase was washed
  7. dry with materialdried over anhydrous magnesium sulphate
  8. customAfter removal of the solvent
  9. customby evaporation the crude product
  10. customwas chromatographed on silica gel using 66% ethyl acetate in petroleum ether as eluent

Sources & evidence

ORD record
ord-ebfaa796ecba432cafec97e28e27746f
Source dataset
uspto-grants-1999_02
Patent number
US05866684

Reaction notes

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