Acetamidomalonic acid diethyl ester → diethyl (E)-2-acetamido-2-(2-butenyl)malonate

HRID 362150Notes

Reaction equation

HRID 362150 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 6375322-Butene, 1-bromo-, (2E)-HCID 5360545Sodium

Product 1

HCID 86753714diethyl (E)-2-acetamido-2-(2-butenyl)malonateYield 87.8%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

3.86 g (168 mmol) of sodium metal were dissolved in 106 ml of anhydrousethanol. 36.35 g (168 mmol) of diethyl acetamidomalonate dissolved in 225 ml of anhydrous ethanol were added and the mixture was heated under refluxfor 10 minutes. 22.66 g (168 mmol) of (E)-1-bromo-2-butene were added dropwise at room temperature and the mixture was stirred overnight and then evaporated to dryness under a vacuum. The residue was partitioned between ethyl acetate and 0.1M hydrochloric acid. The organic phase was washed with saturated sodium hydrogen carbonate solution and then with saturated sodium chloride solution and dried over anhydrous magnesium sulphate. The solvent was evaporated to give 40 g of diethyl (E)-2-acetamido-2-(2-butenyl)malonate as a colourless oil; 1H NMR (250 MHz, CDCl3) δ: 1.25 (t, 6 H), 1.6 (d, 3 H), 2.0 (s, 3 H), 2.9 (d, 2 H), 4.2 (q, 4 H), 5.15 (m, 1 H) 5.5 (m, 1 H), 6.7 s, 1 H).

Workup

  1. additionwere added
  2. temperaturethe mixture was heated under refluxfor 10 minutes
  3. customevaporated to dryness under a vacuum
  4. customThe residue was partitioned between ethyl acetate and 0.1M hydrochloric acid
  5. washThe organic phase was washed with saturated sodium hydrogen carbonate solution
  6. dry with materialwith saturated sodium chloride solution and dried over anhydrous magnesium sulphate
  7. customThe solvent was evaporated

Sources & evidence

ORD record
ord-d0b36201542649e09c8e188c5f1a57f7
Source dataset
uspto-grants-1999_02
Patent number
US05866684

Reaction notes

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