2,3-Dibromopropene → Diethyl (2-Bromoallyl)acetamidomalonate

HRID 893093Notes

Reaction equation

HRID 893093 reaction equation
[NH:1]([CH:5]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])[C:2]([CH3:4])=[O:3].[Br:16][C:17]([CH2:19]Br)=[CH2:18].[H-].[Na+]>O1CCCC1>[Br:16][C:17](=[CH2:18])[CH2:19][CH2:4][C:2]([NH:1][CH:5]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])=[O:3]

Participants

5

Reactant 3

HCID 105522,3-DibromopropeneHCID 14041Acetamidomalonic acid diethyl esterHCID 24758Sodium hydride

Product 1

HCID 53941200Diethyl (2-Bromoallyl)acetamidomalonateYield 89.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred mixture of diethyl acetaminomalonate (217 g, 1.0 mol) and 2,3-dibromopropene (240 g, 1.2 mol) in dry tetrahydrofuran (2.50 L), under nitrogen, was added sodium hydride (26.4 g, 1.1 mol) in several portions. The reaction mixture was stirred at room temperature for 30 min, then heated to reflux. After heating for 18 h, the resultant slurry was cooled to room temperature and suction filtered through a short pad of silica gel. The solid rescue as washed with tetrahydrofuran (2×50 mL), and the filtrates were combined and concentrated. The residue was dissolved in ethyl acetate (2.0 L), washed with water and brine, and then was dried over MgSO4. Filtration and concentration gave a yellow oil which solidified upon drying. The resultant solid was recrystallized from a mixture of hot ethyl acetate/hexane to give 301 g (89%) of the desired product: m.p. 85-87° C.

Workup

  1. temperatureheated to reflux
  2. temperatureAfter heating for 18 h
  3. temperaturethe resultant slurry was cooled to room temperature
  4. filtrationsuction filtered through a short pad of silica gel
  5. washThe solid rescue as washed with tetrahydrofuran (2×50 mL)
  6. concentrationconcentrated
  7. dissolutionThe residue was dissolved in ethyl acetate (2.0 L)
  8. washwashed with water and brine
  9. dry with materialwas dried over MgSO4
  10. filtrationFiltration and concentration
  11. customgave a yellow oil which
  12. customupon drying
  13. customThe resultant solid was recrystallized from a mixture of hot ethyl acetate/hexane

Sources & evidence

ORD record
ord-4d9ed753a79f4570b6ed291d4cf151da
Source dataset
uspto-grants-1992_06
Patent number
US05122514

Reaction notes

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