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

HRID 1197501Notes

Reaction equation

HRID 1197501 reaction equation
[C:1]([NH:4][CH:5]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[C:6]([O:8][CH2:9][CH3:10])=[O:7])(=[O:3])[CH3:2].[Br:16][C:17]([CH2:19]Br)=[CH2:18].[H-].[Na+]>O1CCCC1.C(OCC)(=O)C>[Br:16][C:17](=[CH2:18])[CH2:19][CH2:2][C:1]([NH:4][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

6

Reactant 3

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

Product 1

HCID 53941200Diethyl (2-Bromoallyl)acetamidomalonateYield 89.5%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a stirred mixture of diethyl acetamidomalonate (217 g, 1.0 mol) and 2,3-dibromopropene (240 g, 1.2 mol) in anhydrous 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 ambient temperature for 30 minutes, then heated to reflux. After heating for 18 hours, the resultant slurry was cooled to ambient temperature and suction filtered through a short pad of silica gel. The solid residue was washed with tetrahydrofuran (2×50 mL), and the filtrates were combined and concentrated. The residue obtained was dissolved in ethyl acetate (2.0 L), washed with water and brine, and then was dried over magnesium sulfate. 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. 1H NMR (300 MHz, CDCl3) δ1.28 (t, J=7.4 Hz, 6H), 2.04 (s, 3H), 3.57 (s, 2H), 4.27 (m, 4H), 5.55 (bs, 1H), 5.61 (bs, 1H), 6.82 (broad, 1H); IR (KBr) 1745, 1635 cm-1Anal calcd for C12H18BrNO5 : C, 42.87; H, 5.40; Br, 23.77; N, 4.12. Found: C, 43.25; H, 5.56; Br, 22.97; N, 4.12.

Workup

  1. temperatureheated to reflux
  2. temperatureAfter heating for 18 hours
  3. temperaturethe resultant slurry was cooled to ambient temperature
  4. filtrationsuction filtered through a short pad of silica gel
  5. washThe solid residue was washed with tetrahydrofuran (2×50 mL)
  6. concentrationconcentrated
  7. customThe residue obtained
  8. washwashed with water and brine
  9. dry with materialwas dried over magnesium sulfate
  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-158c6e11cd774822a8b0ef42295b69e3
Source dataset
uspto-grants-1994_01
Patent number
US05275950

Reaction notes

Loading…