Allyl bromide → t-Butyl ethyl 2-allylmalonate

HRID 374249Notes

Reaction equation

HRID 374249 reaction equation
C(=O)([O-])[O-].[K+].[K+].[C:7]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])(=[O:14])[CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10].[CH2:20](Br)[CH:21]=[CH2:22]>CN(C)C=O.O>[CH2:22]([CH:8]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[C:7]([O:15][C:16]([CH3:18])([CH3:17])[CH3:19])=[O:14])[CH:21]=[CH2:20]

Participants

6

Reactant 3

HCID 7841Allyl bromideHCID 11430Potassium CarbonateHCID 96345tert-Butyl ethyl malonate

Product 1

HCID 19809570t-Butyl ethyl 2-allylmalonate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
70 °C

Procedure

Potassium carbonate (28.0 g.) was added to a stirred solution of t-butyl ethyl malonate (37.6 g.) in dry N,N-dimethylformamide (DMF) (100 ml.). After 1 hour allyl bromide (34 ml.) was added. The mixture was heated at 70° C. for 66 hours, cooled to room temperature and diluted with water (900 ml.). The mixture obtained was extracted with ethyl acetate (3×200 ml.). The extracts were dried (MgSO4) and evaporated. The oil obtained was purified by flash column chromatography eluting with 1:15 v/v ethyl acetate/petroleum ether (b.p. 60°-80° C.) to give t-butyl ethyl 2-allylmalonate as a colourless oil (15.6 g.), b.p. 70°-72° C. at 0.2 mmHg; NMR: 1.21 (3H,t), 1.42 (9H,s), 2.66 (2H,m), 3.28 (1H,m), 4.16 (2H,q), 5.06 (2H,m) and 5.76 (1H,m) ppm.

Workup

  1. temperaturecooled to room temperature
  2. customThe mixture obtained
  3. extractionwas extracted with ethyl acetate (3×200 ml.)
  4. dry with materialThe extracts were dried (MgSO4)
  5. customevaporated
  6. customThe oil obtained
  7. customwas purified by flash column chromatography
  8. washeluting with 1:15 v/v ethyl acetate/petroleum ether (b.p. 60°-80° C.)

Sources & evidence

ORD record
ord-64ba6a2633a343bbb02eb462a3100af6
Source dataset
uspto-grants-1992_11
Patent number
US05166377

Reaction notes

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