Acetone → 4-vinylbenzoylacetone

HRID 1831871Notes

Reaction equation

HRID 1831871 reaction equation
[H-].[Na+].[CH:3]([C:5]1[CH:13]=[CH:12][C:8]([C:9]([O-:11])=O)=[C:7](C)[CH:6]=1)=[CH2:4].[CH3:15][C:16]([CH3:18])=[O:17].Cl.S([O-])([O-])(=O)=O.[Mg+2]>CCOCC.O.O1CCCC1>[CH:3]([C:5]1[CH:6]=[CH:7][C:8]([C:9]([CH2:15][C:16](=[O:17])[CH3:18])=[O:11])=[CH:12][CH:13]=1)=[CH2:4]

Participants

9

Reactant 5

HCID 180AcetoneHCID 313Hydrochloric Acid2×HCID 24083Sulfuric acid magnesium salt (1:1)HCID 24758Sodium hydrideHCID 21938742HCID 21938742, compound2×

Product 1

HCID 116224704-vinylbenzoylacetoneYield 43.4%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

Dry tetrahydrofuran (10 mL), sodium hydride (1.7 g, 70 mmol), and 4-vinyl-methylbenzoate (8.0 g, 49 mmol) were placed in a flame dried, three-necked, round bottomed flask equipped with a reflux condenser, nitrogen inlet, addition funnel and magnetic stir bar. Dry tetrahydrofuran (5 mL) and dry acetone (4.3 mL, 59 mmol) was added dropwise to the refluxing mixture containing 4-vinyl-methylbenzoate. The mixture was allowed to reflux for an additional two hours before allowed to cool to room temperature. Concentrated hydrochloric acid (1 mL) was added, the mixture was diluted with ether (50 mL) and water (50 mL), and the mixture was made acidic by a further addition of concentrated hydrochloric acid. The aqueous phase was rinsed with ether (2×50 mL), and the combined organic phase was washed with 1 M sodium hydroxide (3×50 mL). The combined alkali phases were rinsed with pentane. The alkali solution was acidified with concentrated hydrochloric acid, which formed a precipitate. The precipitate was removed from the aqueous phase by rinsing with ether (2×50 mL), and the combined organic phases were rinsed with saturated sodium bicarbonate solution (3×50 mL). The organic phase was dried with magnesium sulfate for 16 hours before filtration and isolation of the yellow material (4 g, 43% yield). 1H-NMR (200 MHz, 25° C., CDCl3): δ 16.12 (s, 1H), 7.83 (d, 2H), 7.45 (d, 2H), 6.70 (dd, 1H), 6.17 (s, 1H), 5.82 (d, 1H), 5.35 (d, 1H), 2.20 (s, 3H).

Workup

  1. customdried
  2. customthree-necked, round bottomed flask equipped with a reflux condenser, nitrogen inlet, addition funnel and magnetic stir bar
  3. temperatureto reflux for an additional two hours
  4. washThe aqueous phase was rinsed with ether (2×50 mL)
  5. washthe combined organic phase was washed with 1 M sodium hydroxide (3×50 mL)
  6. washwere rinsed with pentane
  7. customformed a precipitate
  8. customThe precipitate was removed from the aqueous phase
  9. washby rinsing with ether (2×50 mL)
  10. washthe combined organic phases were rinsed with saturated sodium bicarbonate solution (3×50 mL)

Sources & evidence

ORD record
ord-0eea44d6d021426ba246da10b507edab
Source dataset
uspto-grants-2006_06
Patent number
US07067702B2

Reaction notes

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