Hydrochloric Acid → 4-vinylbenzoylacetone

Temperature

-196 °C

Dimethyl formamide (30 mL), palladium acetate (0.022 g, 0.1 mmol), tri-o-tolyl phosphine (0.060 g, 0.2 mmol), triethylamine (9.1 g, 90 mmol), 4-bromobenzoylacetone (2.41 g, 10 mmol) were added to a 100 mL Parr high pressure reactor with an inner glass liner. The solution was degassed with nitrogen for 10 minutes before the reactor was cooled to −196° C. and ethylene (1.7 g, 61 mmol) was condensed for 20 minutes. The reactor was allowed to warm to room temperature before heating to 100° C. in an oil bath. The pressure was bled off until 300 psi was achieved and the reaction was allowed to proceed for 12 hours. The reaction vessel was cooled to room temperature, the extra pressure bled, and the contents dissolved in water (50 mL) and ether (50 mL). The aqueous phase was made acidic by addition of concentrated hydrochloric acid followed by extraction with ether (2×50 mL). The combined organic phase was rinsed with saturated sodium chloride solution, and the organic phase was dried over magnesium sulfate overnight. The solution was filtered, the solvent was removed by vacuum, and the residue dissolved in chloroform (3 mL). The product was isolated by column chromatography from silica gel (Selecto, mesh size 63-200) with chloroform as eluent. The first band collected resulted in a yellow powder (1.03 g, 55% yield) upon solvent removal. 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).

1. customThe solution was degassed with nitrogen for 10 minutes before the reactor
2. customcondensed for 20 minutes
3. temperatureto warm to room temperature
4. temperaturebefore heating to 100° C. in an oil bath
5. temperatureThe reaction vessel was cooled to room temperature
6. extractionfollowed by extraction with ether (2×50 mL)
7. washThe combined organic phase was rinsed with saturated sodium chloride solution
8. dry with materialthe organic phase was dried over magnesium sulfate overnight
9. filtrationThe solution was filtered
10. customthe solvent was removed by vacuum
11. dissolutionthe residue dissolved in chloroform (3 mL)
12. customThe product was isolated by column chromatography from silica gel (Selecto, mesh size 63-200) with chloroform as eluent
13. customThe first band collected

ORD record

ord-f95b07f151424ed4b4175ae6fbf2dc46

Source dataset

uspto-grants-2006_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07067702B2