Diethyl Carbonate → Ethyl 3-(3-cyanophenyl)-3-oxopropanoate

Temperature

60 °C

Sodium hydride (60% dispersion in oil, 8.27 g, 207 mmol, 3.00 equiv) was added to a solution of 3-acetylbenzonitrile (10.0 g, 68.9 mmol, 1 equiv) in tetrahydrofuran (300 mL). The reaction mixture was stirred at 60° C., and a solution of diethyl carbonate (12.5 mL, 103 mmol, 1.50 equiv) in tetrahydrofuran (60 mL) was added over 45 minutes. The light orange reaction mixture was stirred at 60° C. for an additional 2 h, then was cooled to 22° C. Saturated aqueous ammonium chloride solution was added, and the mixture was concentrated to ˜½ volume by rotary evaporation. The resulting residue was partitioned between ethyl acetate and water. The organic layer was washed with saturated aqueous sodium chloride solution, and the washed solution was dried over sodium sulfate. The dried solution was filtered, and the filtrate was concentrated to afford ethyl 3-(3-cyanophenyl)-3-oxopropanoate (15 g, 100%) as a white solid. The crude reaction product was taken into the next step without further purification. Calcd (M+1)+: 218.1. Found: 218.0.

1. stirringThe light orange reaction mixture was stirred at 60° C. for an additional 2 h
2. temperaturewas cooled to 22° C
3. concentrationthe mixture was concentrated
4. customby rotary evaporation
5. customThe resulting residue was partitioned between ethyl acetate and water
6. washThe organic layer was washed with saturated aqueous sodium chloride solution
7. dry with materialthe washed solution was dried over sodium sulfate
8. filtrationThe dried solution was filtered
9. concentrationthe filtrate was concentrated

ORD record

ord-795b0fa837d64deba63014c5dab8c0f1

Source dataset

uspto-grants-2014_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08871796B2