Dimethyl Sulfate → Ethyl (2Z)-2-(ethoxymethyl)-3-methoxyprop-2-enoate

Temperature

50 °C

Sodium (40.9 g, 1.78 mol) was added to ethanol (750 mL) in portions carefully and the solution was concentrated to give NaOEt powder after all sodium metal disappeared. Under stirring, hexane (1.0 L) was added and the mixture was cooled with ice-water bath. A mixture of 201 (130 g, 0.89 mol) and ethyl formate (131 g, 1.78 mol) was added dropwise at 0-5° C. The reaction mixture was stirred at room temperature overnight. Dimethyl sulfate (224 g, 1.78 mol) was added dropwise with cooling of ice-water bath. The resulting mixture was heated at 50° C. for 2 h. To the mixture was added triethylammonium chloride (122 g) and sodium hydroxide (20 g). The mixture was then stirred at room temperature for 4 h and filtered. The filtrate was washed with water and dried over Na2SO4. It was concentrated to afford the titled compound (140 g, 37%) as a colorless oil which was used in the next step without further purification.

1. temperaturethe mixture was cooled with ice-water bath
2. additionwas added dropwise at 0-5° C
3. stirringThe reaction mixture was stirred at room temperature overnight
4. temperaturewith cooling of ice-water bath
5. stirringThe mixture was then stirred at room temperature for 4 h
6. filtrationfiltered
7. washThe filtrate was washed with water
8. dry with materialdried over Na2SO4
9. concentrationIt was concentrated

ORD record

ord-1f4b74f90d1a4c58a4c4aa2f3444616e

Source dataset

uspto-grants-2016_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09249156B2