Ethyl formate → Ethyl 2-formyl-3-oxopropanoate

Temperatur

0 °C

Ethyl 3,3-diethoxypropionate (100 g, 525.7 mmol) was dissolved in THF (360 ml) at room temp. Ethyl formate (175.1 ml, 2.1 mol) was added at room temp. The solution was cooled in an ice-bath to 0° C. and tBuOK (1M solution in THF, 1,156 ml, 1.156 mol) was added via an addition funnel slowly over 30 min, maintaining internal temperature below 5° C. The color changed instantly from colorless to dark orange. The reaction mixture was allowed to warm up to room temp. and stirred for 2 h. The reaction was allowed to stir at room temp. for 18 h. The reaction mixture was concentrated in vacuo and 1 L of solvent was removed. The remaining brownish solution with white solid in it was cooled in an ice-bath and hydrochloric acid (6N, 200 ml) was added to adjust pH=3, maintaining internal temperature below 20° C. The resulting bright yellow suspension was then warmed up to room temp. and stirred for 1 h. Additional 700 ml solvent was removed in vacuo at room temp. Water (400 ml) was added to dissolve all the white solid and ethyl acetate (500 ml) was added and the mixture transferred to a separatory funnel. The aqueous was extracted once with ethyl acetate (200 ml). The combined organic extracts was washed once with brine (100 ml). After drying over MgSO4 and concentrating in vacuo, 2-formyl-3-oxo-propionic acid ethyl ester (75.85 g) was obtained as yellow oil.

1. temperaturemaintaining internal temperature below 5° C
2. temperatureto warm up to room temp.
3. stirringto stir at room temp. for 18 h
4. concentrationThe reaction mixture was concentrated in vacuo and 1 L of solvent
5. customwas removed
6. temperatureThe remaining brownish solution with white solid in it was cooled in an ice-bath
7. additionhydrochloric acid (6N, 200 ml) was added
8. temperaturemaintaining internal temperature below 20° C
9. temperatureThe resulting bright yellow suspension was then warmed up to room temp.
10. stirringstirred for 1 h
11. customAdditional 700 ml solvent was removed in vacuo at room temp
12. additionWater (400 ml) was added
13. dissolutionto dissolve all the white solid and ethyl acetate (500 ml)
14. additionwas added
15. customthe mixture transferred to a separatory funnel
16. extractionThe aqueous was extracted once with ethyl acetate (200 ml)
17. washThe combined organic extracts was washed once with brine (100 ml)
18. dry with materialAfter drying over MgSO4
19. concentrationconcentrating in vacuo

ORD-Eintrag

ord-f162d2aee57f4371ba5eb6e5a8135f3d

Quelldatensatz

uspto-grants-2010_06

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US07728029B2