Potassium Chloride → 3-(2-Chloro-4-methoxy-phenyl)-propenal

Temperatur

100 °C

To a mixture of 4-bromo-3-chloro anisole (35 g, 0.159 mol), KCl (11.9 g, 0.160 mol, 1 eq.), K2CO3 (33 g, 0.238 mol, 1.5 eq) in 400 mL DMF in a sealed tube was added acrolein diethylacetal (73 mL, 0.479 mol, 3 eq.) and Bu4NOAc (96 g, 0.318 mol, 2 eq.). N2 was bubbled through the mixture and Pd(OAc)2 (1.1 g, 4. mmol, 3 mol %) was added. The reaction mixture was heated in an oil bath for 6 hr at 100° C. then cooled in an ice-bath. 300 mL of water was then added, followed by 500 mL of 1N HCl. The ice-bath was removed and the mixture was stirred for 30 min. The solution was extracted with ethyl acetate once then with diethyl ether 3 times. The combined organic layer washed with water, brine, dried over MgSO4, filtered and concentrated to provide the crude product which was recrystallized from hot ethyl acetate-hexanes to provide 15.5 g of crystalline 3-(2-chloro-4-methoxy-phenyl)-propenal. The mother liquor was concentrated and chromatographed with 10% ethyl acetate to provide another 5.6 g of 3-(2-chloro-4-methoxy-phenyl)-propenal.

1. customN2 was bubbled through the mixture and Pd(OAc)2 (1.1 g, 4. mmol, 3 mol %)
2. additionwas added
3. temperaturethen cooled in an ice-bath
4. addition300 mL of water was then added
5. customThe ice-bath was removed
6. extractionThe solution was extracted with ethyl acetate once
7. washThe combined organic layer washed with water, brine
8. dry with materialdried over MgSO4
9. filtrationfiltered
10. concentrationconcentrated
11. customto provide the crude product which
12. customwas recrystallized from hot ethyl acetate-hexanes

ORD-Eintrag

ord-f8b98ca4099f4e11aa05f87a6731bd22

Quelldatensatz

uspto-grants-2011_03

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US07897601B2