Methanol → HCID 67668396, compound

Temperature

0 °C

To methanol (404 μL, 10 mmol) in THF (10 mL) at 0° C. under nitrogen was added 2.5M n-BuLi (4.0 mL, 10 mmol). After stirring 20 minutes, CS2 (600 μL, 10 mmol) was added and stirring was continued for 4 hours. The reaction was then cooled to 0° C. followed by the addition of Mel (620 μL, 10 mmol) whereupon the reaction was stirred for 4 hours at 0° C. then at ambient temperature overnight. In a separate flask the anion of acetonitrile was prepared by the dropwise addition of acetonitrile (520 μL, 10 mmol) to a solution of LDA (10 mmol) in THF at -78° C. followed by stirring for 30 minutes at that temperature. To the acetonitrile anion was added the solution of the xanthate prepared above. The reaction was stirred for 1 hour at -78° C. then 1 hour at 0° C. The reaction was then cooled to -78° C., treated with ethyl bromoacetate (1.1 mL, 10 mmol), warmed to reflux, treated with 1.0M lithium bistrimethylsilylamide (1 mL) and heated at reflux for 1.5 hours. After cooling the reaction, it was partitioned between saturated NaHCO3 solution and methylene chloride. The organic layer was then dried with sodium sulfate, filtered, concentrated in vacuo and flash chromatographed eluting with 4:1 hexane-ethyl acetate to give 343 mg (17% yield) of the title compound.

1. stirringstirring
2. waitwas continued for 4 hours
3. additionfollowed by the addition of Mel (620 μL, 10 mmol) whereupon the reaction
4. stirringwas stirred for 4 hours at 0° C.
5. customat ambient temperature
6. customovernight
7. stirringby stirring for 30 minutes at that temperature
8. customprepared above
9. stirringThe reaction was stirred for 1 hour at -78° C.
10. custom1 hour
11. customat 0° C
12. temperatureThe reaction was then cooled to -78° C.
13. temperaturewarmed
14. temperatureto reflux
15. temperatureheated
16. temperatureat reflux for 1.5 hours
17. temperatureAfter cooling
18. customthe reaction, it
19. customwas partitioned between saturated NaHCO3 solution and methylene chloride
20. dry with materialThe organic layer was then dried with sodium sulfate
21. filtrationfiltered
22. concentrationconcentrated in vacuo and flash
23. customchromatographed
24. washeluting with 4:1 hexane-ethyl acetate

ORD record

ord-01b469ad6dcf45228f7b46ad91699acd

Source dataset

uspto-grants-1998_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05792767