Methanol → HCID 22405640, 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 MeI (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. stirringwas stirred for 4 hours at 0° C.
4. customat ambient temperature
5. customovernight
6. stirringby stirring for 30 minutes at that temperature
7. customprepared above
8. stirringThe reaction was stirred for 1 hour at -78° C.
9. custom1 hour
10. customat 0° C
11. temperatureThe reaction was then cooled to -78° C.
12. temperaturewarmed
13. temperatureto reflux
14. temperatureheated
15. temperatureat reflux for 1.5 hours
16. temperatureAfter cooling
17. customthe reaction, it
18. customwas partitioned between saturated NaHCO3 solution and methylene chloride
19. dry with materialThe organic layer was then dried with sodium sulfate
20. filtrationfiltered
21. concentrationconcentrated in vacuo and flash
22. customchromatographed
23. washeluting with 4:1 hexane-ethyl acetate

ORD record

ord-cf5cab1ff0fe4483bf9623435fae1a04

Source dataset

uspto-grants-1996_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05521181