Diethyl Ether → HCID 131722977, compound

Temperature

-40 °C

Into a dry flask was placed a solution of [(4RS, 1E)-4-hydroxy-4-methyl-1-octenyl]tri-n-butyltin (1.36 g, 3.15 mmol) in dry tetrahydrofuran (5 ml) under nitrogen atmosphere, and the mixture was cooled to 0° C. To this solution was dropped 5.7 ml (5.99 mmol) of a diethyl ether solution of methyllithium (1.05 mol/liter), and stirring was continued for 1 h, letting the temperature rise gradually to room temperature. After cooling to −40° C., copper (I) cyanide (141 mg, 1.58 mmol) was added and dissolved by letting the temperature rise gradually to 0° C. This reaction liquid was cooled to −78° C. and added with a solution of (±) methyl 7-(3-tert-butyldimethylsilyloxy-5-oxo-1-cyclopentenyl)heptanoate (318 mg, 0.9 mmol) in dry tetrahydrofuran (1.5 ml) was rapidly added. After stirring for 5 min, 20 ml of a saturated aqueous ammonium chloride/aqueous ammonia (9:1) was added, and stirring was continued for 30 min , letting the temperature rise gradually to room temperature. This mixture was extracted with ethyl acetate (80 ml) two times, and the combined organic layer was washed with a saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, and concentrated in vacuo to remove solvent. The residue was purified by silica gel column chromatography [ethyl acetate/hexane (1/5)] to give 413 mg (96% yield) of (±)-methyl(16RS, 13E)-11-tert-butyldimethylsilyloxy-16-hydroxy-16-methyl-9-oxoprost-13-en-1-oate as a colorless oil. The spectral data of IR and 1H NMR were identical with those of the example 2.

1. customInto a dry flask was placed
2. customgradually to room temperature
3. dissolutiondissolved
4. customgradually to 0° C
5. customThis reaction liquid
6. temperaturewas cooled to −78° C.
7. additionwas rapidly added
8. stirringAfter stirring for 5 min
9. stirringstirring
10. waitwas continued for 30 min
11. customgradually to room temperature
12. extractionThis mixture was extracted with ethyl acetate (80 ml) two times
13. washthe combined organic layer was washed with a saturated aqueous sodium chloride
14. dry with materialdried over anhydrous magnesium sulfate
15. concentrationconcentrated in vacuo
16. customto remove solvent
17. customThe residue was purified by silica gel column chromatography [ethyl acetate/hexane (1/5)]

ORD record

ord-f0c1f8103e414a6897080845d32f0525

Source dataset

uspto-grants-2001_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06313341B1