Chlorotrimethylsilane → HCID 56936043, compound

In an argon atmosphere, 40 ml of anhydrous tetrahydrofuran were added to 1.95 g (10.2 mmol) of copper (LiCl) iodide (CuI) and 1.09 g (25.7 mmol) of lithium chloride dried at a reduced pressure and 130° C., and the resultant solution was stirred at room temperature for about 15 minutes. The resultant transparent solution was cooled to about -60° C., and a solution obtained by dissolving 1.16 g of the compound (27) obtained in step h' in 21 ml of tetrahydrofuran was added to the above cooled solution. Subsequently, 2.72 ml (20.4 mmol) of chlorotrimethylsilane (TMSCl) were added to the resultant solution, this solution mixture was stirred for 10 minutes, and 5.04 ml (16.0 mmol) of distilled and purified n-Bu3SnH were added to stirred solution mixture in a small amount each time over about 5 minutes. Cooling was then stopped, and the temperature of the reaction solution was raised to 0° C. at room temperature over about 30 minutes. 60 ml of a 10% aqueous potassium fluoride (KF) solution were added to the above reaction solution, the mixture was stirred, and the produced precipitate was filtered. The organic layer was separated from this filtrate, and the remaining water layer was extracted with 100 ml of ether three times. The extracted solution was concentrated, 90 ml of a 10% aqueous potassium fluoride solution were added to the resultant residue, and the solution mixture was stirred for 15 minutes. Ether was added to this solution and stirred for 15 minutes. The resultant solution was filtered, the filtrate was separated, and its water layer was extracted with 100 ml of ether three times. These organic layers were collected, sequentially washed with water and brine solution, and dried with anhydrous magnesium sulfate. The organic layers were concentrated to obtain a crude product, and the crude product was purified by a column chromatograph using a developing solvent (hexane: diethyl tether=91:9 to 83:17), thereby obtaining 875 mg (4.46 mmol) of a compound (28) as a colorless transparent oily substance (yield:74%). The physical data of the resultant compound (28) were as follows:

1. customdried at a reduced pressure and 130° C.
2. temperatureThe resultant transparent solution was cooled to about -60° C.
3. customa solution obtained
4. additionwas added to the above cooled solution
5. stirringthis solution mixture was stirred for 10 minutes
6. distillation5.04 ml (16.0 mmol) of distilled
7. custompurified n-Bu3SnH
8. additionwere added
9. stirringto stirred solution mixture in a small amount each time over about 5 minutes
10. temperatureCooling
11. temperaturethe temperature of the reaction solution was raised to 0° C. at room temperature over about 30 minutes
12. addition60 ml of a 10% aqueous potassium fluoride (KF) solution were added to the above reaction solution
13. stirringthe mixture was stirred
14. filtrationthe produced precipitate was filtered
15. customThe organic layer was separated from this filtrate
16. extractionthe remaining water layer was extracted with 100 ml of ether three times
17. concentrationThe extracted solution was concentrated
18. addition90 ml of a 10% aqueous potassium fluoride solution were added to the resultant residue
19. stirringthe solution mixture was stirred for 15 minutes
20. additionEther was added to this solution
21. stirringstirred for 15 minutes
22. filtrationThe resultant solution was filtered
23. customthe filtrate was separated
24. extractionits water layer was extracted with 100 ml of ether three times
25. customThese organic layers were collected
26. washsequentially washed with water and brine solution
27. dry with materialdried with anhydrous magnesium sulfate
28. concentrationThe organic layers were concentrated
29. customto obtain a crude product
30. customthe crude product was purified by a column chromatograph

ORD record

ord-bc7cca689c484437b4caabddb367a83e

Source dataset

uspto-grants-1994_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05374744