Hexane → HCID 70150687, compound

Temperature

-20 °C

150 ml of ether were placed in a round-bottomed flask containing 5.08 g (0.039 moles) of 2-methylindene 13; the solution was cooled to −20° C. 17.0 ml of a 2.3 molar solution of butyllithium in hexane (0.039 moles) were added over 5 min to form a yellow solution. After removal of the cooling bath, the solution was heated to room temperature and subsequently stirred for 1 h. The reaction mixture was then cooled to −20° C. and 5.8 g (0.039 moles) of chlorodiisopropylphosphine were added over 5 min to form a precipitate. The cooling bath was then removed and the reaction mixture was stirred for 1 h at room temperature. After cooling to −20° C., 17.0 ml of a 2.3 molar solution of butyllithium in hexane (0.039 moles) were added dropwise. When the addition was complete, the cooling bath was removed and the solution was heated slowly to room temperature and stirred for 1.5 h. After cooling of the suspension to 0° C., 12.4 g (0.038 moles) of chlorotributyltin were added dropwise. The suspension formed was heated to room temperature and stirred for 1.5 h. The ether was removed under vacuum, the crude product was dissolved in hexane again, the solution was filtered and the filtrate was concentrated to dryness under vacuum to leave 20.4 g (yield: 98%) of compound 14 in the form of a heavy yellow oil. Two isomers were identified by 31P NMR. 31P NMR (161.9 MHz, CD2Cl2): δ=−5.9 and −6.6 in a ratio of 2:1.

1. customto form a yellow solution
2. customAfter removal of the cooling bath
3. temperaturethe solution was heated to room temperature
4. temperatureThe reaction mixture was then cooled to −20° C.
5. customto form a precipitate
6. customThe cooling bath was then removed
7. stirringthe reaction mixture was stirred for 1 h at room temperature
8. temperatureAfter cooling to −20° C.
9. additionWhen the addition
10. customthe cooling bath was removed
11. temperaturethe solution was heated slowly to room temperature
12. stirringstirred for 1.5 h
13. temperatureAfter cooling of the suspension to 0° C.
14. customThe suspension formed
15. temperaturewas heated to room temperature
16. stirringstirred for 1.5 h
17. customThe ether was removed under vacuum
18. dissolutionthe crude product was dissolved in hexane again
19. filtrationthe solution was filtered
20. concentrationthe filtrate was concentrated to dryness under vacuum

ORD record

ord-a7051d7bcdde49dea76b169fb081272f

Source dataset

uspto-grants-2002_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06433112B1