Indene → Tributylstannyldimethylphosphinoindene

Temperatur

-20 °C

150 ml of ether were introduced into a round-bottomed flask which contained 5.5 g (0.047 mol) of indene; the mixture was cooled to −20° C. 20.8 ml of a 2.3 molar solution of butyl-lithium in hexane (0.048 mol) were added to this solution in the course of 5 minutes, a yellow solution being formed. After removal of the cooling bath, the solution was warmed to room temperature and subsequently stirred for 1 hour. After the reaction mixture had been cooled to −30° C., 4.6 g of chlorodimethylphosphine (0.048 mol) in 30 ml of ether were added in the course of 20 minutes, a precipitate forming. After stirring at −20° C. for 2 hours, 20.8 ml of a 2.3 molar solution of butyl-lithium in hexane (0.048 mol) were added drop-wise. When the addition was complete, the cooling bath was removed and the solution was warmed slowly to room temperature and subsequently stirred for 1.5 hours. After the suspension had been cooled to 0° C., 15.6 g of chlorotributyltin (0.048 mol) were added dropwise. The suspension formed was warmed to room temperature and stirred for 1.5 hours. The ether was removed in vacuo and the crude product was dissolved again in hexane, the solution was filtered and the filtrate was dried in vacuo, 17.4 g of the compound 3 (yield: 78%) remaining as a heavy yellow oil. 1H NMR (400 MHz, CD2Cl2) δ 7.67 (d, J=7.5 Hz, 1 H), 7.47 (d, J=7.4 Hz, 1 H), 7.18 (m, 2 H), 6.83 (m, 1 H), 4.28 (s with Sn satellites, 1 H), 1.43-0.78 (m, 33 H). 31P NMR (161.9 MHz, CD2Cl2): δ-61.6 ppm.

1. customa yellow solution being formed
2. customAfter removal of the cooling bath
3. temperaturethe solution was warmed to room temperature
4. temperatureAfter the reaction mixture had been cooled to −30° C.
5. customa precipitate forming
6. stirringAfter stirring at −20° C. for 2 hours
7. additionWhen the addition
8. customthe cooling bath was removed
9. temperaturethe solution was warmed slowly to room temperature
10. stirringsubsequently stirred for 1.5 hours
11. temperatureAfter the suspension had been cooled to 0° C.
12. customThe suspension formed
13. temperaturewas warmed to room temperature
14. stirringstirred for 1.5 hours
15. customThe ether was removed in vacuo
16. dissolutionthe crude product was dissolved again in hexane
17. filtrationthe solution was filtered

ORD-Eintrag

ord-25df81eb137a444e8135e05a2151f562

Quelldatensatz

uspto-grants-2001_05

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US06232413B1