Indene → HCID 70151496, compound

Temperature

-20 °C

100 ml of ether were placed in a round-bottomed flask containing 3.8 g (0.033 moles) of indene and the solution was cooled to −20° C. 14.4 ml of a 2.3 molar solution of butyllithium in hexane (0.033 moles) were added over 5 minutes to form a yellow solution. After removal of the cooling bath, the solution was heated to room temperature and subsequently stirred for 1.5 h. The reaction mixture was then cooled to 0° C. and 5.0 g of chlorodiisopropylphosphine (0.033 moles) were added to form a precipitate. After removal of the cooling bath, the solution was heated to room temperature and stirred for 1 h. The solution was then cooled to −20° C. and 14.4 ml of a 2.3 molar solution of butyllithium in hexane (0.033 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., 10.1 g of chlorotributyltin (0.031 moles) 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 16.6 g of compound 8 (yield: 97%) in the form of a heavy yellow oil. Two isomers were obtained in proportions of 1.5:1. The main isomer was identified as follows: 1H NMR (400 MHz, CD2Cl2): δ=7.71 (d, J=7.2 Hz, 1H); 7.41 (d, J=7.3 Hz, 1H); 7.13 (m, 2H); 6.96 (m, 1H); 4.28 (s with Sn satellites, 1H); 2.21 (m, 1H); 1.54 (m, 1H); 1.45-0.65 (m, 39H); 31P NMR (161.9 MHz, CD2Cl2): δ=−11.3 ppm. The secondary isomer was identified as follows: 1H NMR (400 MHz, CD2Cl2): δ=7.6 (d, J=7.4 Hz, 1H); 7.46 (d, J=7.2 Hz, 1H); 7.26 (t, J=7.5 Hz, 1H); 7.1 (m, 1H); 6.71 (m, 1H); 3.48 (m, 1H); 2.21 (m, 1H); 1.54 (m, 1H); 1.45-0.65 (m, 39H); 31P NMR (161.9 MHz, CD2Cl2): d=−1.5 ppm.

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

ORD record

ord-e918516bf23d46d6acd0f8c26787d90b

Source dataset

uspto-grants-2002_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06433112B1