Diisopropylamine → Stannane, benzoyltributyl-

Temperature

-30 °C

This example demonstrates the synthesis and purification of the acylstannane complex Bu3SnC(O)Ph. In a nitrogen-filled glove box, a 250 mL three-neck round bottom flask was charged with diisopropylamine (1.31 g, 13.0 mmol) and 40 mL dry THF. The solution was cooled to about −30° C. and 2.5 M BuLi in hexane (5.2 mL, 13.0 mmol) was added slowly by syringe. The reaction mixture was allowed to warm to room temperature. A dropping funnel containing Bu3SnCH(OH)Ph (5.00 g, 12.6 mmol) dissolved in 20 mL dry THF, a nitrogen inlet, and a glass stopper were attached to the round bottom flask. The apparatus was removed from the glove box. The reaction setup was connected to a nitrogen-filled Schlenk line. The reaction mixture was cooled to about −78° C., and the Bu3SnCH(OH)Ph/THF solution was added dropwise. After the addition, the reaction mixture was allowed to stir for 15-20 min at −78° C., during which time the color changed from yellow to light orange. The glass stopper was then removed, and 1,1′-(azo dicarbonyl)dipiperidine (3.18 g, 12.6 mmol) was quickly added as a solid. The resulting reaction mixture was allowed to stir for 20-30 min at −78° C., during which time the reaction mixture turned dark orange. The reaction mixture was allowed to warm to about 0° C., and stirred for approximately 30 min at that temperature. The reaction was quenched at 0° C. by the addition of approximately 14 mL saturated ammonium chloride; solids formed in the reaction mixture. The reaction mixture was brought into a nitrogen-filled glove-box, filtered, dried (MgSO4), and concentrated to afford an orange oil. Chromatography on silica gel using 95/5 hexane/ethyl acetate as the eluent afforded 1.80 g of Bu3SnC(O)Ph as a yellow-orange oil. 1H NMR (C6D6) δ 7.9 (2H, d, Hortho), 7.3 (3H, mult, Hmeta & Hpara), 1.8-0.9 (27H, Bu's); 119Sn NMR (CDCl3) δ 87.4 relative to SnMe4; 13C NMR (CDCl3) δ 244.8 (CO), 142.9, 132.8, 128.8, 127.7 (Caromatic), 29.1, 27.3, 13.6, 11.5 (Cbutyl).

1. additionIn a nitrogen-filled glove box, a 250 mL three-neck round bottom flask
2. temperatureto warm to room temperature
3. customa nitrogen inlet, and a glass stopper were attached to the round bottom flask
4. customThe apparatus was removed from the glove box
5. additionfilled Schlenk line
6. temperatureThe reaction mixture was cooled to about −78° C.
7. additionthe Bu3SnCH(OH)Ph/THF solution was added dropwise
8. additionAfter the addition
9. customThe glass stopper was then removed
10. customThe resulting reaction mixture
11. stirringto stir for 20-30 min at −78° C., during which time the reaction mixture
12. temperatureto warm to about 0° C.
13. stirringstirred for approximately 30 min at that temperature
14. customThe reaction was quenched at 0° C. by the addition of approximately 14 mL saturated ammonium chloride
15. customsolids formed in the reaction mixture
16. additionfilled glove-box
17. filtrationfiltered
18. dry with materialdried (MgSO4)
19. concentrationconcentrated
20. customto afford an orange oil

ORD record

ord-0597a4d5e5834b3a9a266732dec1b0c0

Source dataset

uspto-grants-2010_03

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07683004B2