Stannane, tributyl(1-ethoxyethenyl)- → HCID 58579338, compound

Temperature

65 °C

To a suspension of 2-chloro-6-methoxy-3-nitropyridine (600 g) and PdCl2(PPh3)2 (33.5 g) in acetonitrile (4200 ml) at 65° C. under N2 was added dropwise over 2 h (1-ethoxyvinyl)-tributyl-stannane (1182 ml). The resulting suspension was stirred at 65° C. for 4 h then left to cool to room temperature overnight. The reaction mixture was quenched with 10% KF aqueous solution (3600 ml) with vigorous stirring and stirred for 1 h. The resulting solid was removed by vacuum filtration and washed with acetonitrile (7×1000 ml). The layers were separated and the organic layer was evaporated to 3000 ml. This was filtered through Whatman, GF/B glass microfibre filter paper and the small amount of brown solid removed was washed with MeCN (1800 ml). EtOAc (3600 ml) was added and the volume reduced to 1800 ml. Cyclohexane (3600 ml) was added and the volume reduced to 3000 ml. Cyclohexane (2400 ml) and silica gel (600 g, 1 wt) were added and allowed to stir at room temperature for 1.5 h. The solid was removed by vacuum filtration and washed with EtOAc/cyclohexane, 1:8 (4200 ml). The filtrate was reduced to 1800 ml. Cyclohexane (2400 ml) was added and the volume reduced to 1800 ml. Cyclohexane (3600 ml) and EtOAc (600 ml) and silica gel (600 g, 1 wt) were added and stirred for 1.5 h. The solid was removed by vacuum filtration and washed with EtOAc/cyclohexane 1:8 (4200 ml). The solvents were evaporated to dryness. MeCN (2000 ml) was added and evaporated to give an orange coloured oil.

1. waitthen left
2. temperatureto cool to room temperature overnight
3. customThe reaction mixture was quenched with 10% KF aqueous solution (3600 ml)
4. stirringwith vigorous stirring
5. stirringstirred for 1 h
6. customThe resulting solid was removed by vacuum filtration
7. washwashed with acetonitrile (7×1000 ml)
8. customThe layers were separated
9. customthe organic layer was evaporated to 3000 ml
10. filtrationThis was filtered through Whatman, GF/B glass microfibre
11. filtrationfilter paper
12. customthe small amount of brown solid removed
13. washwas washed with MeCN (1800 ml)
14. additionEtOAc (3600 ml) was added
15. additionCyclohexane (3600 ml) was added
16. additionCyclohexane (2400 ml) and silica gel (600 g, 1 wt) were added
17. stirringto stir at room temperature for 1.5 h
18. customThe solid was removed by vacuum filtration
19. washwashed with EtOAc/cyclohexane, 1:8 (4200 ml)
20. additionCyclohexane (2400 ml) was added
21. additionCyclohexane (3600 ml) and EtOAc (600 ml) and silica gel (600 g, 1 wt) were added
22. stirringstirred for 1.5 h
23. customThe solid was removed by vacuum filtration
24. washwashed with EtOAc/cyclohexane 1:8 (4200 ml)
25. customThe solvents were evaporated to dryness
26. additionMeCN (2000 ml) was added
27. customevaporated
28. customto give an orange coloured oil

ORD record

ord-7df7db5cf4c14343956ea2137339f1d8

Source dataset

uspto-grants-2012_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08318940B2