1-Fluoro-4-hydroxy-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) → 1-(6-Bromopyridin-2-yl)-2-fluoroethanone

1-(6-Bromopyridin-2-yl)ethanone (2 g, 10.0 mmol) and 1-fluoro-4-hydroxy-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (9.65 g, 15.0 mmol) were combined in MeOH (100 mL) and heated to reflux for 3 days. After cooling to room temperature, the white solid (alumina) was removed by filtration and filtrate was concentrated in vacuo. The residue was taken up in EtOAc and water and extracted with EtOAc (2×). The combined organic extracts were washed with brine, dried over MgSO4, filtered, and concentrated in vacuo. The residue was stirred in a combination of 6 N HCl and Et2O overnight. The organic phase was separated and the aqueous phase extracted with Et2O. The combined organic extracts were washed with brine, dried over MgSO4, filtered, and concentrated in vacuo. Purification of the residue by silica gel column chromatography (0-20% EtOAc-hexanes) gave the title compound as a white solid.

1. temperatureheated
2. temperatureto reflux for 3 days
3. customthe white solid (alumina) was removed by filtration and filtrate
4. concentrationwas concentrated in vacuo
5. extractionwater and extracted with EtOAc (2×)
6. washThe combined organic extracts were washed with brine
7. dry with materialdried over MgSO4
8. filtrationfiltered
9. concentrationconcentrated in vacuo
10. customThe organic phase was separated
11. extractionthe aqueous phase extracted with Et2O
12. washThe combined organic extracts were washed with brine
13. dry with materialdried over MgSO4
14. filtrationfiltered
15. concentrationconcentrated in vacuo
16. customPurification of the residue by silica gel column chromatography (0-20% EtOAc-hexanes)

ORD record

ord-eb637eb3f31640b8b33a6d66c56a8fd6

Source dataset

uspto-grants-2013_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08367706B2