反应详情

To a solution of dipyridin-3-ylmethanol (9 g, 48 mmol) in 9:1 methylene chloride/acetonitrile (100 mL) was added powdered 4A molecular sieves (24 g) and NMO (8.5 g, 72 mmol). The resulting mixture was cooled in an ice bath and TPAP (0.85 g, 2.4 mmol) added carefully in 3 portions at 5 min intervals. After stirring for 15 min the ice bath was removed and stirring was continued at RT. After stirring for 3 days, the reaction mixture was filtered through Celite and the cake washed well with methylene chloride and then chloroform. The filtrate was concentrated to approximately ⅓ the original volume then silica gel was added. The remaining solvent was removed leaving the crude material adsorbed onto the silica gel as a dark green powder. This powder was layered on top of an equal volume of silica gel in a Buchner funnel and flushed with ether. These washings were discarded. The silica pad was then flushed repeatedly first with methylene chloride then with chloroform until no further product eluted. The dark red filtrate was concentrated to give a red brown solid. Trituration with ether gave dipyridin-3-ylmethanone as a white powder. The mother liquors were stripped and the residue chromatographed (eluting with 24:1 methylene chloride/methanol). The fractions enriched in product were combined, stripped, and the residue triturated with ether to give a second crop of pure ketone.

1. temperatureThe resulting mixture was cooled in an ice bath
2. customwas removed
3. customwas continued at RT
4. stirringAfter stirring for 3 days
5. filtrationthe reaction mixture was filtered through Celite
6. washthe cake washed well with methylene chloride
7. concentrationThe filtrate was concentrated
8. additionsilica gel was added
9. customThe remaining solvent was removed
10. customleaving the crude material
11. customflushed with ether
12. customThe silica pad was then flushed repeatedly first with methylene chloride
13. washwith chloroform until no further product eluted
14. concentrationThe dark red filtrate was concentrated
15. customto give a red brown solid