反应详情

To a solution of 2,5-dimethoxy-3,6-dimethylbenzene ethanamine (22.0 g, 105 mmol) in acetonitrile (100 ml) was added dropwise a solution of cerium diammonium nitrate (120.9 g, 220 mmol) in acetonitrile (100 ml) and water (200 ml) with cooling on ice over 20 minutes. After stirring at room temperature for 1 hour, the reaction mixture was poured into a mixture of a solution of sodium hydrogen carbonate (138 g, 1640 mmol) in water (400 ml) and ethyl acetate (400 ml) and stirred at the same temperature for 30 minutes. After removing of insolubles by filtration, the organic layer was separated. The aqueous layer was extracted with ethyl acetate and the organic layers were combined. The combined organic layers were washed with saturated brine, and then treated with a solution of 80% sodium hydrosulfite (48 g, 220 mmol) in water (400 ml). The mixture was made basic using a saturated aqueous solution of sodium hydrogen carbonate, and then extracted with ethyl acetate. The extract was washed with saturated brine, dried over sodium sulfate, purified by silica gel chromatography with a small amount of silica gel and eluted with ethyl acetate. The solvent was removed under reduced pressure, and the resultant oil was crystallized front diethyl ether to obtain 14.4 g of the title compound.

1. temperaturewith cooling on ice over 20 minutes
2. stirringstirred at the same temperature for 30 minutes
3. customAfter removing of insolubles by filtration
4. customthe organic layer was separated
5. extractionThe aqueous layer was extracted with ethyl acetate
6. washThe combined organic layers were washed with saturated brine
7. extractionextracted with ethyl acetate
8. washThe extract was washed with saturated brine
9. dry with materialdried over sodium sulfate
10. custompurified by silica gel chromatography with a small amount of silica gel
11. washeluted with ethyl acetate
12. customThe solvent was removed under reduced pressure
13. customthe resultant oil was crystallized front diethyl ether