反应详情

温度

-78 °C

A solution of 2-(6,11-dihydro-11-oxodibenz[b,e]oxepin-2-yl)acetyl chloride (15.00 g) in 150 ml of dry diglyme was stirred at -78° C. under nitrogen as lithium tri-tert-butoxyaluminohydride (104.6 ml of a 0.5M solution in diglyme) was added slowly dropwise over one hour. The reaction was stirred ten minutes at -78° C. and then quenched with 3 ml of glacial acetic acid added slowly dropwise. After warming the reaction to room temperature 50 ml of pyridine and 2 equiv. of hydroxylamine hydrochloride (7.27 g) was added and the slurry stirred at 50° C. for two hours. The solvent was evaporated using high vacuum and the residue taken up in chloroform and 1N HCl. The layers were separated and the aqueous phase extracted with chloroform. The combined organic phases were dried (MgSO4), filtered, and evaporated. The residue was purified by flash chromatography (silica; 5:2 hex-EtOAc) and recrystallized from ethyl acetate-hexane to give 2-(6,11-dihydro-11-oxodibenz[b,e]oxepin-2-yl)acetaldoxime, as crystals, m.p. 132°-134° C.

1. additionwas added slowly dropwise over one hour
2. customquenched with 3 ml of glacial acetic acid
3. additionadded slowly dropwise
4. temperatureAfter warming
5. additionwas added
6. stirringthe slurry stirred at 50° C. for two hours
7. customThe solvent was evaporated
8. customThe layers were separated
9. extractionthe aqueous phase extracted with chloroform
10. dry with materialThe combined organic phases were dried (MgSO4)
11. filtrationfiltered
12. customevaporated
13. customThe residue was purified by flash chromatography (silica; 5:2 hex-EtOAc)
14. customrecrystallized from ethyl acetate-hexane