Studies on seven-membered heterocycles. XXXI. Synthesis of 1,4-oxazepinones and 1,4-diazepinones from 2-pyridones and their conversion into fully unsaturated 1,4-oxazepines and 1,4-diazepines.
作者:Jyoji KURITA、Takeharu YONEDA、Naoki KAKUSAWA、Takashi TSUCHIYA
DOI:10.1248/cpb.38.2911
日期:——
Thermolysis of the 6-aza-3-oxatricyclo[3.2.0.02, 4]heptan-7-ones(8 and 21) and 3, 6-diazatricyclo[3.2.0.02, 4]heptan-7-ones (9 and 22), prepared from the corresponding 2-pyridones (5) via the 2-azabicyclo[2.2.0]hex-5-en-3-ones (7 and 18), resulted in valence isomerization with ring opening to give the novel 1, 4-oxazepin-5-ones (10a-e and 15a-c) and 1, 4-diazepin-5-ones (11a-e and 16a-c), respectively. Treatment of the N-unsubstituted compounds 15 and 16 with triethyloxonium tetrafluoroborate afforded the fully unsaturated 1, 4-oxazepines (23a-c) and 1H-1, 4-diazepines (24a-c), respectively.
由相应的 2-吡啶酮 (5) 通过 2-氮杂双环[2.2.0]己-5-烯-3-酮(7 和 18),在开环时发生价异构化,分别得到新型 1,4-氧氮杂卓-5-酮(10a-e 和 15a-c)和 1,4-二氮杂卓-5-酮(11a-e 和 16a-c)。用四氟硼酸三乙氧基鎓处理 N-未取代的化合物 15 和 16,可分别得到完全不饱和的 1,4-氧氮杂卓(23a-c)和 1H-1,4-二氮杂卓(24a-c)。