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鉴于某些羟酮肟具有生化活性,本文报道两类羟基酮肟的合成及其异构体的分离。众所周知,酮肟存在几何异构体,但当年Meyer等和Gabriel等报道α-羟基苯乙酮肟时则尚未发现有异构体。我们在制备上述酮肟时获得两种新晶体,一为m.p.67～69℃的鳞片状结晶la;一为m.p.124～126℃的细针晶lb。根据元素分析和红外光谱推测,两者为几何异构体。为确定它们的构型,分别把la和lb以聚磷酸催化,进行Beckmann重排成相应的酰胺,然后用碱水解,一个水解后检出有苯胺;另一个在水解过程中有强烈的氨味,酸化时得苯甲酸,由此推定了la和lb的几何构型。
In view of the biochemical activity of some of the hydroxy ketoximes, two types of hydroxy ketoximes were synthesized and their isomers separated. It is well-known that there are geometrical isomers of ketoxime, but no isomers have been found when Meyer et al. And Gabriel et al. Reported α-hydroxyacetophenone oxime. We prepared two new crystals in the ketoxime obtained, one for the m.p.67 ~ 69 ° C flaky crystals la; a for the m.p.124 ~ 126 ℃ fine needle crystal lb. According to elemental analysis and FTIR speculation, the two are geometric isomers. In order to determine their configuration, la and lb were catalyzed by polyphosphoric acid, respectively, followed by Beckmann rearrangement to the corresponding amides followed by hydrolysis with aniline followed by aniline after hydrolysis; the other was strongly ammoniacal during hydrolysis , When acidified to have benzoic acid, which presumes the geometry of la and lb.