Division of Technology for Society, TNO, P.O. Box 217, 2600, Delft, AE, The Netherlands.
J Chem Ecol. 1982 Feb;8(2):439-51. doi: 10.1007/BF00987792.
Two independently biologically active compounds, periplanone A and periplanone B can be isolated from fecal material of the American cockroach,Periplaneta americana. In fecal material these occur in a ratio of 1 ∶ 10 while, in intestinal tracts only periplanone B has been found. The latter has been identified as (1Z,5E)-1,10(14)-diepoxy-4(15),5-germacradien-9-one; the identification was confirmed by synthesis. Only the CD (-) enantiomer (1R,2R,5E,7S,10R) exhibited activity. The lower threshold of activity of both natural and synthetic CD (-) pheromone, is 10(-6)-10(-7) μg. Periplanone A has been identified (apart from its stereochemical configuration) as 7-methylene-4-isopropyl-12-oxa-tricyclo[4.4.2.0(1,5)]-9-dodecen-2-one). The structure of this rather unstable compound could be deduced by comparing its NMR, UV, IR, and mass spectra with the NMR and mass spectra of its rearrangement product. Both structures still require confirmation by synthesis, but their spectral data are in complete agreement with the proposed structures. The presence of only periplanone B in the gut and the presence of both periplanone A and periplanone B in the feces suggests that periplanone B is a genuine sex pheromone, whereas peri-planone A might be a biologically active transformation product, which in turn can isomerize into a more stable, but inactive compound.
两种具有生物活性的独立化合物，即瓜叶菊内酯 A 和瓜叶菊内酯 B，可以从美洲大蠊（Periplaneta americana）的粪便中分离出来。在粪便中，这两种化合物的比例为 1:10，而在肠道中只发现了瓜叶菊内酯 B。后者被鉴定为（1Z,5E）-1,10(14)-环氧-4(15),5-二烯-9-酮；其鉴定通过合成得到了证实。只有 CD（-）对映异构体（1R,2R,5E,7S,10R）表现出活性。天然和合成的 CD（-）信息素的活性下限为 10(-6)-10(-7)μg。瓜叶菊内酯 A 已被鉴定（除了其立体化学构型）为 7-亚甲基-4-异丙基-12-氧杂三环[4.4.2.0(1,5)]-9-十二烯-2-酮）。通过比较其 NMR、UV、IR 和质谱与重排产物的 NMR 和质谱，可以推断出这种相当不稳定的化合物的结构。这两种结构都需要通过合成来确认，但它们的光谱数据与所提出的结构完全一致。肠道中只存在瓜叶菊内酯 B，粪便中同时存在瓜叶菊内酯 A 和瓜叶菊内酯 B，这表明瓜叶菊内酯 B 是一种真正的性信息素，而瓜叶菊内酯 A 可能是一种具有生物活性的转化产物，它可以进一步异构化为更稳定但无活性的化合物。
