Department of Chemistry, Wrocław University of Environmental and Life Sciences, Wrocław, Poland.
J Agric Food Chem. 2013 Apr 10;61(14):3364-72. doi: 10.1021/jf3052219. Epub 2013 Mar 28.
Two racemic and two enantiomeric pairs of new saturated lactones with the p-menthane system were obtained. The lactones were synthesized from racemic and enantiomerically enriched cis- and trans-piperitols, which were obtained from piperitone. The structures of the compounds were confirmed by spectroscopic data. The antifeedant activity of piperitone to Myzus persicae was studied, and the biological consequences of structural modifications of piperitone, that is, lactonization and chiral center configuration, were examined as well. The behavioral responses of M. persicae to piperitone and piperitone-derived saturated lactones were investigated to reveal the biological background of their deterrent activity. Piperitone appeared rather neutral or weakly deterrent to aphids. The introduction of a lactone moiety into a piperitone molecule dramatically changed its biological activity. All piperitone-derived lactones evoked negative aphid responses. However, the deterrent activity of individual compounds varied in potency, the time of expression, and the duration of the effect, depending on the spatial structure of the lactone. Lactones (1R,3S,6R)-3-isopropyl-6-methyl-9-oxabicyclo[4.3.0]nonan-8-one and trans-3-isopropyl-6-methyl-9-oxabicyclo[4.3.0]nonan-8-one showed the broadest ranges and the highest potencies and durabilities of deterrent activity to M. persicae: they acted immediately after application, caused a cessation of probing before aphids reached phloem elements, and decreased the quality of phloem sap.
从胡椒酮中获得了具有对薄荷烷系统的两个外消旋和两对对映异构体的新饱和内酯。通过从胡椒酮获得的外消旋和对映体富集的顺式和反式胡椒醇合成了内酯。通过光谱数据证实了化合物的结构。研究了胡椒酮对桃蚜的拒食活性，并研究了胡椒酮的结构修饰（内酯化和手性中心构型）的生物学后果。研究了桃蚜对胡椒酮和胡椒酮衍生的饱和内酯的行为反应，以揭示其驱避活性的生物学背景。胡椒酮对蚜虫表现出相当中性或弱的驱避作用。将内酯部分引入胡椒酮分子中会极大地改变其生物学活性。所有胡椒酮衍生的内酯都引起了蚜虫的负面反应。然而，取决于内酯的空间结构，个别化合物的驱避活性在效力、表达时间和效果持续时间方面存在差异。内酯（1R，3S，6R）-3-异丙基-6-甲基-9-氧杂双环[4.3.0]壬烷-8-酮和反式-3-异丙基-6-甲基-9-氧杂双环[4.3.0]壬烷-8-酮表现出对桃蚜最广泛的范围和最高的效力和耐久性：它们在应用后立即起作用，在蚜虫到达韧皮部元素之前阻止探测，并且降低了韧皮部汁液的质量。
