Department of Applied Biological Science, Faculty of Agriculture, Tokyo University of Agriculture and Technology, Fuchu, 183, Tokyo, Japan.
J Chem Ecol. 1993 Apr;19(4):787-98. doi: 10.1007/BF00985009.
Although several sex pheromones of the family Geometridae have been characterized, investigations on Japanese species are limited. In order to obtain more information, screening using known sex pheromones and their analogs was carried out. The (Z,Z,Z)-3,6,9-triunsaturated and (Z,Z)-6,9-diunsaturated hydrocarbons with straight C(19)-C(21) chains were synthesized by the Grignard coupling reaction as a key step starting from linolenic and linoleic acids, respectively. Oxidation of the homoconjugated trienes withm-chloroperoxybenzoic acid yielded a 1∶1∶1 mixture of three monoepoxy derivatives that could be separated by silica gel chromatography. The chemical structure of each positional isomer was confirmed using two-dimensional NMR techniques and MS measurements, which enabled characteristic fragment ions from the isomers to be identified. Field tests using lures incorporating only one of the above six hydrocarbons or nine epoxides were carried out in a forest in Tokyo. Consequently, attraction of male moths of 14 geometrid species in addition to four species in another family, the Noctuidae, was observed. It was concluded that hydrocarbons with a homoconjugated polyene system and the monoepoxy derivatives are important components of sex pheromones produced by Japanese lepidopterous insects, particularly the geometrid moths.
虽然已经对天蛾科的几种性信息素进行了描述，但对日本物种的研究有限。为了获得更多信息，使用已知的性信息素及其类似物进行了筛选。通过格氏偶联反应，分别从亚麻酸和亚油酸出发，作为关键步骤合成了具有直链 C(19)-C(21)链的 (Z,Z,Z)-3,6,9-三不饱和和 (Z,Z)-6,9-二不饱和烃。用间氯过氧苯甲酸氧化同共轭三烯得到三种单环氧化物的 1:1:1 混合物，可通过硅胶色谱分离。使用二维 NMR 技术和 MS 测量对每个位置异构体的化学结构进行了确认，这使得能够识别异构体的特征片段离子。在东京的一片森林中进行了仅包含上述六种碳氢化合物或九种环氧化物之一的诱捕器的田间试验。结果，观察到 14 种天蛾科和另一家族夜蛾科的 4 种雄性蛾对除了 14 种天蛾科和另一家族夜蛾科的 4 种以外的 14 种天蛾科和另一家族夜蛾科的雄性蛾具有吸引力。可以得出结论，具有同共轭多烯系统的碳氢化合物和单环氧化物衍生物是日本鳞翅目昆虫产生性信息素的重要组成部分，特别是天蛾科的蛾类。
