Hydrocarbons with a homoconjugated polyene system and their monoepoxy derivatives: Sex attractants of geometrid and noctuid moths distributed in Japan

Abstract

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.