title: Characterization of epoxytrienes derived from (3Z,6Z,9Z)-1,3,6,9-tetraenes, sex pheromone components of arctiid moths and related compounds.
abstract: Cis-9,10-epoxy-(3Z,6Z)-1,3,6-henicosatriene has been identified from a pheromone gland of arctiid species, such as Hyphantria cunea. Since the diversity of lepidopteran species suggests that structurally related compounds of the 9,10-epoxide are also utilized as a sex pheromone components, epoxytrienes derived from (3Z,6Z,9Z)-1,3,6,9-tetraenes with a C(19)-C(21) chain were systematically synthesized and characterized. While 1,2-epoxy-3,6,9-triene was not obtained, peracid oxidation of each tetraene produced a mixture of three cis-epoxides (3,4-epoxy-1,6,9-triene, 6,7-epoxy-1,3,9-triene, and 9,10-epoxy-1,3,6-triene), which were separable by LC as well as GC. Detailed inspection of the mass spectra of the C(19)-C(21) epoxides indicated the following diagnostic ions for determining the chemical structures: m/z 79, M-70, and M-41 for the 3,4-epoxytrienes; m/z 79, 95, 109, and 149 for the 6,7-epoxytrienes; and m/z 79, 106, 120, M-121, and M-107 for the 9,10-epoxytrienes. Resolution of two enantiomers of each C(21) epoxytriene was accomplished by HPLC equipped with a chiral column, and analysis of the pheromone extracted from virgin females of H. cunea revealed the 9S,10R configuration of the natural epoxytriene as the same configuration of C(21) 9,10-epoxydiene, a main pheromone component of this species. GC-EAD analysis of the optically pure epoxides showed that the antennae of male H. cunea were stimulated more strongly (>100 times) by the (9S,10R)-isomers than the antipodes.
authors: Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan.
authors: Rei
authors: R
authors: Yamakawa
authors: Yoshiko
authors: Y
authors: Takubo
authors: Hiroshi
authors: H
authors: Shibasaki
authors: Yoko
authors: Y
authors: Murakami
authors: Masanobu
authors: M
authors: Yamamoto
authors: Tetsu
authors: T
authors: Ando
mesh_terms: D000818:Animals; D001522:Behavior, Animal / Q000187:drug effects; D002851:Chromatography, High Pressure Liquid; D004852:Epoxy Compounds / Q000737:chemistry*; D005260:Female; D008401:Gas Chromatography-Mass Spectrometry; D009682:Magnetic Resonance Spectroscopy; D008297:Male; D009036:Moths / Q000187:drug effects / Q000378:metabolism*; D011090:Polyenes / Q000737:chemistry* / Q000494:pharmacology; D012724:Sex Attractants / Q000737:chemistry* / Q000494:pharmacology; D013237:Stereoisomerism
chemical_list: D004852:Epoxy Compounds; D011090:Polyenes; D012724:Sex Attractants