(S,S)-2,12-, (S,S)-2,13-, and (S,S)-2,14-Diacetoxyheptadecanes: Sex Pheromone Components of Red Cedar Cone Midge, Mayetiola thujae

Abstract

We identified, synthesized, and field-tested the sex pheromone of female red cedar cone midge Mayetiola thujae (Hedlin) (Diptera: Cecidomyiidae), a pest insect in red cedar Thuja plicata seed orchards. Coupled gas chromatographic (GC)–electroantennographic detection analyses of pheromone extract revealed three components (A, B, C) that elicited responses from antennae of males, all of which occurred below the detection threshold of the mass spectrometer and thus had to be identified without spectroscopic data. Taking into account (1) their retention indices (RI) on three GC columns (DB-5, DB-23, and DB-210), (2) intercolumn RI differentials, and (3) the molecular structures of known cecidomyiid pheromones, we synthesized seven candidate pheromone components: 2,10-, 2,11-, 2,12-, 2,13-, 2,14-, 2,15- and 2,16-diacetoxyheptadecanes. Of these, 2,12-, 2,13-, and 2,14-diacetoxyheptadecane had RIs on all columns consistent with those of A, B, and C and elicited strong antennal responses when tested at picogram levels. In field experiments with the twelve stereoselectively synthesized stereoisomers, only the SS-stereoisomers of 2,12-, 2,13-, and 2,14-diacetoxyheptadecane attracted male M. thujae. The three-component SS-stereoisomer blend was more attractive than the 12-component blend of all stereoisomers, suggesting that one or several nonnatural stereoisomers are inhibitory. One-, two-, and three-component lures of the SS-stereoisomers were equally effective in attracting male M. thujae, indicating redundancy in the pheromone. Identification of the M. thujae sex pheromone will allow development of pheromone-based monitoring, and possibly control, of M. thujae populations in T. plicata seed orchards.