(S,S)-2,12-, (S,S)-2,13-, and (S,S)-2,14-diacetoxyheptadecanes: sex pheromone components of red cedar cone midge, Mayetiola thujae.

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.

(2R,7S)-diacetoxytridecane: sex pheromone of the aphidophagous gall midge, Aphidoletes aphidimyza.

In a recent study, evidence was presented that females of the aphidophagous midge Aphidoletes aphidimyza (Rondi) (Diptera: Cecidomyiidae) release a sex pheromone to attract mates. Our objectives were to identify and bioassay the pheromone. Coupled gas chromatographic-electroantennographic detection(GC-EAD) analyses of untreated and hydrogenated pheromone extract on three fused-silica columns (DB-5, DB-23, DB-210) revealed a single compound that elicited responses from male antennae. Retention index calculations of this candidate pheromone (CP) suggested that it was a di-acetate. Considering that most of the presently identified cecidomyiid pheromones consist of a 13-carbon chain with (at least) one acetate group in C2, we synthesized 2,6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,11-, and 2,12-diacetoxytridecane. In GC analyses of these compounds, only 2,7-diacetoxytridecane cochomatographed with CP on all columns. In laboratory two-choice experiments with stereospecifically synthesized stereoisomers, only (2R,7S)-diacetoxytridecane elicited significant anemotatic responses by male A. aphidimyza. In trapping experiments in greenhouse compartments, only traps baited with (2R,7S)-diacetoxytridecane captured significant numbers of male A. aphidimyza, clearly revealing the absolute configuration of the pheromone. Failure of the stereoisomeric mixture (containing all four stereoisomers including the pheromone) to attract males is due to inhibitory characteristics of the (2R,7R)- and (2S,7R)-stereoisomers. The pheromone of zoophagous A. aphidimyza resembles those from phytophagous cecidomyiid midges, suggesting a common, diet-independent pathway for pheromone biosyntheses.

(Z,Z)-4,7-tridecadien-(S)-2-yl acetate: sex pheromone of Douglas-fir cone gall midge, Contarinia oregonensis.

Our objectives were to identify and field test the sex pheromone of female Douglas-fir cone gall midge, Contarinia oregonensis (Diptera: Ce-cidomyiidae). Coupled gas chromatographic-electroantennographic detection (GC-EAD) analyses of pheromone extract revealed a single compound (A) that elicited responses from male antennae. Hydrogenation of pheromone extract, followed by renewed GC-EAD analysis, revealed a new EAD-active compound with chromatographic characteristics identical to those of tridecan-2-yl acetate on five fused silica columns (DB-5, DB-210, DB-23, SP-1000, and Cyclodex-B). Syntheses, chromatography, and retention index calculations of all possible tridecen-2-yl acetates suggested that the candidate pheromone A was a tridecadien-2-yl acetate with nonconjugated double bonds. Synthetic candidate pheromone component (Z,Z)-4,7-tridecadien-2-yl acetate (Z4Z7) cochromatographed with A on all analytical columns and elicited comparable antennal activity. In GC-EAD analyses that separated the enantiomers (Z,Z)-4,7-tridecadien-(S)-2-yl acetate (2S-Z4Z7) and (Z,Z)-4,7-tridecadien-(R)-2-yl acetate (2R-Z4Z7) with baseline resolution, only 2S-Z4Z7 as a component in a racemic standard or in pheromone extract elicited antennal responses. In Douglas-fir seed orchards, sticky traps baited with 2S-Z4Z7 captured male C. oregonensis, whereas 2R-Z4Z7 was behaviorally benign. Comparable catches of males in traps baited with racemic Z4Z7 (50 microg) or virgin female C. oregonensis suggested that synthetic pheromone baits could be developed for monitoring C. oregonensis populations in commercial Douglas-fir seed orchards.