role of autoxidation of alpha-pinene in the production of pheromones of Dendroctonus ponderosae (Coleoptera: Scolytidae)

The monoterpene α-pinene, a major component of the terpene composition of Pinus spp., has been reported to act as a host-produced kairomone for a variety of bark beetle species, including the mountain pine beetle, Dendroctonusponderosae Hopkins. However, our experiments indicate that α-pinene autoxidizes under normal temperature and atmospheric conditions to form significant quantities of trans-verbenol, an aggregation pheromone for many species of bark beetles. The quantities of α-pinene present in the resin that can flow from small wounds in pine trees appear to be sufficient to produce trans-verbenol at rates similar to those by female beetles that are actively synthesizing the compound.trans-Verbenol can then autoxidize rapidly to form verbenone, with the content of this compound reaching 8% within 13 weeks of exposure to air. Verbenone is often used by scolytids as an antiaggregation pheromone. Approximately 1.9% of the trans-verbenol and 2.7% of the verbenone found in Porapak Q aerations of phloem with boring spruce beetle, Dendroctonusrufipennis (Kirby), females, as well as 0.8% of the trans-verbenol and 0.8% of the verbenone found in aerations of phloem with boring D. ponderosae females, was due to the autoxidation of α-pinene and (or) the release of oxygenated compounds found in the phloem before bark beetle attack. The natural interconversion of α-pinene, trans-verbenol, and verbenone under ambient conditions suggests that many experiments involving the behavioral activity of these compounds require re-evaluation.