Sex Pheromone of the Azalea Mealybug With a Non-Terpene Structure

Mealybug females release sex pheromones to attract conspecific males for mating. It is critical for mealybug males, which are fragile and short-lived, to respond to the pheromone of their species without time- and energy-consuming cross-attractions to other species. Thus, mealybug pheromone systems are considered to have evolved to be species-specific with unique structures in each species and offer an opportunity to study the diversity of pheromone chemistry that mediates intersexual courtship signals. More than 20 mealybug pheromones are reported to be monoterpenes in general, with only one exception, a hemiterpene alcohol esterified with a medium-chain fatty acid (MCFA), found in the Matsumoto mealybug, Crisicoccus matsumotoi. However, it is unknown whether this is truly exceptional, or if similar compounds are used in other related mealybugs. In this study, we isolated and characterized the pheromone of an allied species, the azalea mealybug C. azaleae. Using gas chromatography-mass spectrometry, nuclear magnetic resonance spectroscopy, and bioassays with synthetics, the pheromone was shown to be composed of isopropyl (E)-7-methyl-4-nonenoate, isopropyl (E)-7-methyl-4-octenoate, and ethyl (E)-7-methyl-4-nonenoate. Surprisingly, the structures of these compounds do not include hemiterpene nor monoterpene motifs but have methyl-branched MCFA parts that are similar to an acid moiety of the C. matsumotoi pheromone. This study implies irregular events for the divergence of pheromone structures in ancestors of the genus Crisicoccus and other mealybugs.