Chemical composition of the defensive secretion of the longhorned beetle, Chloridolum loochooanum.

Adults of the longhorned beetle, Chloridolum loochooanum Gressitt (Coleoptera: Cerambycidae) emit a white frothy secretion from their metasternal glands. This defensive substance contains cyclopentanoid monoterpenoids (iridodials), whose structures were elucidated by gas chromatography-mass spectrometry (GC-MS) and nuclear magnetic resonance (NMR) analyses that compared the naturally occurring structures with synthesized versions. Optically active citronellals, [(S)-, (R)-, and (S)/(R)- mixture], were used as starting materials for synthesizing the corresponding iridodials for the determination of the absolute configuration of the natural product. The retention time of (2S)-iridodial, derived from (S)-citronellal, corresponded to that of C. loochooanum iridodial by enantioselective GC analysis. Thus, we suggest that the absolute configuration of C. loochooanum iridodial is (1R,2S,5S)-iridodial.