Identification, synthesis, and bioassay of a male-specific aggregation pheromone from the harlequin bug, Murgantia histrionica

Sexually mature male harlequin bugs produced a sex-specific compound, identified as one of the stereoisomers of the sesquiterpene epoxyalcohol 4-[3-(3,3-dimethyloxiran-2-yl)-1-methylpropyl]-1-methylcyclohex-2-en-1-ol (henceforth murgantiol), a compound with four chiral centers and 16 possible stereoisomers. Production of the compound was highest during the middle of the day. Individual virgin male bugs in separate containers produced the compound at a higher rate than virgin males in groups. The carbon skeleton was verified by synthesis of several mixtures which, in total, contained all possible isomers, one of which matched the insect-produced compound. The relative and absolute configurations of the insect-produced compound remain to be determined. In laboratory bioassays, insect-produced and synthetic murgantiol attracted harlequin bugs of both sexes, suggesting that murgantiol is a male-produced aggregation pheromone, analogous to those found in a number of other phytophagous bug species.