Electrophilic derivatives antagonise pheromone attraction in Cydia pomonella.

BACKGROUND: Pheromone antagonists are good disruptants of the pheromone communication in insects and, as such, have been used in mating disruption experiments. In this study, new non-fluorinated electrophilic keto derivatives structurally related to the pheromone of Cydia pomonella (codlemone) have been synthesised and tested as putative pheromone antagonists. RESULTS: Codlemone (1) was prepared in excellent stereoselectivity in a new, iterative approach involving two Horner-Wadsworth-Emmons reactions. Methyl ketone (2), keto ester (3) and diketone (4) were obtained from codlemone in straightforward approaches in good overall yields and excellent stereochemical purity (≥98% E,E). In electrophysiology, only compound 2 displayed inhibition of the antennal response to the pheromone after presaturation of the antennal receptors. Compounds 2 to 4 did not inhibit the pheromone-degrading enzyme responsible for codlemone metabolism, but mixtures of ketone 2 and diketone 4 with codlemone elicited erratic flights on males in a wind tunnel. In the field, blends of either compound (2 or 4) with the pheromone caught significantly fewer males than codlemone alone. CONCLUSION: Codlemone and the potential antagonists 2 to 4 have been synthesised in good yields and excellent stereoselectivity. These chemicals behave as pheromone antagonists of the codling moth both in the laboratory and in the field.

[Mechanism of cis-8-dodecenyl acetate suppression of male Laspeyresia pomonella codling moth responses to the sex attractant trans-8,10-dodecadienol]. / O mekhanizme podavleniia tsis-8-dodetsenilatsetatom reaktsii na polovoi attraktant trans-8,10-dodekadienol u samtsov iablonnoi plodozhorki Laspeyresia pomonella.

In field experiments, studies have been made on sex attractiopn of males in the moth L. pomonella. Cis-8-dodecenyl acetate (DDA) was confirmed to be a potent inhibitor of male attraction to the traps baited with virgin females or to a synthetic sex attractant (sex pheromone) trans-8,10-dodecadienol (DDD). DDA also slightly reduced the mating activity under laboratory conditions. The inhibitory effect of DDA on male sex attraction was studied by means of electroantennogram technique. Male antennae were stimulated by DDD and DDA either separately or in combination, DDA vapours being superimposed on the constant DDD background. DDD evoked always negative (excitatory) EAGs, but DDA elicited complex EAGs including both negative and positive (excitatory) EAGs, but DDA elicited complex EAGs including both negative and positive waves. Experiments with double stimulation showed that DDD and DDA produce excitation in different groups of the olfactory receptor cells. Besides, DDA was found to inhibit the EAG evoked by DDD. This inhibition is presumably due to hyperpolarization of the DDD-sensitive cells. Both physiological effects may be involved into inhibition of behavioural reactions in males. The inhibitory mechanism based on competition between DDA and DDD molecules for common receptor sites, seems to be lessprobable.