Differential activity of non-fluorinated and fluorinated analogues of the European corn borer pheromone

Summary.  The differing antagonist activity of (Z)-13-hexadecen-2-one (Z11 – 14 :MK, 1) and its 1,1,1-trifluoro derivative (Z11 –14 :TFMK, 2), two closely related analogues of the European corn borer pheromone Ostrinia nubilalis (Z strain), and their rationale is reported. Both chemicals exhibited some electrophysiological activity, and topical application of 10 pg of pheromone analogue on male antennae was sufficient to induce significantly lower depolarization responses to the pheromone versus untreated insects. In a wind tunnel, the number of European corn borer males attracted to sources containing mixtures of 1 + pheromone in ratios ≥ 1 :1 was significantly lower than the number attracted to a source containing pheromone alone. Source contact behaviour was dramatically impaired when the 1 + pheromone blend reached a ratio of 10 :1, in which only 2% of males displayed source contact in the presence of antagonist. When compound 1 was present at the source, males usually flew upwind with occasional downwind reversals; when compound 2 was present at the lure, males performed wider crosswind reversals, with little progress toward the source. In the field, traps baited with mixtures of both compounds with the pheromone in ratios of 5 :1 and 10 :1 elicited a significantly decreased number of male catches. In esterase inhibition assays, compound 2 was a potent inhibitor (IC₅₀ = 70 nM), whereas the non-fluorinated compound 1 was not. The different activity of both compounds is presumed to be due to different mechanisms of action; considerations for using methyl ketone analogues as new behavioural antagonists of the pheromone are outlined.