Structural significance of the geminal-dimethyl group of (+)-trans-verbenyl acetate, sex pheromone mimic of the American cockroach.

The significance of the geminal dimethyl group at C-6 of (+)-trans-veibenyl acetate (Ib), a sex pheromone mimic of the American cockroach, was investigated. Our interest was first directed to eliminating either methyl group of the geminal dimethyl group. Consequently, alcohols (IIIa and IVa) possessing a monomethyl group at C-6 were successfully obtained. Acetate (IVb) and propionate (IVc) of alcohol (IVa) possessing only a C-9 methyl group induced sex pheromonal activity at the 0.5 (IVb) and 0.02 mg (IVc) dose levels, respectively, while acetate (IIIb) of a alcohol (IIIa) with only C-8 methyl group was inactive. Alcohol (Va), which has an ethyl group at the C-6 instead of C-9 methyl, was also synthesized and converted into its acetate (Vb), which showed no activity. From these results, the significance of the dimethyl group is discussed relative to spatial requirements of the molecule for the receptor space. The M/F ratio in EAG was also evaluated for the synthesized esters. The M/F ratio index represented well the potency of pheromonal activity.