Abstract
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.
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References
Corey, E.J., andSuggs, J.W. 1975. Pyridinium chlorochromate. An efficient reagent for oxidation of primary and secondary alcohols to carbonyl compounds.Tetrahedron Lett. 1975:2647–2650.
Nishino, C., andKimura, R. 1981. Isolation of sex pheromone mimic of the American cockroach by monitoring with male/female ratio in electroantennogram.J. Insect Physiol. 27:305–311.
Nishino, C., andTakayanagi, H. 1979a. Studies on the sex pheromone mimic of the American cockroach, (+)-trans-verbenyl acetate. Part I: Synthesis of verbenols and related alcohols and their PMR spectra with shift reagent.Agric. Biol. Chem. 43:1967–1974.
Nishino, C., andTakayanagi, H. 1979b. Studies on the sex pheromone mimic of the American cockroach, (+)-trans-verbenyl acetate. Part II: Conformational analysis of verbenols and related alcohols by PMR spectra with a chemical shift reagent.Agric. Biol. Chem. 43:2323–2329.
Nishino, C., andTakayanagi, H. 1981a. Studies on the sex pheromone mimic of the American cockroach, (+)-trans-verbenyl acetate. Part VI: Sex pheromonal activity of (+)-trans-verbenyl acetate and related compounds to the American cockroach,Periplaneta americana L.J. Chem. Ecol 7:853–865.
Nishino, C., andTakayanagi, H. 1981b. Studies on the sex pheromone mimic of the American cockroach, (+)-trans-verbenyl aceate. Part VII: Male/female ratio in electroantennogram responses of the American cockroach to (+)-trans-verbenyl acetate and related compounds: Relationship between the ratio and sex pheromonal activity.Comp. Biochem. Physiol. 70A:229–234.
Nishino, C., Tobin, T.R., andBowers, W.S. 1977a. Sex pheromone mimics of the American cockroach (Orthoptera: Blattidae) in monoterpenoids.Appl. Entomol. Zool. 12:287–290.
Nishino, C., Tobin, T.R., andBowers, W.S. 1977b. Electroantennogram responses of the American cockroach to germacrene-D sex pheromone mimic.J. Insect Physiol. 23:415–419.
Nishino, C., Takayanagi, H., andKimura, R. 1980. Electroantennogram and behavioral responses of the American cockroach to sex pheromone mimics.Comp. Biochem. Physiol. 66A:393–398.
Nishino, C., Takayanagi, H.,andManabe, S. 1982. Studies on the sex pheromone mimic of the American cockroach, (+)-trans-verbenyl acetate. Part IX: Comparison of sex pheromonal activity to the American cockroach between acetates and propionates of verbenyl type alcohols. Agric. Biol. Chem. 46:2781–2785.
Takayanagi, H., andNishino, C. 1982. Studies on the sex pheromone mimic of the American cockroach, (+)-trans-verbenyl acetate. Part VIII: Structural significance of the alkyl substituent at the C-4 of (+)-trans-verbenyl acetate in sex pheromonal activity of the American cockroach.J. Chem. Ecol. 8:883–895.
Washio, H., Nishino, C., andBowers, W.S. 1976. Antennal receptor response to sex pheromone mimics in the American cockroach.Nature 262:487–489.
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Studies on the sex pheromone mimic of the American cockroach, (+)-trans-verbenyl acetate. Part X. For Part IX, see Nishino et al.,Agric. Biol. Chem. 46:2781 (1982).
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Manabe, S., Takayanagi, H. & Nishino, C. Structural significance of the geminal-dimethyl group of (+)-trans-verbenyl acetate, sex pheromone mimic of the American cockroach. J Chem Ecol 9, 533–549 (1983). https://doi.org/10.1007/BF00990225
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DOI: https://doi.org/10.1007/BF00990225