Abstract
Sex pheromone candidates with a conjugated triene system, 8,10,12-, 9,11,13- and 11,13,15-hexadecatrienyl acetates (double bond positional isomers of theGlyphodes pyloalis pheromone, 10,12,14-triene) were synthesized by introducing anE configuration stereospecifically to two of three double bonds and rather nonspecifically to another double bond, so as to obtain two geometrical isomers;E,E,E andE,E,Z orE,Z,E isomers. The two geometrical isomers of each triene acetate were separated on a reverse-phase HPLC column and characterized by1H NMR analysis. The13C NMR signals in the olefinic region of each isomer were assigned by two-dimensional NMR techniques and also by an empirical rule based on the changes of the chemical shifts by converting the configuration. Based on the assignments, substituent parameters for calculating the chemical shifts of 1,6-dialkyl conjugated trienes were generated. Electron impact mass spectrometry showed characteristic fragment ions that enabled the double bond positional isomers to be distinguished from each other.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Ando, T., Kurotsu, Y., Kaiya, M., andUchiyama, M. 1985. Systematic syntheses and characterization of dodecadien-1-ols with conjugated double bond, lepidopterous sex pheromones.Agric. Biol. Chem. 49:141–148.
Ando, T., Ogura, Y., andUchiyama, M. 1988a. Mass spectra of lepidopterous sex pheromones with a conjugated diene system.Agric. Biol. Chem, 52:1415–1423.
Ando, T., Ogura, Y., Koyama, M., Kurane, M., Uchiyama, M., andSeol, K.Y. 1988b. Syntheses and NMR analyses of eight geometrical isomers of 10,12,14-hexadecatrienyl acetate, sex pheromone candidates of the mulberry pyralid.Agric. Biol. Chem. 52:2459–2468.
Ando, T.,Aburatani, M.,Koseki, N.,Asakawa, S.,Mouri, T., andAbe, H. 1993.13C NMR assignments of brassinosteroids by two-dimensional techniques.Magn. Reson. Chem. 31: In press.
Arn, H.,Toth, M., andPriesner, E. 1986. List of sex pheromones of Lepidoptera and related attractants. OILB-SROP/IOBC-WPRS, Secretariat General, 149 Rue de Bercy, F-75595 Paris cedex 12; ISBN 92-9067-002-9, 123 pp.
Baker, T.C., Francke, W., Löfstedt, C., Hansson, B.S., Du, J.-W., Phelan, P.L., Vetter, R.S., andYoungman, R. 1989. Isolation, identification and synthesis of sex pheromone components of the carob moth,Ectomyelois ceratoniae.Tetrahedron Lett. 30:2901–2902.
Doolittle, R.E., Brabham, A., andTumlinson, J.H. 1990. Sex pheromone ofManduca sexta (L). Stereoselective synthesis of (10E,12E,14Z)-10,12,14-hexadecatrienal and isomers.J. Chem. Ecol. 16:1131–1153.
Dorman, D.E., Jautelat, M., andRoberts, J.D. 1971. Carbon-13 nuclear magnetic resonance spectroscopy. Quantitative correlations of the carbon chemical shifts of acyclic alkenes.J. Org. Chem. 36:2757–2766.
Gaudin, J.-M., andMorel, C. 1990. Two new stereoselective syntheses of (3E,5Z)-1,3,5-undecatriene.Tetrahedron Lett. 31:5749–5752.
Honda, H., Ando, T., Ogura, Y., Teramine, T., andUeda, R. 1990. Identification of the sex pheromone of the mulberry pyralid,Glyphodes pyloalis Walker (Lepidoptera: Pyralidae).Appl. Entomol. Zool. 25:265–272.
Kuwahara, Y., Yonekawa, Y., Kamikihara, T., andSuzuki, T. 1986. Identification of the double bond position in insect sex pheromones by mass spectrometry; trial comparison of methyl undecenoates with the natural pheromone of the varied carpet beetle.Agric. Biol. Chem. 50:2017–2024.
Levy, G.C., Lichter, R.L., andNelson, G.L. 1980. Carbon-13 Nuclear Magnetic Resonance Spectroscopy, 2nd ed., John Wiley & Sons, New York, pp. 78–79.
Millar, J.G. 1990. Synthesis of 9Z, 11E,13-tetradecatrienal, the major component of the sex pheromone of the carob moth,Ectomyelois ceratoniae (Lepidoptera: Pyralidae).Agric. Biol. Chem. 54:2473–2476.
Roelofs, W., andBjostad, L. 1984. Biosynthesis of lepidopteran pheromones.Bioorg. Chem. 12:279–298.
Seol, K.Y., Honda, H., Usui, K., Ando, T., andMatsumoto, Y. 1987. 10,12,14-Hexadecatrienyl acetate: Sex pheromone of the mulberry pyralid,Glyphodes pyloalis Walker (Lepidoptera: Pyralidae).Agric. Biol. Chem. 51:2285–2287.
Tellier, F., andDescoins, C. 1990. Stereospecific synthesis of (Z,E)-9,11,13-tetradecatrien-1-yl acetate and aldehyde sex pheromone components ofStenoma cecropia andEctomyelois ceratoninae.Tetrahedron Lett. 31:2295–2298.
Tellier, F. 1991. Stereospecific synthesis of (E,E)-9,11,13-tetradecatrienyl acetate and aldehyde (geometrical isomers of the major components of two sex pheromone of Lepidoptera).Synth. Commun. 21:2287–2294.
Tellier, F., Descoins, C., andSauvetre, R. 1991. Stereospecific synthesis of 1,5-dien-3-ynes and 1,3,5-trienes application to the stereochemical identification of trienic sex pheromones.Tetrahedron 47:7767–7774.
Tumlinson, J.H., Brennan, M.M., Doolittle, R.E., Mitchell, E.R., Brabham, A., Mazomenos, B.E., Baumhover, A.H., andJackson, D.M. 1989. Identification of a heromone blend attractive toManduca sexta (L.) males in a wind tunnel.Arch. Insect Biochem. Physiol. 10:255–271.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Ando, T., Ohsawa, H. Sex pheromone candidates with a conjugated triene system: Synthesis and chemical characterization. J Chem Ecol 19, 119–132 (1993). https://doi.org/10.1007/BF00987477
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00987477