Syntheses and Behaviour Activity of Conjugated Polyenic Pheromone Components

This thesis deals with the synthesis of conjugated dienic and trienic pheromone componentsC12-C16 alcohols, acetates and aldehydes and their applications in pheromone communication studies. Insect pheromones are widely used in modern pest management. The development of effective tools for plant protection is a result of complex broad, interdisciplinary basic and applied research. A practical use of pheromones for pest management usually requires that specific active chemicals must be isolated, identified and produced synthetically. The creation of pheromone materials besides requires the identification of the active components, determination of the roles of other possible isomers or degradation products, the design of dispensers of suitable substrates and evaporation parameters. The aim of the thesis was critically to survey methods for the syntheses of conjugated polyenic compounds and to focus to the synthesis of several conjugated polyenic pheromone components providing sufficient quantities of chemically and isomerically pure compounds for bioassaying. The principal objective of the thesis was concerned with the further aim of developing effective synthetic materials for plant protection. The work was focussed: ⇒ To identify the compounds collected from the leafminer moth Phyllonorycter emberizaepenella (Lepidoptera: Gracillaridae) and perform a detailed identification of the pheromones of the Brazilian apple leafroller Bonagota cranaodes (Meyrick) (Lepidoptera: Tortricidae) and of the codling moth Cydia pomonella (L.) (Lepidoptera: Tortricidae). ⇒ To study the effect of non-pheromonal isomers of the main pheromone component on the sex attraction of B. cranaodes and C. pomonella in wind tunnel and field tests. ⇒ To study the role of identified pheromone components in the pheromone communication of the currant shoot borer Lampronia capitella (Cl.) (Lepidoptera: Prodoxidae), and to design and optimize the dispenser for effective trapping. ⇒ To investigate the presence of sex pheromone components in the tobacco hawk moth Manduca sexta (L.) (Lepidoptera: Sphingidae). The syntheses of four geometrical isomers of 3,5-dodecadienyl acetate; (10E,12E,14Z)and (10E,12E,14E)-(10,12,14)-hexadecatrien-1-als; (E,Z)-, (Z,E)-, and (Z,Z)-8,10-dodecadienol, codlemone acetate and aldehyde; (9Z,11Z)-9,11-tetradecadienol, corresponding acetate and aldehyde; all geometrical isomers of 8,10-and 10,12-tetradecadienols and corresponding acetates were performed to ensure all these bioassays with synthetic pheromone components. All compounds were made in high chemical and stereochemical purity, most of them more than 99% isomerically pure or by using several separation and purification techniques. The suitable synthetic schemes for the synthesis of all four geometrical isomers of four conjugated dienic pheromone components are presented in this thesis. The reactions and purification methods used here exemplify the wide range of possibilities realized for such syntheses: they present the successful application of many synthetic methods. The importance of this synthetic work is that the compounds synthesized are not commercially available or on the other hand the purity of the purchasable compounds is not satisfactory for research in the field of chemical ecology.