Syntheses and behaviour activity of conjugated polyenic pheromone components

• Main Author: Liblikas, Ilme
• Format: Doctoral Thesis
• Language: English
• Published: KTH, Kemi 2004
• Subjects: Organic chemistry; entomology; environmental sciences
• Online Access: http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-3790; http://nbn-resolving.de/urn:isbn:91-7283-787-X

This thesis deals with the synthesis of conjugated dienicand trienic pheromone components- C12-C16alcohols, acetates and aldehydes and theirapplications in pheromone communication studies. Insect pheromones are widely used in modern pest management.The development of effective tools for plant protection is aresult of complex broad, interdisciplinary basic and appliedresearch. A practical use of pheromones for pest managementusually requires that specific active chemicals must beisolated,identified and produced synthetically. The creationof pheromone materials besides requires the identification ofthe active components, determination of the roles of otherpossible isomers or degradation products, the design ofdispensers of suitable substrates and evaporationparameters. The aim of the thesiswas critically to survey methods for the syntheses ofconjugated polyenic compounds and to focus to the synthesis ofseveral conjugated polyenic pheromone components providingsufficient quantities of chemically and isomerically purecompounds for bioassaying. The principal objective of the thesiswas concerned withthe further aim of developing effective synthetic materials forplant protection. The work was focussed: =>To identify the compoundscollected from the leafminer mothPhyllonorycter emberizaepenella(Lepidoptera:Gracillaridae) and perform a detailed identification of thepheromones of the Brazilian apple leafrollerBonagota cranaodes(Meyrick) (Lepidoptera: Tortricidae)and of the codling mothCydia pomonella(L.) (Lepidoptera: Tortricidae). =>Tostudy the effect of non-pheromonal isomers of the mainpheromone component on the sex attraction of B. cranaodes andC.pomonellain wind tunnel and field tests.=>To study the role of identified pheromonecomponents in the pheromone communication of the currant shootborer Lampronia capitella (Cl.) (Lepidoptera: Prodoxidae), andto design and optimize the dispenser for effective trapping.=>To investigate the presence of sex pheromonecomponents in the tobacco hawk mothManduca sexta(L.) (Lepidoptera: Sphingidae). The syntheses of four geometrical isomers of3,5-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 andaldehyde; all geometrical isomers of 8,10-and10,12-tetradecadienols and corresponding acetates wereperformed to ensure all these bioassays with syntheticpheromone components. All compounds were made in high chemicaland stereochemical purity, most of them more than 99%isomerically pure or by using several separation andpurification techniques. The suitable synthetic schemes for the synthesis of all fourgeometrical isomers of four conjugated dienic pheromonecomponents are presented in this thesis. The reactions and purification methods used here exemplifythe wide range of possibilities realized for such syntheses:they present the successful application of many syntheticmethods. The importance of this synthetic work is that thecompounds synthesized are not commercially available or on theother hand the purity of the purchasable compounds is notsatisfactory for research in the field of chemical ecology. Key words:Lepidoptera, sex pheromone, pheromonedispenser, 3,5-dodecadienyl acetate, 10,12,14-hexadecatrienal,8,10-dodecadienol, codlemone atsetate, codlemone aldehyde,8,10- tetradecadienol, 8,10-tetradecadienyl acetate,10,12-tetradecadienol, 10,12-tetradecadienyl acetate,Lampronia capitella, Manduca sexta, Bonagota cranaodes,Cydia pomonella, Phyllonorycter emberizaepenella,conjugated polyenic pheromone, conjugated diene, MPLC,(9Z,11Z)-9,11-tetradecadien-1-ol,(9Z,11Z)-9,11-tetradecadien-1-al