Syntheses and Behaviour Activity of Conjugated Polyenic Pheromone Components ILME LIBLIKAS Doctoral Thesis Stockholm, Sweden 2004 Syntheses and Behaviour Activity of Conjugated Polyenic Pheromone Components Ilme Liblikas Doctoral Thesis Stockholm 2004 ——————————————————————————————————— Akademisk avhandling som med tillstånd av Kungliga Tekniska Högskolan i Stockholm framlägges till offentlig granskning för avläggande av filosofie doktorsexamen i kemi, tisdagen den 8 juni 2004 kl. 14 i Kollegiesalen, Valhallavägen 79, KTH, Stockholm. Avhandlingen försvaras på engelska. Opponent är Professor Dr. Wittko Francke, Institute of Organic Chemistry, Hamburg University, Germany. Cover: Main pheromone component of codling moth Cydia pomonella (L.), (8E,10E)-8,10-dodecadien-1-ol ISBN 91-7283-787-X ISRN KTH/IOK/FR-04/91-SE ISSN 1100-7974 TRITA-IOK Forskningsrapport 2004:91 © Ilme Liblikas 2004 Liblikas, Ilme. Syntheses and behaviour activity of conjugated polyenic pheromone components. Royal Institute of Technology, Stockholm, June 2004. ABSTRACT This thesis deals with the synthesis of conjugated dienic and trienic pheromone components- C12-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. Key words: Lepidoptera, sex pheromone, pheromone dispenser, 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 APPENDICES AND PAPERS Appendices: 1. Synthetic scheme of the synthesis of four geometric isomers of 10,12- tetradecadienol and of their acetates 2. Synthetic schemes of the syntheses of EZ-, ZE-, and ZZ-isomers of 8,10- dodecadienol 3. Synthetic schemes of the syntheses of EEE- and EEZ-isomers of 10,12,14- hexadecatrienal 4. Synthesized compounds This thesis is based on the following publications and manuscripts, which will be referred to by their Roman numerals I-X. I Effect of Codlemone Isomers on Codling Moth (Lepidoptera: Tortricidae) Male Attraction. El-Sayed, A., Unelius, R.C., Liblikas, I., Löfqvist, J., Bengtsson, M. and Witzgall, P. Environ. Entomol. (1998) 27(5): 1250-1254. II Synthesis and Characterization of the Four Geometrical Isomers of 3,5- Dodecadienyl Acetate. Unelius, C.R., Liblikas, I. and Mozuraitis, R. Acta Chem. Scand. (1998) 52: (7): 930-934. III Sex Pheromone of the Brazilian Apple Leafroller, Bonagota cranaodes Meyrick (Lepidoptera, Tortricidae). Eiras, A.E., Kovaleski, A., Vilela, E.F., Chambon, J.P., Unelius, C.R., Borg-Karlson, A.-K., Liblikas, I., Mozuraitis, R., Bengtsson, M. and Witzgall, P. Z. Naturforsch., C: J. Biosci. (1999) 54(7/8): 595-601. IV Flight and Molecular Modelling Study on the Response of Codling Moth, Cydia pomonella (Lepidoptera: Tortricidae) to (E,E)-8,10-Dodecadien-1-ol and Its Geometrical Isomers. El-Sayed, A., Liblikas, I. and Unelius, R. Z. Naturforsch., C: J. Biosci. (2000) 55(11/12): 1011-1017. V Detection of Sex Pheromone Components in Manduca sexta (L.). Kalinova, B., Hoskovec, M., Liblikas, I., Unelius, C.R. and Hansson, B.S. Chem. Senses (2001) 26(9): 1175-1186. VI Identification of Further Sex Pheromone Synergists in the Codling Moth, Cydia pomonella. Witzgall, P., Bengtsson, M., Rauscher, S., Liblikas, I., Bäckman, A.-C., Coracini, M., Anderson, P. and Löfqvist, J. Ent. Exp. Appl. (2001) 101(2): 131-141. VII Parthenogenesis, Calling Behaviour and Insect Released Volatiles of the Leaf Miner Moth Phyllonorycter emberizaepenella. Mozūraitis R., Būda V., Liblikas I., Unelius C.R. and Borg-Karlson A-K. J. Chem. Ecol. (2002) 28(6): 1191-1208. VIII Activity Sex Pheromone components on the Currant Shoot Borer males (Lampronia capitella (Cl.) (Lepidoptera: Prodoxidae). Liblikas, I., Mõttus, E., Kännaste, A., Kuusik, S., Ojarand, A., Mozuraitis, R., Santangelo, E., Mõttus, M., Unelius, R.C. and Borg-Karlson, A.-K. Manuscript for Chemoecology. IX On the Variability of Genitalia and Pheromone Communication Channel of Archips podana (Scopoli) (Lepidoptera: Tortricidae). Liblikas, I., Mõttus, E., Nikolaeva, Z.V., Ojarand, A., Ovsyannikova, E.I., Grichanov, I.Ya., Ivanova, T.V. and Yemeljanov, V.A. Proc. Estonian Acad. Sci. Biol. Ecol (2004) 53(2): in press. X Synthesis of Some Alkenoic Plant Volatiles. Liblikas, I., Mõttus, E. and Nilson, A. Proc. Estonian Acad. Sci. Chem. (1996) 45(3/4): 146-151. LIST OF CONTENTS ABSTRACT LIST OF APPENDICES AND PAPERS ABBREVIATIONS I. INTRODUCTION 1 II. BACKGROUND AND AIM OF THE THESIS 2 1. Pheromones in insect pest management 2 1.1. General characterization of the Lepidopteran sex pheromones 2 1.2. Methods of application of insect sex pheromones in pest management 3 1.3. The advantages of pheromone-based methods in plant protection 5 2. Aim of the thesis 6 III. SYNTHESES OF CONJUGATED POLYENIC COMPOUNDS 11 1. Selection of methods for the syntheses of conjugated polyenic compounds 11 2. General reactions, methods and transformations 13 2.1. Methods of purification 13 2.1.1. Methods of chemical purification 13 2.1.2. Methods of isomeric purification of conjugated polyenic compounds 13 2.2. Oxidation reactions 14 2.2.1. Oxidation of alcohols to aldehydes 14 2.2.2. Oxidation of bromides to aldehydes 16 2.3. Semihydrogenations 16 2.3.1. Semihydrogenations of triple bonds in alkenynes 16 2.3.2. Semihydrogenations of triple bonds in diynes 17 2.4. Monobromination and monotetrahydropyranylation 18 3. Results of syntheses of polyenic pheromone components 18 3.1. General aspects of the Wittig reaction 1 18 3.2. Wittig reactions in the synthetic schemes of conjugated dienic pheromone components 21 3.2.1. Syntheses of (Z,E)-isomers 21 3.2.2. Syntheses of (E,Z)-isomers 22 3.3. Modifications of the Wittig reaction 24 3.3.1. Schlosser`s modification of the Wittig reaction 24 3.3.2. Horner-Wadsworth-Emmon’s reaction 24 3.4. Alternative syntheses of the trienic pheromone components of Manduca sexta 26 3.5. Syntheses of (3E,5Z)-3,5-dodecadienyl and (3E,5E)-3,5-dodeca- dienyl acetates via Horner-Wadsworth-Emmon’s condensation 27 3.6. Alternative synthetic methods for the syntheses of (3E,5Z)- and (3Z,5E)-isomers of conjugated dienic pheromone components 27 3.6.1. Synthesis of (3E,5Z)-3,5-dodecadienyl