Abstract
Here, we report the identification and synthesis of the sex pheromone of female Margarodes prieskaensis (Jakubski), and the attractiveness of the synthetic pheromone to males in field trapping tests. Volatile organic compounds were collected from virgin females using a sample enrichment probe (SEP). Analyses by gas chromatography coupled to mass spectrometry revealed the presence of only two constituents. By scaling up the SEP, sufficient of the major constituent was collected for 1H and 13C nuclear magnetic resonance (NMR) analyses and ancillary NMR techniques. The sex attractant was identified as (2R,4R,6R,8R)-2,4,6,8-tetramethylundecan-1-ol. The enantiomerically pure compound was synthesized from octadecyl (2R,4R,6R,8R)-2,4,6,8-tetramethylundecanoate, a minor component of the uropygial (preen) gland secretion of the domestic goose, Anser domesticus. Field trapping experiments, carried out in vineyards in the Northern Cape Province of South Africa, showed that the synthetic compound was as attractive to winged males of M. prieskaensis as virgin females. The second compound detected was identified as the corresponding acetate, but addition of this did not affect the attractiveness of the major component. We believe this to be the first identification of a sex attractant of the Margarodidae.
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References
Allsopp E, Barnes BN, Blomefield TL, Pringle KP (2015) Grapevine. In: Prinsloo GL, Uys VM (eds) Insects of cultivated plants and natural pastures in Southern Africa. Entomol Soc Southern Africa, Hatfield, pp 420–437
Ando T, Yamakawa R (2015) Chiral methyl-branched ketones. Nat Prod Rep 32:1007–1041
Ben-Dov Y (2005) A systematic catalogue of the scale insect family Margarodidae (Hemiptera: Coccoidea) of the world. Intercept Ltd., Wimborne, UK
Burger BV, Marx B, Le Roux M, Burger WJG (2006) Simplified analysis of organic compounds in headspace and aqueous samples by high-capacity sample enrichment probe. J Chromatogr A 1121:259–267
Burger BV, le Roux M, Marx B, Herbert SA, Amakali KT (2011) Development of second-generation sample enrichment probe for improved sorptive analysis of volatile organic compounds. J Chromatogr A 1218:1567–1575
Chow S, Fletcher MT, Lambert LK, Gallagher OP, Moore CJ, Cribb BW, Allsopp PG, Kitching W (2005) Novel cuticular hydrocarbons from the cane beetle Antitrogus parvuluss–4,6,8,10,16-penta- and 4,6,8,10,16,18-hexamethyldocosanes–unprecedented anti-anti-anti-stereochemistry in the 4,6,8,10-methyltetrad. J Organomet Chem 70:1808–1827
De Klerk CA (1981) Wingerdplae. In: Burger J, Deist J (eds) Wingerdbou in Suid-Afrika. ARC Infruitec-Nietvoorbij, Stellenbosch, South Africa, pp 433–437
De Klerk CA (1983) Two new species of margarodes (Homoptera: Coccoidea: Margarodidae) from South Africa. Phytophylactica 15:85–94
De Klerk CA, Ben-Dov Y, Gilliomee JH (1982a) Redescriptions of four vine infesting species of Margarodes Guilding (Homoptera: Coccoidea: Margarodidae) from South Africa. Phytophylactica 14:61–76
De Klerk CA, Ben-Dov Y, Gilliomee JH (1982b) Redescriptions of three Margarodes Guilding species (Homoptera: Coccoidea: Margarodidae) found on grasses in South Africa. Phytophylactica 14:77–83
De Klerk CA, Ben-Dov Y, Gilliomee JH (1983) General morphology of south African species of Margarodes (Homoptera: Coccoidea: Margarodidae) with keys to nymphs and adult females. Phytophylactica 15:133–144
De Klerk CA, Vermeulen A, Du Toit E (2011) Seasonal occurrence of margarodes in the Orange River irrigation area. SA fruit. Journal:44–46
Du Toit GDG (1975) Notes on the biology and behavior of Sphaeraspis prieskaensis Jak. (Hemiptera: Coccoidea) a pest on grape vine roots. In: Durr HJR, Giliomee JH, Neser S (eds) Proceedings of the first congress of the Entomol Soc Southern Africa 1974. Entomol Soc Southern Africa, Pretoria, pp 255–257
Foldi I (2005) Ground pearls: a generic revision of the Margarodidae sensu stricto (Hemiptera: Sternorrhyncha: Coccoidea). Ann Soc Entomol Fr (ns) 41:81–125
Herber C, Breit B (2007) Enantioselective total synthesis and determination of the absolute configuration of the 4,6,8,10,16,18-hexamethyldocosane from Antitrogus parvulus. Eur J Org Chem:3512–3519. doi:10.1002/ejoc.200700282
Hofmeyr JH, Burger BV (1995) Controlled-release pheromone dispenser for use in traps to monitor flight activity of false codling moth. J Chem Ecol 21:355–363
Kuwahara Y, Yen LTM, Tominaga Y, Matsumoto K, Wada Y (1982) 1,3,5,7-Tertramethyldecyl formate, lardolure: aggregation pheromone on the acarid mite, Lardoglyphus konoi Sasa et Asanuma Acarina: acaridae. Agric Biol Chem 46:2283–2291
Mori K, Kuwahara S (1987) Synthesis of the methyl ester of (2R,4R,6R,8R)-2,4,6,8-tetramethylundecanoic acid, an acid component of the preen-gland wax of the graylag goose. Liebigs Ann Chem:555–556. doi:10.1002/jlac.198719870377
Morr M, Wray V, Fortkamp J, Schmid RD (1992) (2R,4R,6R,8R)-2,4,6,8-Tetramethyldecan- und -undecansäure aus dem Bürzeldrüsenwachs der Hausgans, Anser a.f. domesticus: Isolierung, Synthese einiger Derivate sowie der rac-2,4,6,8-Tetramethyldecansäure. Liebigs Ann Chem 433–439
Morr M, Proppe C, Wray V (1995) Synthesis of asymmetrical methyl-branched chiral ketones from the corresponding homologous wax esters. A new synthesis of the insect pheromone lardolure and of 9-norlardolure. Liebigs Ann:2001–2004. doi:10.1002/jlac.1995199511280
Ott RL (1998) An introduction to statistical methods and data analysis. Duxbury Press, Belmont, pp. 591–837
Reiter B, Burger B, Dry J (2003) Mammalian exocrine secretions XVIII. Chemical characterization of interdigital secretion of red hartebeest, Alcelaphus buselaphus. J Chem Ecol 29:2235–2252
Schmidt Y, Breit B (2012) Direct assignment of the relative configuration in 1,3,n-methyl-branched carbon chains by 1H NMR spectroscopy. Org Lett 12:2218–2221
Schmidt Y, Lehr K, Colas L, Breit B (2012) Assignment of relative configuration of desoxypropionates by 1H NMR spectroscopy: method development, proof of principle by asymmetric total synthesis of xylarinic acid a and applications. Chem Eur J 18:7071–7708
Shapiro SS, Wilk MB (1965) An analysis of variance test for normality (complete samples). Biometrica 52:951–611
Snedecor GW, Cochran WG (1980) Statistical methods, 7th edn. Iowa State University Press, Ames
Weitzel G, Fretzdorff A-M, Wojahn J (1952) Die Fettstoffe der Bürzeldrüsen von Gänsen. Hoppe-Seyler’s. Z Physiol Chem 291:46–57
Acknowledgements
We are indebted to Prof B Breit (Universtät Freiburg, Germany) for the donation of a sample of (2S,4R,6S,8R)-2,4,6,8-tetramethylundecan-1-ol and for advice on the determination of the relative stereochemistry of its 2R,4R,6R,8R diastereomer. We thank Dr. M. Nimtz (Helmholtz Zentrum für Infektionsforschung, Braunschweig, Germany) for the GC analysis of the crude uropygial wax of the goose. We also thank Karsten Boerderye Bpk for permission to carry out field experiments on the farm Klein Pella, and Khaki Goosen and staff for adjusting their pruning and irrigation programs to accommodate our research, and for invaluable advice and assistance. We thank the anonymous reviewers for constructive comments on the first version of this manuscript. The research was funded by the South African Table Grape Industry, the Dried Grape Industry, and the Wine Grape Industry.
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Burger, B.V., de Klerk, C.A., Morr, M. et al. Identification, Synthesis, and Field Tests of the Sex Pheromone of Margarodes prieskaensis (Jakubski). J Chem Ecol 43, 94–105 (2017). https://doi.org/10.1007/s10886-016-0801-0
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DOI: https://doi.org/10.1007/s10886-016-0801-0