(2S,8Z)-2-Butyroxy-8-heptadecene: Major Component of the Sex Pheromone of Chrysanthemum Gall Midge, Rhopalomyia longicauda
The sex pheromone of the chrysanthemum gall midge, Rhopalomyia longicauda (Diptera: Cecidomyiidae), the most important insect pest in commercial plantations of chrysanthemum, Dendranthema morifolium (Ramat.) Tzvel., in China, was identified, synthesized, and field-tested. Volatile chemicals from virgin females and males were collected on Porapak in China and sent to the United Kingdom for analysis. Coupled gas chromatographic–electroantennographic detection (GC-EAG) analysis of volatile collections from females revealed two compounds that elicited responses from antennae of males. These compounds were not present in collections from males. The major EAG-active compound was identified as 2-butyroxy-8-heptadecene by gas chromatographic (GC) retention indices, mass spectra, in both electron impact and chemical ionization modes, hydrogenation, epoxidation, and derivatization with dimethyldisulfide. The lesser EAG-active compound was identified as the corresponding alcohol. The ratio of butyrate to alcohol in the collections was 1:0.26. Racemic (Z)-8-heptadecen-2-ol and the corresponding butyrate ester were synthesized from (Z)-7-hexadecenyl acetate, and the synthetic compounds found to have identical GC retention indices and mass spectra to those of the natural, female-specific components. Analysis of the volatile collections on an enantioselective cyclodextrin GC column showed the natural pheromone contained (2S,8Z)-2-butyroxy-8-heptadecene. Field tests showed that rubber septa containing racemic (Z)-2-butyroxy-8-heptadecene were attractive to R. longicauda males. The (naturally occurring) S-enantiomer was equally as attractive as the racemate, while the R-enantiomer was not attractive to males, and did not inhibit the activity of the S-enantiomer. The attractiveness of the butyrate was significantly reduced by the presence of even small amounts of the corresponding alcohol.
KeywordsChrysanthemum gall midge Rhopalomyia longicauda Cecidomyiidae Sex pheromone (2S,8Z)-2-butyroxy-8-heptadecene (2S,8Z)-8-heptadecen-2-ol Field trapping
This work was funded by the National Science and Technology Support Projects in the 11th Five-year Plan of China (No. 2006BAD15B03, 2006BAD08A03 and 2006BAD02A16-4) and in part by the UK Horticultural Development Council and the Worshipful Company of Fruiterers. We thank Dr. K. M. Harris (former director of International Institute of Entomology, UK) and Prof. Junichi Yukawa (Entomological Laboratory, Faculty of Agriculture, Kyushu University, Japan) for identifying this insect species.
- Bierl-Leonhardt, B. A., DeVilbiss, E. D., and Plimmer, J. R. 1980. Location of double-bond position in long-chain aldehydes and acetates by mass spectral analysis of epoxide derivatives. J. Chromatogr. Sci. 18:364–367.Google Scholar
- Cheng, F. Z., Yang, Z. Z., Liu, Z. F., and Yang W. B. 1990. Studies of the biology and control of the chrysanthemum gall midge, Epirmgiu sp. Baoding Sci. Tech. Inform. 1:30–35. (in Chinese).Google Scholar
- Cork, A., Beevor, P. S., Gough, J. E., and Hall, D. R. 1990. Gas chromatography linked to electroantennography: a versatile technique for identifying insect semiochemicals, pp. 271–279, in A. R. McCaffery and I. D. Wilson (eds.). Chromatography and Isolation of Insect Hormones and Pheromones. Plenum, London.Google Scholar
- Cross, J. V. and Hall, D. R. 2005. Pheromones. PCT/GB2005/002504.Google Scholar
- Cross, J., Baroffio, C., Grassi, A., Hall, D., Labanowska, B., Milenković, S., Nilsson, T., Shternshis, M., Tornéus, C., Trandem, N., and Vétek, G. 2008. Monitoring raspberry cane midge, Resseliella theobaldi, with sex pheromone traps: results from 2006, pp. 11–17, in Ch. Linder and J. V. Cross (eds.). Integrated Plant Protection in Soft Fruits. IOBC/WPRS Bulletin 39.Google Scholar
- Cross, J. V., Hall, D. R., Shaw, P., and Anfora, G. 2009. Exploitation of the sex pheromone of apple leaf midge Dasineura mali Kieffer (Diptera: Cecidomyiidae): Part 2. use of sex pheromone traps for pest monitoring. Crop Prot. 28:128–133.Google Scholar
- Jorgenson, M. 1970. Preparation of ketones from the reaction of organolithium reagents with carboxylic acids. Org. React. 18:1–97.Google Scholar
- Liu, Z. F., Yang, W. B., Cheng, F. Z., and Yang, Z. Z. 1987. Preliminary report on the chrysanthemum gall midge. Plant Protection Technology and Extension 2: 34–36. (in Chinese).Google Scholar
- Liu, H. Y., Wu, R. H., Lu, C. T., Song, F. X., Yin, X. M., Wang, T. I., Zhao, Z. W., and Zhang, B. H. 2003. Field study of the chemical control of the chrysanthemum gall midge. Chinese Traditional and Herbal Drugs 34:181–183. (in Chinese with English abstract).Google Scholar
- Molnár, B., Kárpáti, Z., Szőcs, G., and Hall, D. R. 2009. Identification of female-produced sex pheromone of the honey locust gall midge, Dasineura gleditchiae. J. Chem Ecol. doi: 10.1007/s10886-009-9641-5.
- Sato, S., Ganaha, T., Yukawa, J., Liu, Y. J., Xu, H.L., Paik, J.C., Uechi, N., and Mishima, M. 2009. A new species, Rhopalomyia longicauda (Diptera: Cecidomyiidae), inducing large galls on wild and cultivated Chrysanthemum (Asteraceae) in China and on Jeju Island, Korea. Appl. Entomol. Zool. 44:61–72.CrossRefGoogle Scholar
- Wu, R. H., Liu, H. Y., Wang, F., Lu, C. H. T., and Yin, X. M. 2007. Integrated control techniques of chrysanthemum gall midge. Henan Agri. Sci. 7:95–98. (in Chinese).Google Scholar