Journal of Chemical Ecology

, Volume 33, Issue 5, pp 963–970

Biosynthesis of Tiglic, Ethacrylic, and 2-Methylbutyric Acids in a Carabid Beetle, Pterostichus (Hypherpes) californicus

  • Athula B. Attygalle
  • Xiaogang Wu
  • Kipling W. Will
Article

Abstract

Tiglic, 2-methylbutyric, and ethacrylic acids are found in the pygidial gland defensive fluid of many carabid beetles. By injecting a deuterium-labeled precursor into the carabid beetle Pterostichus (Hypherpes) californicus, and analyzing the defensive fluid by gas chromatography/mass spectrometry, we were able to demonstrate that tiglic and ethacrylic acids are biosynthesized from isoleucine via 2-methylbutyric acid. Moreover, we observed that the injection of l-isoleucine induces an increased production of tiglic acid in P. californicus. A strong primary kinetic isotope effect was found to operate in the dehydrogenation step of 2-methylbutyric acid to tiglic and ethacrylic acids. Consequently, ethacrylic acid was found to preferentially accumulate the deuterium labeling from [2,3,4,4-2H4]isoleucine during our biosynthetic experiments.

Keywords

Biosynthesis Defensive allomones Tiglic acid 2-Methylbutyric acid Ethacrylic acid Isoleucine Carabid beetles Pterostichus (Hypherpes) californicus Carabidae 

References

  1. Adachi, Y., Kanehisa, K., and Tsumuki, H. 1985. Catabolic formation of methacrylic acid and tiglic acid from the branched chain amino acids in the pygidial defensive glands of Carabus yaconinus Bates (Coleoptera: Carabidae). Appl. Entomol. Zool. 20:492–493.Google Scholar
  2. Attygalle, A. B., Meinwald, J., and Eisner, T. 1991. Biosynthesis of methacrylic and isobutyric acids in a carabid beetle, Scarites subterraneus. Tetrahedron Lett. 32:4489–4852.CrossRefGoogle Scholar
  3. Attygalle, A. B., Wu, X., Ruzicka, J., Rao, S., Garcia, S., Herath, K., Meinwald, J., Maddison, D., and Will, K. W. 2004. Defensive chemicals of two species of Trachypachus Motschulski (Coleoptera: Trachypachidae). J. Chem. Ecol. 20:567–578.Google Scholar
  4. Basey, K. and Woolley, J. G. 1973. Biosynthesis of the tigloyl esters in Datura: The role of 2-methylbutyric acid. Phytochemistry 12:2197–2201.CrossRefGoogle Scholar
  5. Benn, M. H., Lencucha, A., Maxie, S., and Telang, S. A. 1973. The pygidial defensive secretion of Carabus taedatus. J. Insect. Physiol. 19:2173–2176.CrossRefGoogle Scholar
  6. Leete, E. 1973. Biosynthetic conversion of α-methylbutyric acid to tiglic acid in Datura meteloides. Phytochemistry 12:2203–2205.CrossRefGoogle Scholar
  7. Leete, E. and Murrill, S. J. B. 1967. Biosynthesis of the tiglic acid moiety of meteloidine in Datura meteloides. Tetrahedron Lett. 18:1727–1730.PubMedCrossRefGoogle Scholar
  8. Will, K. W., Attygalle, A. B., and Herath, K. 2000. New defensive chemical data for ground beetles (Coleoptera: Carabidae): Interpretations in a phylogenetic framework. Biol. J. Linn. Soc. 71:459–481.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2007

Authors and Affiliations

  • Athula B. Attygalle
    • 1
  • Xiaogang Wu
    • 1
  • Kipling W. Will
    • 2
  1. 1.Department of Chemistry and Chemical BiologyStevens Institute of TechnologyHobokenUSA
  2. 2.ESPM-Division of Insect BiologyUniversity of CaliforniaBerkeleyUSA

Personalised recommendations