Journal of Chemical Ecology

, Volume 19, Issue 7, pp 1355–1369 | Cite as

Cardenolides fromErysimum cheiranthoides: Feeding deterrents toPieris rapae larvae

  • K. Sachdev-Gupta
  • Cd. Radke
  • J. A. A. Renwick
  • M. B. Dimock
Article

Abstract

Larvae of the cabbage butterfly,Pieris rapae, refuse to feed on the wild mustard,Erysimum cheiranthoides, due to the presence of alcoholextractable deterrents. The active components were extracted inton-BuOH, and this extract was separated into four fractions (I–IV) by reverse-phase HPLC. Fractions III and IV retained the feeding deterrent activity. The activity of fraction III was found to be due to the cardenolide diglycosides 1 and 2, which were previously reported as oviposition deterrents for gravidP. rapae butterflies. Three active compounds were isolated from fraction IV by column chromatography on silica gel followed by reverse-phase HPLC. These compounds were identified as a monoglycoside, digitoxigenin 3-O-β-D-glucoside (4), and two diglycosides, glucodigigulomethyloside (5) and glucodigifucoside (6). An additional cardenolide isolated from fraction II was identified as cheirotoxin (7). All compounds were identified by UV, NMR (1H and13C), and mass spectrometry, as well as hydrolysis experiments. The feeding deterrent activity of these compounds was compared with that of related commercially available chemicals and other compounds isolated fromE. cheiranthoides.

Key Words

Pieris rapae Erysimum cheiranthoides feeding deterrents cardenolides digitoxigenin 3-O-β-D-glucoside glucodigigulomethyloside glucodigifucoside erychroside cheirotoxin strophanthidin glycosides digitoxigenin glycosides Lepidoptera Pyridae 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Bax, A., andMorris, G.A. 1981. An improved method for heteronuclear chemical shift correlation by two-dimensional NMR.J. Magn. Reson. 42:501–505.Google Scholar
  2. Beale, J.M., Floss, H.G., Lehmann, T., andLuckner, M. 1988. Digitoxigenin-3β-0-[β-D- fucopranosyl-4-β-glucopyranoside], the main cardenolide of somatic embryos ofDigitalis lanata.Phytochemistry 27:3143–3146.Google Scholar
  3. Brauchli, P., Schindler, O., andReichstein, T. 1961. Die cardenolide vonCastillo elastica Cerv.Helv. Chim. Acta 44:904–919.Google Scholar
  4. Cheung, H.T.A., Brown, L., Boutagy, J., andThomas, R. 1981. Cardenolide analogues. Part 12.13C NMR of semi-synthetic glycosides and side-chain modified genins.J. Chem. Soc. Perkin Trans. I 1981(6):1773–1778.Google Scholar
  5. Dimock, M.B., Renwick, J.A.A., Radke, C.D., andSachdev-Gupta, K. 1991. Chemical constituents of an unacceptable crucifer,Erysimum cheiranthoides, deter feeding byPieris rapae.J. Chem. Ecol. 17:525–533.Google Scholar
  6. Doddrell, D.M., Pegg, D.T., andBendall, M.R. 1982. Distortionless enhancement of NMR signals by polarization transfer.J. Magn. Reson. 48:323–327.Google Scholar
  7. Krebs, K.G., Heusser, D., andWimmer, H. 1969. Spray reagents, pp. 854–911,in E. Stahl (ed.). Thin-Layer Chromatography (English translation). Springer-Verlag, Berlin.Google Scholar
  8. Makarevich, I.F. 1965. Presence of glucodigifucoside inErysimum cheiranthoides.Khim. Prir. Soedin. No. 2:67–69 (English translation).Google Scholar
  9. Makarevich, I.F., Kolesnikov, D.D., andBelokon, V.F. 1974. Cardiac glycosides ofCheiranthus allionii.Khim. Prir. Soedin. No. 5:616–618 (English translation).Google Scholar
  10. Makarevich, I.F., Kolesnikov, D.D., Kovalev, I.P., Gordienko, V.G., andKabanov, V.S. 1975. Cardiac glycosides ofCheiranthus allioni.Khim. Prir. Soedin. No. 6:778–781 (English translation).Google Scholar
  11. Makarevich, I.F., Zolot'ko, Z.S., andKolesnikov, D.D. 1980. Extraction of strophanthidin and accompanying cardenolides fromErysimum canescens Roth.Farm. Zh. (Kiev) 6:33–35;Chem. Abstr. 94:180555g.Google Scholar
  12. Maslennikova, V.A., Umarova, R.U., andAbubakirov, N.K. 1975. Cardenolides ofErysimum cuspidatum.Khim. Prir. Soedin. No. 2:179–182 (English translation).Google Scholar
  13. Moore, J.A., Tamm, C., andReichstein, T. 1954. Glycosides of the wallflower,Cheiranthus cheiri.Helv. Chim. Acta 37:755–770.Google Scholar
  14. Ooi, Y., Hashimoto, T., Mitsuo, N., andSatoh, T. 1985. Enzymic formation ofβ-alkyl glycosides byβ-galactosidase fromAspergillus oryzae and its application to the synthesis of chemically unstable cardiac glycosides.Chem. Pharm. Bull. 33:1808–1814.Google Scholar
  15. Okano, A. 1957. Studies on the constituents ofDigitalis purpurea L. VI. Glucodigifucoside, a new cardiotonic glycoside.Chem. Pharm. Bull. 5:272–276.Google Scholar
  16. Reichstein, T., andWeiss, E. 1962. The sugars of the cardiac glycosides.Adv. Carb. Chem. 17:65–120.Google Scholar
  17. Renwick, J.A.A., andRadke, C.D. 1985. Constituents of host and non-host plants deterring oviposition by the cabbage butterfly,Pieris rapae.Entomol. Exp. Appl. 39:21–26.Google Scholar
  18. Renwick, J.A.A., andRadke, C.D. 1987. Chemical stimulants and deterrents regulating acceptance or rejection of crucifers by cabbage butterflies.J. Chem. Ecol. 13:1771–1776.Google Scholar
  19. Renwick, J.A.A., Radke, C.D., andSachdev-Gupta, K. 1989. Chemical constituents ofErysimum cheiranthoides deterring oviposition by the cabbage butterfly,Pieris rapae.J. Chem. Ecol. 15:2161–2169.Google Scholar
  20. Robien, W., Kopp, B., Schable, D., andSchwarz, H. 1987. Carbon-13 NMR spectroscopy of cardenolides and bufadienolides.Prog. NMR Spectrosc. 19:131–181.Google Scholar
  21. Sachdev-Gupta, K., Renwick, J.A.A., andRadke, C.D. 1990. Isolation and identification of oviposition deterrents to the cabbage butterfly,Pieris rapae, fromErysimum cheiranthoides.J. Chem. Ecol. 16:1059–1067.Google Scholar
  22. Stahl, E. (ed.) 1969. Thin-Layer Chromatography. Springer-Verlag, New York, 1041 pp.Google Scholar
  23. Verschaffelt, E. 1911. The cause determining the selection of food in some herbivorous insects.Proc. R. Acad. Amsterdam 13:536–542.Google Scholar
  24. von Euw, J., andReichstein, T. 1948. Die Glykoside der Samen vonStrophanthus nicholsonii Holm. Glykoside und Aglykone.Helv. Chim. Acta 31:883–892.Google Scholar

Copyright information

© Plenum Publishing Corporation 1993

Authors and Affiliations

  • K. Sachdev-Gupta
    • 1
  • Cd. Radke
    • 1
  • J. A. A. Renwick
    • 1
  • M. B. Dimock
    • 1
  1. 1.Boyce Thompson InstituteIthaca

Personalised recommendations