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.
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References
Bax, A., andMorris, G.A. 1981. An improved method for heteronuclear chemical shift correlation by two-dimensional NMR.J. Magn. Reson. 42:501–505.
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.
Brauchli, P., Schindler, O., andReichstein, T. 1961. Die cardenolide vonCastillo elastica Cerv.Helv. Chim. Acta 44:904–919.
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.
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.
Doddrell, D.M., Pegg, D.T., andBendall, M.R. 1982. Distortionless enhancement of NMR signals by polarization transfer.J. Magn. Reson. 48:323–327.
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.
Makarevich, I.F. 1965. Presence of glucodigifucoside inErysimum cheiranthoides.Khim. Prir. Soedin. No. 2:67–69 (English translation).
Makarevich, I.F., Kolesnikov, D.D., andBelokon, V.F. 1974. Cardiac glycosides ofCheiranthus allionii.Khim. Prir. Soedin. No. 5:616–618 (English translation).
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).
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.
Maslennikova, V.A., Umarova, R.U., andAbubakirov, N.K. 1975. Cardenolides ofErysimum cuspidatum.Khim. Prir. Soedin. No. 2:179–182 (English translation).
Moore, J.A., Tamm, C., andReichstein, T. 1954. Glycosides of the wallflower,Cheiranthus cheiri.Helv. Chim. Acta 37:755–770.
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.
Okano, A. 1957. Studies on the constituents ofDigitalis purpurea L. VI. Glucodigifucoside, a new cardiotonic glycoside.Chem. Pharm. Bull. 5:272–276.
Reichstein, T., andWeiss, E. 1962. The sugars of the cardiac glycosides.Adv. Carb. Chem. 17:65–120.
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.
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.
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.
Robien, W., Kopp, B., Schable, D., andSchwarz, H. 1987. Carbon-13 NMR spectroscopy of cardenolides and bufadienolides.Prog. NMR Spectrosc. 19:131–181.
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.
Stahl, E. (ed.) 1969. Thin-Layer Chromatography. Springer-Verlag, New York, 1041 pp.
Verschaffelt, E. 1911. The cause determining the selection of food in some herbivorous insects.Proc. R. Acad. Amsterdam 13:536–542.
von Euw, J., andReichstein, T. 1948. Die Glykoside der Samen vonStrophanthus nicholsonii Holm. Glykoside und Aglykone.Helv. Chim. Acta 31:883–892.
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Sachdev-Gupta, K., Radke, C., Renwick, J.A.A. et al. Cardenolides fromErysimum cheiranthoides: Feeding deterrents toPieris rapae larvae. J Chem Ecol 19, 1355–1369 (1993). https://doi.org/10.1007/BF00984881
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DOI: https://doi.org/10.1007/BF00984881