Abstract
Three alkaloids—two minor decahydroquinolines (DHQs) and a major quinolizidine—were detected in an extract of a Brazilian myrmicine ant (Solenopsis (Diplorhoptrum) sp. picea group). One DHQ (3) was identical to a known frog-skin alkaloid, cis-195A (cis-5-methyl-2-propyldecahydroquinoline), while the second DHQ, an isomer of 3, designated 195J, was assigned a tentative cis-2-methyl-5-propyldecahydroquinoline structure (2) based on mass and infrared spectra. The third alkaloid proved identical to the frog-skin alkaloid 195C, for which a structure had not been previously proposed. Mass and infrared spectral analysis, including chemical ionization tandem mass spectrometry, indicated a 4-methyl-6-propylquinolizidine structure (1) for 195C. The four possible diastereomers were synthesized and the (6Z,10E)-4-methyl-6-propylquinolizidine diastereomer (1b) was identical to the natural alkaloid. Skin extracts of a population of a Madagascan mantelline frog contained, among other alkaloids, minor amounts of the same alkaloid triad 1–3 with 1 again predominating. The common occurrence of alkaloids 1–3 in both ant and frog supports the hypothesis that ants are a likely dietary source for sequestered frog-skin alkaloids and brings to six, the alkaloid classes common to ant and frog.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
REFERENCES
Caldwell, J. P. 1996. The evolution of myrmecophagy and its correlates in poison frogs (family Dendrobatidae). J. Zool. (London). 240:75–101.
Daly, J. W. 1995. Alkaloids from frog skin: Selective probes for ion channels and nicotinic receptors. Braz. J. Med. Biol. Res. 28:1033–1042.
Daly, J. W., Myers, C. W., and Whittaker, N. 1987. Further classification of skin alkaloids from neotropical poison frogs (Dendrobatidae), with a general survey of toxic/noxious substances in the Amphibia. Toxicon 25:1023–1095.
Daly, J. W., Secunda, S. I., Garraffo, H. M., Spande, T. F., Wisnieski, A., Nishihara, C., and Cover, J. F., Jr. 1992. Variability in alkaloid profiles in neotropical poison frogs (Dendrobatidae): Genetic versus environmental determinants. Toxicon 30:887–898.
Daly, J. W., Garraffo, H. M., and Spande, T. F. 1993. Amphibian alkaloids, pp. 185–288, in G. A. Cordell (ed.). The Alkaloids, Vol. 43. Academic Press, San Diego.
Daly, J. W., Secunda, S. I., Garraffo, H. M., Spande, T. F., Wisnieski, A., and Cover, J. F., Jr. 1994a. An uptake system for dietary alkaloids in poison frogs (Dendrobatidae). Toxicon 32:657–663.
Daly, J. W., Garraffo, H. M., Spande, T. F., Jaramillo, C., and Rand, A. S. 1994b. Dietary source for skin alkaloids of poison frogs (Dendrobatidae)? J. Chem. Ecol. 20:943–955.
Daly, J. W., Andriamaharavo, N. R., Andriantsiferana, M., and Myers, C. W. 1996. Madagascan poison frogs (Mantella) and their skin alkaloids. Am. Mus. Novit. No. 3177:1–34.
Daly, J. W., Garraffo, H. M., and Myers, C. W. 1997. The origin of frog skin alkaloids: An enigma. Pharm. News 4:9–14.
Donnelly, M. A. 1991. Feeding patterns of the strawberry poison frog, Dendrobates pumilio (Anura: Dendrobatidae). Copeia 3:723–730.
Garraffo, H. M., Caceres, J., Daly, J. W., and Spande, T. F. 1993a. Alkaloids in Madagascan frogs (Mantella): Pumiliotoxins, indolizidines, quinolizidines, and pyrrolizidines. J. Nat. Prod. 56:1016–1038.
Garraffo, H. M., Spande, T. F., Daly, J. W. Baldessari, A., and Gros, E. G. 1993b. Alkaloids from bufonid toads (Melanophryniscus): Decahydroquinolines, pumiliotoxins and homopumiliotoxins, indolizidines, pyrrolizidines and quinolizidines. J. Nat. Prod. 56:357–373.
Garraffo, H. M., Simon, L. D., Daly, J. W., Spande, T. F., and Jones, T. H. 1994. cis- and trans-Configurations of α,α′-disubstituted piperidines and pyrrolidines by GC-FTIR; application to decahydroquinoline stereochemistry. Tetrahedron 50:11329–11338.
Garraffo, H. M., Jain, P., Spande, T. F., and Daly, J. W. 1997. Alkaloid 223A: The first trisubstituted indolizidine from dendrobatid frogs. J. Nat. Prod. 60:2–5.
Grieco, P. A., and Parker, D. T. 1988. Octahydroquinoline synthesis via immonium ion based Diels-Alder chemistry: Synthesis of (−)-8a-epi-pumiliotoxin C. J. Org. Chem. 53:3658–3662.
Grierson, D. S., Royer, J., Guerrier, L., and Husson, H.-P. 1986. Asymmetric synthesis. 6. Practical synthesis of (+)-solenopsin A. J. Org. Chem. 51:4475–4477.
Jain, P., Garraffo, H. M., Yeh, H. J. C., Spande, T. F., Daly, J. W., Andriamaharavo, N. R., and Andriantsiferana, M. 1996. A 1,4-disubstituted quinolizidine from a Madagascan mantelline frog (Mantella). J. Nat. Prod. 59:1174–1178.
Johns, S. R., Lamberton, J. A., Sioumis, A. A., and Suares, H. 1974. The alkaloids of Poranthera corymbosa (Euphorbiacae). Aust. J. Chem. 27:2025–2034.
Jones, T. H., and Blum, M. S. 1983. Arthropod alkaloids: Distribution, functions, and chemistry, pp. 33–84, in S. W. Pelletier (ed.). Alkaloids, Chemical and Biological Perspectives, Vol. 1. John Wiley & Sons, New York.
Jones, T. H., Blum, M. S., and Robertson, H. G. 1990. Novel dialkylpiperidines in the venom of the ant Monomorium delagoense. J. Nat. Prod. 53:429–435.
Jones, T. H., Torres, J. A., Spande, T. F., Garraffo, H. M., Blum, M. S., and Snelling, R. R. 1996. Chemistry of venom alkaloids in some Solenopsis (Diplorhoptrum) species from Puerto Rico. J. Chem. Ecol. 22:1221–1236.
MacConnell, J. G., Blum, M. S., and Fales, H. M. 1971. The chemistry of fire ant venom. Tetrahedron 27:1129–1139.
Matsunaga, T., Kawasaki, I., and Kaneko, T. 1967. 2-Hydroxy-4-phenylquinolizidine. Tetrahedron Lett. 2471–2473.
Silverstone, P. A. 1975. A revision of the poison-arrow frogs of the genus Dendrobates Wagler. Nat. Hist. Mus. Los Angeles Cty. Sci. Bull. 21:1–55.
Silverstone, P. A. 1976. A revision of the poison-arrow frogs of the genus Phyllobates Bibron in Sagra (family Dendrobatidae). Nat. Hist. Mus. Los Angeles Cty. Sci. Bull. 27:1–53.
Spande, T. F., Jain, P., Garraffo, H. M., Pannell, L. K., Yeh, H. J. C., Daly, J. W., Fukumoto, S., Imamura, K., Tokuyama, T., Torres, J. A., Snelling, R. R., and Jones, T. H. 1999. Occurrence and significance of decahydroquinolines from dendrobatid poison frogs and a myrmicine ant: Use of 1H-and 13-CNMR in their conformational analysis. J. Nat. Prod. 65:5–21.
Toft, C. A. 1980. Feeding ecology of thirteen syntopic species of anurans in a seasonal tropical environment. Oecologia 45:131–141.
Toft, C. A. 1995. Evolution of diet specialization in poison-dart frogs (Dendrobatidae). Herpetologica 51:202–216.
Tokuyama, T., Tsujita, T., Shimada, A., Garraffo, H. M., Spande, T. F., and Daly, J. W. 1991. Alkaloids from dendrobatid poison frogs: Further cis-decahydroquinolines and 8-methylindolizidines. Tetrahedron 47:5401–5414.
Yasuda, S., Hanaoka, M., and Arata, Y. 1977. A new synthesis of (±)-7-epideoxynupharidine and (±)-1-epi-7-epi-deoxynupharidine. Heterocycles 6:391–394.
Yu, C. K., Oldfield, D., and Macklean, D. B. 1970. Mass spectra of decahydroquinolines. Org. Mass Spect. 4:147–155.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Jones, T.H., Gorman, J.S.T., Snelling, R.R. et al. Further Alkaloids Common to Ants and Frogs: Decahydroquinolines and a Quinolizidine. J Chem Ecol 25, 1179–1193 (1999). https://doi.org/10.1023/A:1020898229304
Issue Date:
DOI: https://doi.org/10.1023/A:1020898229304