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Journal of Chemical Ecology

, Volume 21, Issue 11, pp 1745–1762 | Cite as

Neutral compounds from male castoreum of North American beaver,Castor canadensis

  • Rong Tang
  • Francis X. Webster
  • Dietland Müller-Schwarze
Article

Abstract

North American beavers (Castor canadensis) mark their territories with castoreum, the strong-smelling paste in their castor sacs. In their own territories, beavers respond with scent marking to experimental scent marks that consist of strange castoreum (or selected components). In part, the unique odor of castoreum is due to large amounts of phenolic compounds and neutral compounds. Purified neutral compounds were analyzed by GC. GC-MS, and NMR; identities of the neutral compounds were confirmed by comparing the properties of authentic compounds with those of the isolated compounds. We identified 13 neutral compounds that had not been reported before for castoreum. Most of these are oxygen-containing monoterpenes. Of the nine neutral compounds reported by Lederer (1949), only three are confirmed in our analysis; the other six neutral compounds are either absent or are not volatile enough to be detected by our methods. Eight compounds—6-methyl-l-heptanol, 4,6-dimethyl-l-heptanol, isopinocamphone, pinocamphone, two linalool oxides, and their acetates—were synthesized for structure identification and bioassays.

Key Words

beaver Castor canadensis castoreum neutral compounds monoterpenes co-injection fractionation identification synthesis territory marking 

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References

  1. Augustine, R.L. 1965. Catalytic Hydrogenation, Techniques and Applications in Organic Synthesis, 57. Marcel Dekker, New York.Google Scholar
  2. Bates, R.B., andThalacker, V.P. 1988. Nuclear magnetic resonance spectral parameters in bicyclo-[3.1.1]-heptanes, α-pinene, myrtenol and verbenone.J. Org. Chem. 33:1730–1739.Google Scholar
  3. Bollinger, K.S. 1980. Scent marking behavior of beaver (Castor canadensis). M.S. thesis. University of Massachusetts, Amherst. 186 pp.Google Scholar
  4. Brownlee, R.G., andSilverstein, R.M. 1968. A micro-preparative gas chromatography and a modified carbon skeleton determinator.Anal. Chem. 40:2077–2080.Google Scholar
  5. Corey, E.J., andSuggs, J.W. 1975. Pyridinium chlorochromate. An efficient reagent for oxidation of primary and secondary alcohols to carbonyl compounds.Tetrahedron Lett. 31:2647–2650.Google Scholar
  6. Couchman, F.M., Pinder, A.R., andBroraham, N.H. 1964. Studies on the essential oil ofCyperus africulatus L.Tetrahedron 20:2037–2045.Google Scholar
  7. Darby, U., Lamb, N., andMoney, T. 1978. Synthesis and absolute configuration of nojigiku alcohol.Can. J. Chem. 57:742–749.Google Scholar
  8. Dev, S., Narula, A.P.S., andYadav, J.S. 1982. CRC Handbook of Terpenoids. I: p. 137.Google Scholar
  9. Dreger, E. 1941,n-Hexyl alcohol.Org. Syn. Coll. 1:306–308.Google Scholar
  10. Duddeck, H., andDietrich, W. 1989. Structure Elucidation by Modern NMR. Steinkopff Verlag, Darmstadt. pp. 7–28.Google Scholar
  11. Erskin, R.L., andKnight, S.A. 1960. NMR study of the isomeric pinocamphones.Chem. Ind. 1160–1161.Google Scholar
  12. Felin, D., Melera, A., Seibl, J., andKováts. 1963. 167. Zur Kenntnis ätherischer Öle 2. Mitteilung. Die Struktur der sogenannten «Linalooloxide».Helv. Chim. Acta 46:1513–1536.Google Scholar
  13. Grønneberg, T. Ø. 1978. Analysis of a wax ester fraction from the anal gland secretion of beaver (Castor fiber) by chemical ionization mass spectrometry.Chem. Scr. 13:56–58.Google Scholar
  14. Grønneberg, T. Ø., andLie, T. 1984. Lipids of the anal gland secretion of beaver (Castor fiber).Chem. Scr. 24:100–103.Google Scholar
  15. Guenther, E. 1949. Individual essential oils of the plant families.Essent. Oils 3:437–439.Google Scholar
  16. Heikman, H., Baectstrom, P., andTorssell, K. 1968. Perester oxidation and NBS bromination of α-pinene.Acta Chem. Scand. 22:2034–2035.Google Scholar
  17. Herout, V., Motl, O., andŠorm, F. 1954.Coll. Czech. Chem. Commun. 19:990.Google Scholar
  18. Hodgdon, H.E. 1978. Social dynamics and behavior within an unexploited beaver (Castor canadensis) population. Ph.D. thesis. University of Massachusetts, Amherst. 292 pp.Google Scholar
  19. Houlihan, P.M. 1989. Scent mounding by beaver (Castor canadensis): Functional and semiochemical aspects. M.S. thesis. State University of New York, College of Environmental Science and Forestry, Syracuse. 184 pp.Google Scholar
  20. Jashi, V.S., Damedaran, N.P., andDev, S. 1968. Organic reactions in a solid matrix—I alumina-induced oxrane rearrangements.Tetrahedron 24:5817–5830.Google Scholar
  21. Johnson, W.S., Werthemann, L., Bartlett, R., Brocksom, T.J., Li, T., Faulkener, J.J., andPeterson, M.R. 1970. A simple stereoselective version of the Claisen rearrangement leading totrans-trisubstituted olefinic bonds. Synthesis of squalene.J. Am. Chem. Soc. 92:741–743.Google Scholar
  22. Julia, M., Descoins, C., andRise, C. 1966. Preparation and stereochemistry study of polyunsaturated alcohols obtained by homoallylic transfer.Tetrahedron Suppl. 2:443–462.Google Scholar
  23. Julia, S., Julia, M., Tchen, S., andGraffin, P. 1961. Some cases of vinylogous homoallylic rearrangement.Compt. Rend. 253(4):678–680.Google Scholar
  24. Kerschbaum, M. 1900. Ueber die aldehydischen Bestandtheile des Verbenaöles und über Verbenon.Chem. Ber. 33:885–893.Google Scholar
  25. Klein, E., Farnoe, H., andRojahn, W. 1964. Chemistry of linalool oxides.Ann. Chem. 675:73–82.Google Scholar
  26. Lederer, E. 1946. Chemistry and biochemistry of the scent glands of the beaver (Castor fiber).Nature 157:231–232.Google Scholar
  27. Lederer, E. 1949. Castoreum and ambergris: Chemical and biochemical constituents.Perfum. Essent. Oil Rec. 40:353–359.Google Scholar
  28. Levene, P.A., andAllen, C.H. 1916. The oxidation of branched chain fatty acids.J. Biol. Chem. 27:433–462.Google Scholar
  29. Marvel, C.S., andSekera, V.C. 1955.n-Dodecyl (lauryl)p-tolunesulfonate.Org. Syn. Coll. 3:366–367.Google Scholar
  30. Maurer, B., andOhloff, G. 1976. Zur Kenntnis der stickstoffhaltigen Inhaltsstoffe von Castoreum.Helv. Chim. Acta 59:1169–1185.Google Scholar
  31. Moffett, R.B. 1963. 2-(l-Pyrrolidyl)propanol.Org. Syn. Coll. 4:834–836.Google Scholar
  32. Müller-Schwarze, D. 1992. Castoreum of beaver (Castor canadensis): Function, chemistry and biological activity of its components. pp. 457–464.in R.L. Doty and D. Müller-Schwarze (eds.). Chemical Signals in Vertebrates 6. Plenum, New York.Google Scholar
  33. Müller-Schwarze D., andHeckman, S. 1980. The social role of scent marking in beaver (Castor canadensis).J. Chem. Ecol. 6:81–95.Google Scholar
  34. Müller-Schwarze D., andHoulihan, P.W. 1990. Pheromonal activity of single castoreum constituents in behaver,Castor canadensis.J. Chem. Ecol. 17:715–734.Google Scholar
  35. Müller-Schwarze, D., Morehouse, L., Corradi, R., Zhao, C.-H., andSilverstein, R.M. 1986. Odor images: Responses of beaver to castoreum fractions, pp. 561–570,in D. Duvall, D. Müller-Schwarze, and R.M. Silverstein (eds.). Chemical Signals in Vertebrates 4. Plenum, New York.Google Scholar
  36. Naves, Y.-R., Alves, H.M., Arndt, V.H., Gottlieb, O.R., andMagalhaes, M.T. 1963. 114. Etudes sur les matières végétales. CLXXXV. Sur les huiles essentielles de deux especes appartenant au genreCryptocaria.Helv. Chim. Acta 46:1056–1059.Google Scholar
  37. Nigam, I.C., andLevi, L. 1968. Essential oils and their constituents. XLII: Isomerization of epoxides on active alumina.Can. J. Chem. 46:1944–1947.Google Scholar
  38. Sadtler. 1980. Standard Spectra, NMR spectrum 52:30795M.Google Scholar
  39. Sadtler. 1981. Standard Carbon-13 NMR Spectra, 57:11298C.Google Scholar
  40. Scheline, R.R. 1991. Handbook of Mammalian Metabolism of Plant Compounds. CRC Press. Boca Raton, Florida, 514 pp.Google Scholar
  41. Schmidt, H. 1944. Zur Raumisomerie in der Pinanreihe (IV. Mitteil.*): Pinocarvon und die beiden diastereomeren Pinocarveole.Chem. Ber. 77:167–174.Google Scholar
  42. Schulte, B.A., Müller-Schwarze, D., Webster, F.X., andTang, R. 1994. Beaver (Castor canadensis) response to major phenolic and neutral compounds in castoreum.J. Chem. Ecol. 21:3063–3081.Google Scholar
  43. Schwartz, M.A., Crowell, J.D., andMusser, J.H. 1972. Biogenetically patterned approaches to eudesmane sesquiterpenes.J. Am. Chem. Soc. 94:4361–4363.PubMedGoogle Scholar
  44. Shaligram, A.S.R., andBhattacharyya, S.C. 1962. Terpenoids—XXXII. Absolute configuration of junenol and laevojunenol and synthesis of junenol from costunolide.Tetrahedron 18:969–977.Google Scholar
  45. Shimizu, S., Karasawa, D., andIkeda, N. 1966. A new mint (variety ofMentha aquatica L.) containing (—)-isopinocamphone as a major constituent of essential oil.Agric. Biol. Chem. 30:200–201.Google Scholar
  46. Stevens, P.G. 1943. American musk. II. A preliminary note on the scent glands of the beaver.J. Am. Chem. Soc. 65:2471.Google Scholar
  47. Svendsen, G.E. 1980. Patterns of scent-mounding in a population of beaver (Castor canadensis).J. Chem. Ecol. 6:133–148.Google Scholar
  48. Svendsen, G.E., andHuntsman, W.D. 1988. A field bioassay of beaver castoreum and some of its components.Am. Midl. Nat. 120:144–149.Google Scholar
  49. Tang, R., Webster, F.X., andMüller-Schwarze, D. 1993. Phenolic compounds from male castoreum of the North American beaver,Castor canadensis.J. Chem. Ecol. 19:1491–1500.Google Scholar
  50. Uchio, Y. 1977. Constituents of the essential oil ofChrysanthemum japonnense. Nojigiku alcohol and its acetate.Bull. Chem. Soc. Jpn. 51(8):2342–2346.Google Scholar
  51. Valenta, Z., Khaleque, A., andRashid, M.H. 1960.cis-Cyclohexane-1,2-diol in the beaver gland.Experientia 17:130.Google Scholar
  52. Walbaum, H., andRosenthal, A. 1927. Odoriferous substances in castoreum.J. Prakt. Chem. 117:225–232.Google Scholar
  53. Welsh, R.G., andMüller-Schwarze, D. 1989. Experimental habitat scenting inhibits colonization by beaver,Castor canadensis.J. Chem. Ecol. 15:887–893.Google Scholar
  54. Wilt, J.W., Massie, S.N., andDabet, R.B. 1970. Reaction of 2-(3-cyclopentenyl)-ethyl bromide with tri-n-butyltin hydride. Cyclization to norbonane.J. Org. Chem. 35:2803–2806.Google Scholar
  55. Zweifel G., andBrown, H.C. 1964. Hydrogenation of terpenes.J. Am. Chem. Soc. 86:393–397.Google Scholar

Copyright information

© Plenum Publishing Corporation 1995

Authors and Affiliations

  • Rong Tang
    • 1
  • Francis X. Webster
    • 1
  • Dietland Müller-Schwarze
    • 2
  1. 1.Department of ChemistryState University of New York College of Environmental Science and ForestrySyracuse
  2. 2.Department of BiologyState University of New York College of Environmental Science and ForestrySyracuse

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