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Planta Med 2004; 70(10): 967-977
DOI: 10.1055/s-2004-832624
Original Paper
Natural Product Chemistry
© Georg Thieme Verlag KG Stuttgart · New York

New Triterpene Esters from Flowerheads of Arnica lonchophylla

Thomas J. Schmidt1 , Jeanette von Raison1 , Günter Willuhn1
  • 1Institut für Pharmazeutische Biologie der Heinrich-Heine-Universität Düsseldorf, Düsseldorf, Germany
Part of the dissertation of JvR. Some of these results have been presented as posters at the annual meetings of the GA in Regensburg, 1997 and Vienna 1998
Further Information

Publication History

Received: May 4, 2004

Accepted: July 19, 2004

Publication Date:
18 October 2004 (online)

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Abstract

From the flowerheads of Arnica lonchophylla Greene ssp. lonchophylla Maguire (Asteraceae), a variety of mono-, di- and trihydroxytriterpenes of the oleanane, ursane, lupane and dammarane types were isolated and their structures elucidated by EI and CI mass spectrometry and extensive NMR spectroscopic analysis. Most of the compounds are esterified at position 3 with lauric, myristic, palmitic and stearic acids. Several ester derivatives of known triterpenes represent new natural products. The triterpenetriols 20(30)-taraxasten-3β,16β,21α-triol (arnitriol A) and lupane-3β,16β,20-triol, both isolated in the form of their C3-fatty acid ester derivatives, possess hydroxylation patterns which have not been described previously. Besides small amounts of triterpenetriol esters, the lauric, myristic, palmitic and stearic acid esters of arnidiol, faradiol, maniladiol and calenduladiol were also identified in the flowerheads of A. montana (Arnicae flos Ph. Eur.), A. chamissonis ssp. foliosa and A. angustifolia ssp. attenuata. A search for sesquiterpene lactones in the flowers of A. lonchophylla resulted in the identification of small amounts of helenalin and 11α,13-dihydrohelenalin.

Key words

Arnica lonchophylla - Asteraceae - triterpene esters - sesquiterpene lactones

References

  • 1 von Raison J. Untersuchungen zur Sekundärstofführung der Blüten von Arnica lonchophylla sowie zur systematischen Stellung der Gattung Arnica innerhalb der Asteraceae anhand der RbcL-Basensequenzen. Dissertation Universität Düsseldorf; 1999
    Search in Google Scholar
  • 2 Willuhn G, Merfort I, Paßreiter C M, Schmidt T J. Chemistry and Systematics of the Genus Arnica .  In: Advances in Compositae Systematics. Hind DJN, Jeffrey C, Pope GV editors Kew: Royal Botanic Gardens; 1994: pp 167-95
    Search in Google Scholar
  • 3 Maguire B. A monograph of the genus Arnica .  Brittonia. 1943;  4 386-510
    PubMedSearch in Google Scholar
  • 4 Schmidt T J, Willuhn G, Steigel A, Wendisch D. Sesquiterpene lactones and inositol esters from Arnica angustifolia .  Planta Med. 1995;  61 544-50
    PubMedSearch in Google Scholar
  • 5 Schmidt T J, Willuhn G. Sesquiterpene lactone and flavonoid variability of the Arnica angustifolia aggregate (Asteraceae).  Biochem Syst Ecol. 2000;  28 133-42
    PubMedSearch in Google Scholar
  • 6 Della Loggia R, Tubaro A, Sosa S, Becker H, Saar S, Isaak O. The role of triterpenoids in the topical anti-inflammatory activity of Calendula officinalis flowers.  Planta Med. 1994;  60 516-20
    Thieme ConnectPubMedSearch in Google Scholar
  • 7 Asukawa K, Akihisa T, Oinuma H, Kasahara Y, Kimura Y, Yamanouchi S, Kumaki K, Tamura T, Takido M. Inhibitory effect of di- and trihydroxy triterpenes from the flowers of Compositae on 12-O-tetradecanoylphorbol-13-acetate-induced inflammation.  Biol Pharm Bull. 1996;  19 1329-31
    PubMedSearch in Google Scholar
  • 8 Zitterl-Eglseer K, Sosa S, Jurenitsch J, Schubert-Zsilavecz M, Della Loggia R, Tubaro A, Bertoldi M, Franz C. Anti-oedematous activities of the main triterpendiol esters of marigold (Calendula officinalis L.)  J Ethnopharmacol. 1997;  57 139-44
    CrossrefPubMedSearch in Google Scholar
  • 9 Pinchon T M, Pinkas M. Le genre Arnica .  Plant Med Phytother. 1988;  22 124-56
    PubMedSearch in Google Scholar
  • 10 Budzikiewicz H, Wilson J M, Djerassi C. Mass spectrometry in structural and stereochemical problems. XXXII. Pentacyclic triterpenes.  J Am Chem Soc. 1963;  85 3688-99
    PubMedSearch in Google Scholar
  • 11 Lee H D, Eichmeier L S, Piatak D M. Mass spectral study of ring E of taraxasterol and compounds with similar ring substitution.  Org Mass Spectrom. 1985;  20 247-52
    CrossrefPubMedSearch in Google Scholar
  • 12 Willuhn G, Leven W, Luley C. Arnikablüten DAB 10. Untersuchungen zur qualitativen und quantitativen Variabilität des Sesquiterpenlactongehaltes der offizinellen Arnikadrogen.  Dtsch Apotheker Ztg. 1994;  134 4077-85
    PubMedSearch in Google Scholar
  • 13 Pyrek J S. Terpenes of Compositae plants. Part VI. Faradiol and arnidiol, revision of their structure.  Pol J Chem (Rocz Chem). 1977;  51 2331-42
    PubMedSearch in Google Scholar
  • 14 Schwartz N N, Blumbergs J H. Epoxidations with m-chloroperbenzoic acid.  J Org Chem. 1964;  29 1976-9
    CrossrefPubMedSearch in Google Scholar
  • 15 Torres P, Chinchilla R, Grande M. Triterpenes from Senecio linifolius .  Stud Chem. 1992;  17 53-7
    PubMedSearch in Google Scholar
  • 16 Pyrek J S. Terpene of Compositae plants. Part IX. Structure of two new ψ-taraxene derivatives: heliantriols C and F. Mass spectrometry of 16-substituted ψ-taraxenes.  Pol J Chem (Rocz Chem). 1979;  53 1071-84
    PubMedSearch in Google Scholar
  • 17 Wilkomirsky B. Pentacyclic triterpene triols from Calendula officinalis flowers.  Phytochemistry. 1985;  24 3066-7
    CrossrefPubMedSearch in Google Scholar
  • 18 Pyrek J S. Terpenes of Compositae plants. Part XI. Structures of heliantriols B0, B1, B2 and A1, new pentacyclic triterpenes from Helianthus annuus L. and Calendula officinalis L.  Pol J Chem (Rocz Chem). 1979;  53 2465-90
    PubMedSearch in Google Scholar
  • 19 Morales G, McLaughlin J L. 3β-O-Palmityl longispinogenin from Trichocereus chilensis .  J Nat Prod. 1989;  52 381-4
    CrossrefPubMedSearch in Google Scholar
  • 20 Tori K, Yoshimura Y, Seo S, Sakurawi K, Tomita Y, Ishii H. Carbon-13 NMR spectra of saikogenins. Stereochemical dependence in hydroxylation effects upon carbon-13 chemical shifts of oleanene-type triterpenoids.  Tetrahedron Lett. 1976;  46 4163-6
    PubMedSearch in Google Scholar
  • 21 Díaz J G, Barba B, Herz W, Bierner M W. Sesquiterpene lactones and monoterpene glucopyranosides of Tetraneuris linearifolia var. arenicola .  Phytochemistry. 1992;  31 3471-7
    CrossrefPubMedSearch in Google Scholar
  • 22 Öksüz S, Topcu G. Triterpene fatty acid esters and flavonoids from Inula britannica .  Phytochemistry. 1987;  26 3082-4
    CrossrefPubMedSearch in Google Scholar
  • 23 Wenkert E, Baddeley G V, Burfitt I R, Moreno L N. Carbon-13 nuclear magnetic resonance spectroscopy of naturally-occuring substances. LVII. Triterpenes related to lupane and hopane.  Org Magn Reson. 1978;  11 337-43
    CrossrefPubMedSearch in Google Scholar
  • 24 Grande M, Torres P, Piera F, Bellido I S. Triterpenoids from Dittrichia viscosa .  Phytochemistry. 1992;  31 1826-8
    CrossrefPubMedSearch in Google Scholar
  • 25 Butruille D, Dominguez X A. Fouquierol et isofouquierol: deux nouveaux triterpenes de la serie du dammarane.  Tetrahedron Lett. 1974;  8 639-42
    PubMedSearch in Google Scholar

Priv.-Doz. Dr. Thomas J. Schmidt

Institut für Pharmazeutische Biologie der Heinrich-Heine-Universität Düsseldorf

Universitätsstraße 1, Geb. 26.23

40225 Düsseldorf

Germany

Phone: +49-211-8114179

Fax: +49-211-8111923

Email: schmidtt@uni-duesseldorf.de