New triterpene esters from flowerheads of Arnica lonchophylla

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-3beta,16beta,21alpha-triol (arnitriol A) and lupane-3beta,16beta,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 11alpha,13-dihydrohelenalin.