Terpenoid composition of three fossil resins from Cretaceous and Tertiary conifers

The terpenoid composition of three fossil resins from macrofossils of Cretaceous and Tertiary conifers has been analyzed by gas chromatography-mass spectrometry (GC-MS). The mono-, sesqui- and diterpenoids which have been identified in the resin extracts are derived from precursors produced by the respective source plants and may be used as chemosystematic markers when compared with terpenoids in extant conifers. Sesquiterpenoids (cedrene, cuparene, cadinanes) and phenolic diterpenoids (ferruginol and derivatives) are the major components in Cupressospermum saxonicum Mai (Miocene). The terpenoid characteristics strongly support a relationship to the Cupressaceae s. str. The resin of Doliostrobus taxiformis (Sternberg) Kvacek (Eocene) consists of abietane and pimarane type resin acids accompanied by minor amounts of phenolic diterpenoids (ferruginol, hinokiol). According to morphological and anatomical characteristics, D. taxiformis was previously compared to both, extant Araucariaceae and Cupressaceae s.l., but the terpenoid pattern of the resin now supports a relationship to the Cupressaceae s.l. rather than to Araucariaceae. Degraded diterpenoids of the abietane type are the major compounds in the extract of Tritaenia linkii (Roemer) Magdefrau et Rudolf (Lower Cretaceous) indicating considerable oxidative alteration of the resin. Since the terpenoids in the resin of T. linkii are highly degraded or belong to the common abietane class, the leaves cannot be assigned or compared to any modern family based on their terpenoid composition. The presence of ferruginol probably excludes pinaceous affinities. Terpenoids proved to be valuable chemosystematic markers for fossil conifers once they are adequately preserved. The analysis of resin extracts by GC-MS is a suitable tool for the investigation of soluble compounds in fossil plants. (C) 2002 Elsevier Science B.V. All rights reserved.