Wax Composition of Serbian spp. (Caryophyllaceae): Identification of New Metabolites and Chemotaxonomic Implications.

Although ethnopharmacologically renowned, wax constituents of species were sporadically studied. A combination of GC-MS analysis, synthesis, and chemical transformations enabled the identification of 275 constituents of diethyl-ether washings of aerial parts and/or flowers of six taxa (, , subsp. , subsp. , , and ) and one taxon () from Serbia. Seventeen of these constituents (nonacosyl benzoate, additional 12 benzoates with -branched 1-alkanols, eicosyl tiglate, triacontane-14,16-dione, dotriacontane-14,16-dione, and tetratriacontane-16,18-dione) and two additional synthesized eicosyl esters (angelate and senecioate) represent completely new compounds. The structures of the tentatively identified β-ketones were confirmed by analysis of the mass fragmentation of the corresponding pyrazoles and silyl enol ethers obtained by transformations of crude extracts and extract fractions. Silylation allowed the identification of 114 additional constituents, including a completely new natural product (30-methylhentriacontan-1-ol). The results obtained by multivariate statistical analyses showed that the chemical profile of taxa's surface waxes is subject to both genetic and ecological factors, whereas the latter seemingly takes a more important role for the studied samples.