Beschreibung:
<jats:title>Abstract</jats:title><jats:p><jats:italic>Mercurialis annua</jats:italic> and <jats:italic>M. perennis</jats:italic> are medicinal plants used in complementary medicine. In the present work, analytical methods to allow a chemotaxonomic differentiation of <jats:italic>M. annua</jats:italic> and <jats:italic>M. perennis</jats:italic> by means of chemical marker compounds were established. In addition to previously published compounds, the exclusive presence of pyridine‐3‐carbonitrile and nicotinamide in CH<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub> extracts obtained from the herbal parts of <jats:italic>M. annua</jats:italic> was demonstrated by GC/MS. Notably, pyridine‐3‐carbonitrile was identified for the first time as a natural product. Further chromatographic separation of the CH<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub> extracts <jats:italic>via</jats:italic> polyamide yielded a MeOH fraction exhibiting a broad spectrum of side‐chain saturated <jats:italic>n‐</jats:italic>alkylresorcinols. While the <jats:italic>n‐</jats:italic>alkylresorcinol pattern was similar for both plant species, some specific differences were observed for particular <jats:italic>n‐</jats:italic>alkylresorcinol homologs. Finally, the investigation of H<jats:sub>2</jats:sub>O extracts by LC/MS/MS revealed the presence of depside constituents. Whereas, in <jats:italic>M. perennis</jats:italic>, a mixture of mercurialis acid (=(2<jats:italic>R</jats:italic>)‐[(<jats:italic>E</jats:italic>)‐caffeoyl]‐2‐oxoglutarate) and phaselic acid (=(<jats:italic>E</jats:italic>)‐caffeoyl‐2‐malate) could be detected, in <jats:italic>M. annua</jats:italic> solely phaselic acid was found. By comparison with synthesized enantiomerically pure (2<jats:italic>R</jats:italic>)‐ and (2<jats:italic>S</jats:italic>)‐phaselic acids, the configuration of the depside could be determined as (2<jats:italic>S</jats:italic>) in <jats:italic>M. annua</jats:italic> and as (2<jats:italic>R</jats:italic>) in <jats:italic>M. perennis.</jats:italic></jats:p>