The range of natural simple coumarins is extended by discovery of the
highly oxygenated representatives 6,8-dihydroxy-7-methoxycoumarin, 6,7
,8-trihydroxycoumarin, 6,8-dihydroxy-5,7-dimethoxycoumarin, and 7-acet
oxy-5,6-dimethoxycoumarin. They are accompanied in the roots of Pelarg
onium sidoides by the widely occurring scopoletin, associated with the
uncommon analogues 5,6,7-trimethoxycoumarin, 7-hydroxy-5,6-dimethoxyc
oumarin (umckalin), and 5,6,7,8-tetramethoxycoumarin (artelin), these
being reported from a plant source for the second time. The structures
of these compounds were established from chemical and spectroscopic s
tudies. Differentiation between oxygenation patterns is discussed on t
he basis of chemical shift data.