Orphan flavonoids and dihydrochalcones from Primula exudates.

Two orphan flavonoids containing an oxepin structure in ring A and named as Primcortusin (1) and 3'-OH-Primcortusin (2) were isolated from leaf exudates of Primula cortusoides, while P. glutinosa exudates yielded two dihydrochalcone derivatives (3,4). These novel structures have not been detected in other species of Primula so far. Chemical structures were elucidated by 2D NMR and mas spectrometry. The nature of compounds 1 and 2 is discussed, and ideas about their possible origin and that of unsubstituted flavone and other irregular substituted Primula flavones are presented.

Diversification of exudate flavonoid profiles in further Primula spp.

In continuation of previous work, exudate flavonoid profiles of 22 new accessions of the genus Primula L. aligned to different subgenera were studied for the first time. Profiling was done by comparative TLC and UV-HPLC against authentic marker compounds. Most of the studied species accumulated the typical Primula flavonoids, comprising derivatives of unsubstituted flavone, of 5,8- or 5,6-hydroxyflavones including partly highly oxygenated flavones, together with 2,2'-diOH-chalcone in their exudate. The profile of P. edelbergii belonging to subgen. Sphondylia differed largely from the majority of Primula species studied so far, showing accumulation tendencies similar to those observed earlier for the closely related genus Dionysia. The phylogenetic significance of this diversification is shortly addressed.

Flavonoids in selected Primula spp.: bridging micromorphology with chemodiversity.

A combined study was carried out on the micromorphology and chemistry of glandular trichomes with focus on Primula vialii and P. vulgaris, respectively. Epifluorescence microscopy was applied to study the auto-fluorescent properties of flavonoids and their localization in glandular trichomes. Both species differed in the morphology of the glandular trichomes and in the exudate flavonoid composition. Leaf glands from P. vialii and from some species of subgen. Primula exhibited uniform glandular fluorescence, but notable differentiation was observed within a single leaf of P. vulgaris. Our observations indicate that exudate flavonoids are not transported from the tissue to the glandular hairs. Conversely, only the newly isolated glycoside 1 (kaempferol 3-O-(2"'-rhamnosyl)-robinobioside) was obtained from leaf tissue of P. vialii after removal of the exudate. Its structure was confirmed by NMR and mass spectrometry. This glycoside was not detected in tissue extracts of P. vulgaris after similar treatment. The observed chemical diversity is discussed, with focus on possible correlation with glandular structures and tissue differentiation in Primula, and also against other studied species. Aspects of biosynthesis in relation to tissue-specific flavonoid diversification are shortly addressed.

Unusual compounds from exudates of Dionysia diapensifolia and D. gaubae var. megalantha (Primulaceae).

Exudates of Dionysia diapensifolia yielded (R)-(+)-3-acetoxy-3-phenyl-propiophenone as a new natural product with a basic dihydrochalcone structure, which was elucidated unequivocally by mass spectrometry and NMR spectroscopy. The sesquiterpenoidcarissone was found as the major compound in the exudate of D. gaubae var. megalantha. Sesquiterpenoids have so far not been described as exudate constituents of Primula and Dionysia. Structural identifications are discussed in detail, and the significance of the occurrence of these unusual compounds in exudates of Primulaceae is shortly addressed.

Exudate flavonoids of Primula spp: structural and biogenetic chemodiversity.

Several new accessions of the genus Primula and of the closely related Cortusa matthioli have been studied for their exudate flavonoid profiles. Unsubstituted flavone, 5-hydroxy-, 2'-hydroxyflavone and 5,2'-dihydroxyflavone were found as main components. Several other rather unusual substitution patterns were also found. 8-O-Substituted flavones appear to be accumulated more often than 6-O-substituted products. Chalcones with corresponding substitution patterns were of scattered occurrence, while flavanones could so far not be detected in exudates of Primula species. The distribution of externally accumulated flavonoids, including literature data, is related to current taxonomic views on the infrageneric grouping of Primula and related taxa. Organ-specific accumulation, biosynthetic and chemosystematic aspects are briefly addressed.