Johann Jurenitsch

Anti-oedematous activities of the main triterpendiol esters of marigold (Calendula officinalis L.)

Separation and isolation of the genuine faradiol esters (1, 2) from flower heads of Marigold (Calendula (officinalis L., Asteraceae) could be achieved by means of repeated column chromatography (CC) and HPLC for the first time. Structure elucidation of faradiol-3-myristic acid ester 1, faradiol-3-palmitic acid ester 2 and psi-taraxasterol 3 has been also performed, without any previous degradation by means of MS, 1H-NMR, 13C-NMR and 2D-NMR experiments. The anti-oedematous activities of these three compounds were tested by means of inhibition of Croton oil-induced oedema of the mouse ear. Both faradiol esters showed nearly the same dose dependent anti-oedematous activity and no significant synergism appeared with their mixture. The free monol, psi-taraxasterol, had a slightly lower effect. Furthermore, faradiol was more active than its esters and than psi-taraxasterol and showed the same effect as an equimolar dose of indomethacin.

Chemotaxonomic relevance of sesquiterpenes within the Achillea millefolium group

Abstract The chemotaxonomic relevance of sesquiterpenoids within the Achillea millefolium group has been evaluated by means of morphological, anatomical, cytological and phytochemical data. The sesquiterpene patterns of Achillea setacea Waldst. & Kit, Achillea asplenifolia Vent., Achillea roseoalba Ehrend., Achillea collina Becker, Achillea ceretanica Sennen, Achillea pratensis Saukel & Langer, Achillea distans subsp. styriaca Saukel in edit., Achillea millefolium L. and Achillea pannonica Scheele are described and shown to be characteristic for each species.

Sesquiterpenes and flavonoid aglycones from a Hungarian taxon of the Achillea millefolium group.

The investigation of a dichloromethane extract of flower heads of a Hungarian taxon of the Achillea millefolium group led to the isolation of three flavonoid aglycones, one triterpene, one germacranolide and five guaianolides. Their structures were elucidated by UV-VIS, EI- and CI-MS, 1H NMR and 13C NMR spectroscopic methods as well as by 2D-NMR studies and by selective 1D-NOE experiments. Besides apigenin, luteolin and centaureidin, β-sitosterol, 3β-hydroxy-11α,13-dihydro-costunolide, desacetylmatricarin, leucodin, achillin, 8α-angeloxy-leucodin and 8α-angeloxy-achillin were isolated. Both latter substances are reported here for the first time. Their NMR data were compared with those of the other guaianolides. The stereochemistry of 3β-hydroxy-11α,13-dihydro-costunolide was discussed and compared with data of the literature.

Gaschromatographische erfassung von 6-desoxyhexosen, pentosen und hexosen aus herzwirksamen glykosiden

Abstract A new, relatively simple and accurate method allows the identification and quantification of the monosaccharide compnents of cardiac glycosides. After hydrolysis under standard conditions the trimethylsilyl ethers of digitoxose, cymarose, fucose, rhamnose, 6-deoxyallose, 6-deoxygulose, 6-deoxyglucose, 6-dexyidose, 6-deoxytalose, 3-O-methylglucose, allose, altrose, gulose, idose, glucose, mannose, galactose, talose, arabinose, lyxose, ribose and xylose can be identified by gas chromatography on OV-101 or OV-17 as stationary phases. The retention times of the main peaks of each of the analysed monosaccharides, and the ratios of the peak areas of the different anomers were found to be characteristic and of good reproducibility. With phenyl-β- d -glucopyranoside as internal standard the quantification of the absolute amount of sugar present in cardiac glycosides of known constitution is possible, the recovery after hydrolysis being 71–92%. The method allows determination of the composition of the sugar chain in new cardiac glycosides and gives better information in a shorter time of analysis than other methods.

A triterpene saponin from Herniaria glabra

A new acetylated triterpene saponin was isolated from Herniaria glabra. GC, GC-MS, FAB-MS analysis and the use of 2D NMR techniques allowed the elucidation of its structure as 28-O-(beta-D-glucopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)- [beta-D-glucopyranosyl-(1-->3)]-4-acetyl-beta-D-fucopyranosyl(1-->))- medicagenic acid-3-O-beta-D-glucuronide.

Four major saponins from Solidago canadensis

Four new bisdesmosidic saponins each containing eight carbohydrate units were isolated from Solidago canadensis. GC, GC-MS, FABMS analysis and mainly the use of 2D NMR techniques allowed their identification as bayogeninglycosides (canadensissaponins 1-4) 3-O- [beta-D-glucopyranosyl-(1----3)-beta-D-glucopyranosyl]-28-O-[alpha-L- rhamnopyranosyl-(1----3)-beta-D-xylopyranosyl-(1----4)-[beta-D- xylopyranosyl-(1----3)]-alpha-L-rhamnopyranosyl-(1----2)-[beta-D- apio-D-furanosyl-(1----3)]-beta-D-6-deoxyglucopyranosyl- (1----]-bayogenin; -(1----2)-[beta-D-apio-D-furanosyl-(1----3)]-ara- binopyranosyl-(1----]-bayogenin; -[alpha-L-rhamnopyranosyl-(1----3)]-beta- D-6-deoxyglucopyranosyl-(1----]-bayogenin and - [alpha-L-rhamnopyranosyl- (1----3)]-arabinopyranosyl-(1----]-bayogenin.

Eudesmanolides from Achillea pratensis

Abstract From flower heads of Achillea pratensis five eudesmanolides were isolated by repeated column chromatography and HPLC. The compounds were identified as tauremisin, arglanin, 4-epi-arglanin, 4α-hydroperoxy-4α-dehydroxy-arglanin and santamarin.

The first structurally confirmed saponin from Solidago gigantea: structure elucidation by modern NMR techniques

Abstract A new bisdesmosidic triterpene saponin, containing ten carbohydrate residues has been isolated from Solidago gigantea var. serotina. The structure was determined mainly by NMR, using selective excitation by Gaus-shaped pulses in combination with multi-step relayed coherence transfer experiments.

Highly hydroxylated guaianolides of Achillea asiatica and Middle European Achillea species.

From flower heads of Achillea asiatica (L.) Serg., three new guaianolides were isolated by repeated column chromatography and HPLC. The constitution and the stereochemistry of these new, labile compounds were determined by MS, one ((1)H, (13)C, selective (1)H-TOCSY and (1)H-NOESY) and two-dimensional NMR experiments ((1)H, (1)H-COSY, (1)H, (13)C-HSQC, (1)H, (13)C-HMBC). The substances were identified as 8 alpha-angeloxy-2 alpha, 4 alpha,10 beta-trihydroxy-6 beta H,7 alpha H, 11 beta H-1(5)-guaien-12,6 alpha-olide (1), 8 alpha-angeloxy-1 beta,2 beta:4 beta,5 beta-diepoxy-10 beta-hydroxy-6 beta H, 7 alpha H, 11 beta H-12,6 alpha-guaianolide (2) and 8 alpha-angeloxy-4 alpha,10 beta-dihydroxy-2-oxo-6 beta H,7 alpha H, 11 beta H-1(5)-guaien-12,6 alpha-olide (3). They were also detected in Middle European species (Achillea collina, Achillea ceretanica (2x and 4x), Achillea roseoalba, Achillea asplenifolia) by HPLC, TLC and off line MS and have not been described before. The possibility that these compounds might be products of an oxidation process is discussed.

Saponins in Cyclamen species: configuration of cyclamiretin C and structure of isocyclamin

Abstract Five sapogenins and three saponins were identified in bulbs of 14 cytologically defined Cyclamen species and their structures were determined by means of mass, 1H and 13C NMR spectroscopy. In addition to the known products of hydrolysis, primulagenin A was found, and cyclamiretin C was shown to be identical with cyclamigenin C. The new saponin isocyclamin was identified as 3β-{O-β- d -glucopyranosyl-(1–6)-[O-β- d -xylopyranosyl-(1–2)]-O-β- d -glucopyranosyl-(1–4)-[O-β- d -glucopyranosyl-(1–2)] -α- l -arabinopyranosyl}-16α-hydroxy-13β, 28-epoxy-olean-30-al.