Kurt Jentzsch

Zur biogenese von strophanthidin-glykosiden: Convallatoxol als vorstufe von convallatoxin in Convallaria majalis

Labelled convallatoxin was isolated from leaves of Convallaria majalis after administration of convallatoxol-19-3H and convallatoxol-U-14C, resp. Oxidation of-CH2OH → -CHO at the glycoside level therefore is a possible step in the biogenesis of strophanthidin glycosides.

Untersuchungen über Wachstum, Morphogenese und Glykosidbildung an Wurzelorgankulturen von Digitalis purpurea L.

Summary Growth of isolated Digitalis purpurea roots of different origin have been tested in several basal media for a period of several months and for a series of cultivation passages.Among the roots used, i.e.roots of sterile little plants, of multiple bud cultures and roots grown on callus or leaf tissues, the last mentioned proved to be best suited for the start of organ cultures.Among the different media tested (HELLER, MURASHIGE and SKOOG, TORREY) the medium of TORREY supplemented by 2 % saccharose and 10 -7 g/ml IAA was optimally suited.Addition of vitamins proved to be no requirement for uniformly continued root growth of the organ cultures.Increase of IAA-concentrations and addition of 2,4-D affected the morphology: IAA increase led to the development of especially tender roots, and addition of 2,4-D elicited local callus formation over the total length extension of the roots. The capacity of root cells for glycoside formation has been followed by determination of the extend and the spectrum of cardenolid-synthesis of isolated and continually cultivated roots.Roots that emerged on leaf explants in vitro were best suited, since they are in similar developmental stages.After isolation they can be induced to uniform and continued growth. The glycoside analysis demonstrate that after isolation the root cells continue to synthetisize glycosides in extent and composition similar to the primer tissue.Also the cardenolid spectra of the primer roots and of the isolated roots after 2 months of growth are similar.In the subsequent passage glycoside synthesis decrease so strongly that the cardioactive glycosides exist only as traces and could no more be detected exactly.

Biogenese von cardenolid-glycosiden in Convallaria majalis: Umwandlungen auf der monoglycosidstufe

Abstract The sequence periplorhamnoside → convallatoxol → convallatoxin → convalloside,i.e. stepwise oxidation of C-19 followed by glucosidation, is one of the major biosynthetic routes of cardenolide metabolism in Convallaria majalis . Two different pathways lead to lokundjoside: one involving 5β-hydroxylation of rhodexin A, the other involving 11α-hydroxylation of periplorhamnoside. Glucosidation takes place mainly with convallatoxin and to a smaller extent with convallatoxol and rhodexin A.

Beiträge zur Massenspektrometrie der Gelsemium-Alkaloide

From the minor alkaloids ofGelsemium sempervirens (L.) Ait., one compound, preliminary designated as Gelsemiumalkaloid A, could be isolated and was identified as N-1-Methoxy-gelsemine. For the structure-elucidation mass-spectrometry has been proven to be of great value. Mass spectra of some Gelsemium-alkaloids are reported and the fragmentation of these compounds is discussed.There were further detected a quantity of new alkaloids in small amounts.ZusammenfassungVon den Nebenalkaloiden vonGelsemium sempervirens (L.) Ait. konnte eine Verbindung, zunächst als Gelsemium-Alkaloid A bezeichnet, in reiner Form dargestellt und ihre Konstitution als N-1-Methoxygelsemin aufgeklärt werden. Für die Strukturermittlung erwies sich die Massenspektrometrie als besonders wertvoll. Die Massenspektren einiger Gelsemiumalkaloide sind wiedergegeben, die Fragmentierung dieser Verbindungen wird diskutiert.Au\erdem wurde eine größere Anzahl neuer Basen in kleiner Menge nachgewiesen.

Die Strukturermittlung von Gelsemium-Alkaloid C (14-Hydroxygelsemicin) durch NMR- und Massenspektrometrie

The structur of a further minor alkaloid ofGelsemium sempervirens (L.) Ait., preliminary designated as Gelsemium alkaloid C, could be elucidated as 14-hydroxygelsemicin. NMR- and mass-spectrometry was most useful for this purpose, beside chemical reactions; the spectra are discussed in detail.ZusammenfassungDie Struktur eines weiteren Nebenalkaloides ausGelsemium sempervirens (L.) Ait., vorläufig als Gelsemium-Alkaloid C bezeichnet, konnte als 14-Hydroxygelsemicin erkannt werden, wobei sich neben chemischen Befunden vor allem die Ergebnisse der NMR- und Massenspektrometrie als wertvoll erwiesen; die Spektren werden näher besprochen.

Strophanthidin-fucosid, ein neues Cardenolidglykosid ausAdonis vernalis L.

Unter den zahlreichen Nebenglykosiden vonAdonis vernalis konnte in reiner Form eine zunachst als „Glykosidg” bezeichnete Substanz isoliert werden. Auf Grund von chromatographischen (Dunnschicht-, Papierchromatographie, Papierelektrophorese) und spektroskopischen Untersuchungen (UV-, NMR-Spektren) handelt es sich um Strophanthidinfucosid, das damit erstmals als naturlich vorkommendes Cardenolidglykosid nachgewiesen wird. Es ist in Herba Adonidis in einer Menge von etwa 0,025% enthalten, sein Anteil am Gesamtglykosidgehalt betragt etwa 10%.

Fluorodaturatin und Homofluorodaturatin—zwei neue β-Carbolinderivate in Samen von

In the transverse section of the seeds ofDatura stramonium L. var.stramonium a conspicuous sea-green fluorescence under UV-light (365 nm) can be observed. Thinlayer chromatography of a methanolic extract shows many blue and sea-green fluorescing substances, the main component being a polar, sea-green fluorescing compound. This substance is characteristic for all of the four varieties ofDatura stramonium L., and therefore of taxonomic interest. Isolation was tried by means of different chromatographic techniques. Combination of column chromatography and preparative thinlayer chromatography allowed the isolation of the main product, which was shown to consist of two substances (GF andGFa). Application of chemical and spectroscopic methods established the structure ofGF, named Fluorodaturatin, as 2,3,5,6-Tetrahydro-9-hydroxy-1H-pyrido-[1,2,3-l, m]-β-carboline-3-one. The second substanceGFa, called Homofluorodaturatin, was identified as analogue ofGF and the structure could be determined as 1,2,3,4,6,7-Hexahydro-10-hydroxyazepino-[1,2,3-l, m]-β-carboline-4-one.

Über die Konfiguration des Prolins im Ergotamin

It is well known that in the ergot alkaloids of the peptide type the proline appears in thel-configuration. Different methods of acid hydrolysis may lead to various cleavage products; hydrolysis by HCl yieldsd-proline, on the other hand hydrolytic cleavage by means of strongly acid cation exchange resin preserved the orginall-configuration.

Über eine wasserdampfflüchtige Verbindung aus der Faulbaumrinde

Es wird uber die Isolierung, Charakterisierung und Konstitutionsermittlung eines wasserdampffluchtigen Stoffes aus Cortex Frangulae (Faulbaumrinde), des 1,8-Dihydroxy-2-acetylnaphthalins (I) berichtet. Die mogliche Biogenese dieses Korpers im Rahmen der Acetattheorie wird diskutiert.