N-(17-Phosphonooxylinolenoyl)glutamine and N-(17-phosphonooxylinoleoyl)glutamine from insect gut: the first backbone-phosphorylated fatty acid derivatives in nature

N-(17-Phosphonooxylinolenoyl)glutamine (1) and N-(17-phosphonooxylinoleoyl)glutamine (2) were isolated from the regurgitate of Spodoptora exigua and identified as the first natural alkyl chain-phosphorylated fatty acid derivatives. The compounds were characterized by HPLC-MS/MS and the assigned structures confirmed by synthesis via a dissymmetric bis-Wittig approach as the key reaction. Rearing of the larvae on a diet enriched with inorganic phosphate increased the amount of the phosphorylated N-acyl glutamines in the regurgitate.     

Reaktionen von o-Chinolacetaten mit Diazoalkanen, 4. Mitt.: Über die Einwirkung von Diazomethan auf o-Chinole

Zusammenfassung o-Chinole lagern je nach ihrer Konstitution ein oder zwei Mole Diazomethan an. Die Struktur dieser Additionsverbindungen wurde durch chemische und spektroskopische Untersuchungen geklärt.Mit 2 Abbildungen3. Mitt.:G. Spiteller undF. Wessely, Mh. Chem.90, 839 (1959).     

Über die Strukturaufklärung von (Hydroxy-oxo-cyclopentenyl)alkansäuren,den Aldolkondensationsprodukten von Dioxoencarbonsäuren aus Rinderleber

Structure Elucidation of (Hydroxy-oxo-cyclopentenyl)alkanoic Acids, the Aldol-Condensation Products of Dioxoene Acids from Cattle Liver During homogenization of cattle liver the highly instable dioxoene acids 13a , 13b , and 13c are formed. These acids cyclize in alkaline solution to yield pairs of stable (hydroxy-oxo-cyclopentenyl)alkanoic acids, which were isolated as methyl esters 4a / 5a , 4b / 5b , and 4c / 5c . The structures of these compounds were deduced from an enriched 3-mg mixture sample by microchemical reactions combined with a GC/MS analysis of the reaction products. Compound 13a was obtained as methyl ester by oxidation of the methyl ester of the corresponding F-acid with NaOCl. It was not possible to isolate 13a in pure form due to its high sensitivity. Instead of the methyl ester of 13a , 4a and 5a were isolated, of which the structures were established.     

Zur Lokalisierung funktioneller Gruppen mit Hilfe der Massenspektrometrie. XVII—Massenspektren von 3,6,20β-Trihydroxy-pregnanen

Mass spectra of 3,6,20β-trihydroxypregnanes differ greatly, depending upon the nature of the A/B ring fusion and the positions of the hydroxy groups. Of all the isomers only 3α,6β,20β-trihydroxy-5β-pregnane produces an intense, structurally significant, ion at m/e 263. For 3β,6α,20β-trihydroxy-5α-pregnane an ion of m/e 141 is typical.     

Über die Reaktion von tertiären Aminen mit p-Chinonen, 1. Mitt.: Über die Reaktion von Pyridin mit p-Chinon

Zusammenfassung Pyridin reagiert mit p-Chinon in Gegenwart von Acetanhydrid unter Ausbildung von Hydrochinonpyridiniumsalzen der Formel I und II. Die beständigen Verbindungen der Konstitution I nehmen bei der katalytischen Hydrierung 4 Mol H₂ auf und liefern die entsprechenden 2-Piperidinohydrochinonderivate. Die Verbindungen des Typus II hingegen sind sehr instabil und werden bei der katalytischen Hydrierung unter Aufnahme von nur einem Mol H₂ in Pyridin und Hydrochinonderivat gespalten.     

Characterisation of humic substances using atmospheric pressure chemical ionisation and electrospray ionisation mass spectrometry combined with size-exclusion chromatography

Humic substances were analysed by atmospheric pressure chemical ionisation (APCI) and electrospray ionisation (ESI) mass spectrometry in positive and negative modes. Using APCI the average m/z range of humic substances was reduced 5-fold compared to ESI. High-resolution time-of-flight mass spectrometry revealed the formation of multiply charged molecules in the ESI mode. Moreover, it was possible to obtain daughter ion mass spectra of humic substances by nanospray tandem mass spectrometry. The size-exclusion chromatography elution profile of humic substances was highly influenced by the pH of the analyte solution. By contrast, the pH had no significant influence on the observed mass spectra of humic substances.     

Die Struktur des Paucins

Zusammenfassung Beim Abbau von Paucin wird Brenzcatechin, Kaffeesäure und Putrescin erhalten. Daraus und aus spektroskopischen Befunden ergibt sich für das Paucin die Strukturformel3.

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The structure of Paucine

Paucine can be degradated to catechol, caffeic acid and putrescine. This together with spectroscopic data allows us to deduce formula3 for paucine.

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Mit 6 Abbildungen

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Meinem Lehrer, Prof. Dr.H. Bretschneider, zum 65. Geburtstag gewidmet.