Fundamental Aspects of Ionic Dissociations: The Fragmentation Pathways of Excited Bicyclobutane Cations

A most recently developed method to quantify the fragmentation pathways of excited radical cations is presented. Using bicyclobutane cation as an illustrative example, the RRKM analysis of the breakdown diagram determined by He-Iα photoelectron-photoion coincidence spectroscopy is outlined. The results imply complete isomerization to 1,3-butadiene cation preceding the dissociative processes. The rate-energy functions of four competitive primary fragmentation reactions, leading to C₃H, C₄H, C₄H and C₂H are established. There is compelling evidence that the production of C₂H fragment ions does not compete effectively with these four reactions. The extent of kinetic and competitive shift effects is determined. The derived enthalpies of formation are in excellent accord with the available high quality reference data. The relative importance of different fragmentation pathways which ultimately lead to fragment ions of identical mass to charge ratio is assessed.     

Umweltchemie 1998

Nachdem im Trendbericht des letzten Jahres ausgewählte Beispiele aus Bereichen der Umweltchemie besprochen wurden,¹⁾ sollen in diesem Jahr Ergebnisse aus Ökotoxikologie and Humantoxikologie behandelt werden. Zunächst werden einige Arbeiten aus den Bereichen der Entsorgungsverfahren und neue Entwicklungen bei Spurenstoffen vorgestellt. Da das Gebiet der nachhaltigen Chemie immer mehr in den Brennpunkt des Interesses rückt, werden auch neue umweltfreundliche Synthesen und Produkte ausführlich diskutiert.     

The Structure of the Alkaloid Peduncularine. Communication no. 172 on organic natural products

The revised structure 1 is put forward for peduncularine, the main alkaloid of Aristotelia peduncularis (Labill.) HOOK. F. (Elaeocarpaceae), on the basis of its spectroscopic properties and those of its degradation products, the Hofmann base 3 and the hydrogenation product 4 . Structure 1 represents the relative configuration of the alkaloid. Peduncularine belongs to the class of indole alkaloids with a monoterpene unit as the aliphatic portion. To our knowledge it constitutes the first example in which an isopropyl group has become detached from the terpene unit and occurs as a substituent on nitrogen.     

Untersuchung der Komplexierung von Na+, K+, Ca2+ und Ba2+ mit einigen elektrisch neutralen Liganden durch Messung von 13C-chemischen Verschiebungen und Spin-Gitter-Relaxationszeiten

Investigation of the complexing of Na⁺, K⁺, Ca²⁺ and Ba²⁺ with some uncharged ligands by ¹³C-chemical shift and spin-lattice relaxation time measurements The influence of Na⁺, K⁺, Ca²⁺ and Ba²⁺ ions on ¹³C chemical shifts and on spin-lattice relaxation times of some electrically neutral ion carriers was investigated. In the solvents CD₃CN and CD₃OD and in presence of an excess of metal ions ligand 4 (see the Scheme) forms complexes of 1:1 stoichiometry. All four oxygen atoms of the ligand as well as solvent molecules take part in the coordination. In CDCl₃ as solvent, for all ions investigated except sodium, only 1:2 complexes (metal/ligand) were observed with 4 . Sodium ions form both 1:1 and 1:2 complexes in this solvent. In the 1:2 complexes of the investigated monovalent ions only one, in those of the divalent ions both amide carbonyl groups of ligand 4 take part in the coordination.     

The crystal and molecular structure of the cycloadduct from an activated carbodiimide and methyl isothiocyanate

The crystal and molecular structures of the cycloadduct from isopropyl[α-(dimethylthio-carbamoyl)isopropyl]carbodiimide and methyl isothiocyanate were determined by single-crystal X-ray methods. The product was established to be 2-(1-isopropyl-3,5-dimethyl-4,6-dithioxo-hexahydro-1,3,5-triazine-2-ylidenamino)-N,N-dimethylthioisoburyramide, in which contrary to expectations based on hybridisation the heterocyclic ring adopts a boat conformation.     

Dialkyldithiocarbamate als Reagentien zur gas-chromatographischen Bestimmung von Metallen

Zusammenfassung Kleine Mengen Ni, Cu und Zn in wäßrigen Lösungen können nach Ausschütteln ihrer Dipropyldithiocarbamatochelate gas-chromatographisch bestimmt werden. Arbeitsbedingungen für den 0,01–1 ppm-Bereich werden angegeben. Die Reproduzierbarkeit der Bestimmung wird durch Zusatz eines inneren Standards verbessert.

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Dialkyldithiocarbamates as reagents for the gas-chromatographic determination of metalsII. Determination of zinc, copper and nickel as dipropyldithiocarbamato chelates after extraction from aqueous solution

Summary Small amounts of Ni, Cu and Zn in aqueous solutions can be determined by gas chromatography after extraction of their dipropyldithiocarbamatochelates. Working details for the 0.01–1 ppm range are reported. Reproducibility is markedly improved by addition of an inner standard.

Die Untersuchungen wurden in dankenswerter Weise durch Mittel der Deutschen Forschungsgemeinschaft und des Verbands der chemischen Industrie unterstützt.