Synthesis of Naturally Occurring Pyrazine and Imidazole Alkaloids from Botryllus LeachiRID=”a”ID=”a”?Dedicated to Prof. G. M?rkl on the occasion of his 75th birthday

The synthesis of the naturally occurring and biologically active alkaloids 1 and 2, first isolated from the red ascidian Botryllus leachi by Duran et al. [1], is described and the structure proposed for Botryllazine B (1) is confirmed. The analytical data for 2-(p-hydroxybenzoyl)-4-(p-hydroxyphenyl)imidazole (2) are discussed and compared with the literature. With special emphasis of ¹H NMR data the tautomerism of aroylimidazolemethanones is described.     

Fluordiazadiphosphetidine, 3. Mitt.: Die thermische Behandlung von 2,2,2,4,4,4-Hexafluoro-1,3-dimethyl-1,3,2,4-diazadiphosphetidin unter Druck in Gegenwart von Phosphor(V)fluorid und Alkalimetallfluoriden

Prolonged heating of (CH₃NPF₃)₂ in a sealed tube at 120°C yields (CH₃N)₄P₃F₇ and PF₅. Under the experimental conditions these compounds react to (CH₃N)₄P₃F₆ ⁺PF₆ ^–. Reaction of (CH₃NPF₃)₂ in the presence of PF₅ leads to a marked decrease in the formation of the ionic compound. The influence of the fluoride donating saltsMF (M=Li, Na, K, Cs) is investigated.

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Früher: Alkyliminophosphorsäuretrihalogenide, 1. und 2. Mitt.     

Theoretische Untersuchungen zum Charge-Transfer in Akzeptorligand-d6-Metall-Komplexen

Theoretical Investigations on the Charge Transfer of d⁶-Metal Complexes with Acceptor Ligands On the basis of the electronic structure of pentaammineruthenium(II) and pentacyanoferrate(II) complexes with aromatic N-heterocyclic ligands L the different tendency of the complex fragments to charge-transfer interactions with acceptor molecules is discussed. The increased energy and the reduced absorption intensity of the metal oxidation band of [Fe(CN)₅L]^3? are due to the diminished orbital interaction between the pentacyanoferrate(II) fragment and the nitrogen acceptor ligand caused by π-bonding interaction of the central metal with the cyanide co-ligands. The possibility of the variation of the energy of the acceptor levels connected with the position of the MLCT bands of the mixed-ligand complexes has been investigated by numerous azine and α-diimine ligands of different structure. Besides inductive and mesomeric effects the steric influences on the π-acceptor ability of the ligand and on the energy and absorption intensity of the MLCT band are examined.     

Neutral and ionic aluminum,gallium, and indium compounds carrying two or three terminal ethynyl groups

The syntheses of the ionic compounds [Li(+).2 dioxane (2,6-iPr(2)C(6)H(3)N(SiMe(3))Al(C triplebond CSiMe(3))(3))(-)].0.75 dioxane (1), [(Li(+))(2).(dioxane)(7)](0.5) [2,6-iPr(2)C(6)H(3)N(SiMe(3))Ga(C triplebond CSiMe(3))(3)(-)].1.5 dioxane (2), and [(Li(+))(2).(dioxane)(7)](0.5) [2,6-iPr(2)C(6)H(3)N(SiMe(3))In(C triplebond CSiMe(3))(3)(-)].1.5 dioxane (3) by the reaction of the corresponding organo metal chloride with LiC triplebond CSiMe(3) are reported. The neutral ethynyl compounds Br-Al(C triplebond CtBu)(2).2 THF (4), Cl-Ga(C triplebond CtBu)(2).THF (5), Cl-In(C triplebond CtBu)(2).2 THF (6), Al(C triplebond CtBu)(3).C[N(Me)CMe](2) (7), Ga(C triplebond CtBu)(3).dioxane (8), and In(C triplebond CtBu)(3).NEt(3) (9) have been obtained in good yields from the reaction of AlBr(3), GaCl(3), and InCl(3) with LiC triplebond CtBu in the presence of a Lewis base. Compound 7 is the first heterocyclic carbene substituted ethynyl derivative. Aluminum and gallium compounds with three terminal ethynyl groups Al(C triplebond CPh)(3).NMe(3) (10) and Ga(C triplebond CPh)(3).NMe(3) (11) have been prepared by the reaction of AlH(3).NMe(3) or GaH(3).NMe(3) with three equivalents of phenylethyne. All the above-mentioned compounds have been structurally studied. In compound 1 the lithium ion is coordinated to the three terminal ethynyl groups, whereas in compounds 2 and 3 the lithium is coordinated to the solvent (dioxane). Compound 8 crystallizes as a coordination polymer with dioxane molecules bridging the individual gallium units.     

Behaviour of Solochrome Dark Blue B as a colloidal electrolyte

Summary The electrical conductance of Solochrome Dark Blue B at various dilutions and temperatures have been measured. TheWaldens product has been calculated at different temperatures and it varies with the temperature. The reagent has been found to behave as a colloidal electrolyte. The temperature of zero conductance has been determined to be –20 °C and temperature coefficient per degree centigrade per hundred of conductance 35 °C varies between 1.81 and 1.87.

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Zusammenfassung Die elektrische Leitfähigkeit von Solochrome Dark Blue B bei verschiedener Verdünnung und verschiedenen Temperaturen wurde gemessen, dasWaldensche Produkt bei verschiedenen Temperaturen berechnet. Es variiert mit der Temperatur. Das Reagens benimmt sich wie ein Kolloid. Die Temperatur der Null-Leitfähigkeit wurde zu –20 °C bestimmt und der Temperaturkoeffizient pro Grad in Prozenten der Leitfähigkeit bei 35 °C liegt zwischen 1,81 und 1,87.

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With 2 figures and 3 tables     

Weighted majority games and the matrix of homogeneity

If a weighted majority game (not necessarily constant sum or super additive) is described by the weights (voting strength) of the players involved and a majority level, then it is desirable to know whether the game is in addition homogeneous. The paper provides a recursive procedure defining a test for homogeneity. This procedure involves the computation of a number theoretical function, the matrix of homogeneity. If this matrix is knownall majority levels with respect to which the given set of weights represents a homogeneous simple weighted majority game are known at once.

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Zusammenfassung Ein gewichtetes Majoritätsspiel (nicht notwendig superadditiv oder mit Konstantsummeneigenschaft) kann beschrieben werden durch die Gewichte (die Abstimmungsstärke) der beteiligten Spieler und durch eine Mehrheitsschranke. Wenn eine solche Darstellung gegeben ist, so ist es wünschenswert, das Spiel zusätzlich auf die Eigenschaft der Homogenität hin zu untersuchen. Die vorliegende Arbeit stellt eine rekursive Prozedur zur Verfügung, die einen Test auf Homogenität einer vorgelegten Darstellung eines Spieles impliziert. Die Prozedur ermöglicht die Berechnung einer zahlentechnischen Funktion, der Homogenitätsmatrix. Wenn diese Matrix bekannt ist, kann man bei einem vorgegebenen Gewichtssatz alle Majoritätsschranken angeben, bezüglich welcher die vorgelegten Gewichte ein homogenes einfaches gewichtetes Majoritätsspiel darstellen.

     

Application of the ellipsoid method in an interactive procedure for multicriteria linear programming

The research reported in this paper is concerned with an application of the ellipsoid algorithm in the interactive multicriteria linear programming step method (STEM) byBenayoun et al. [1971]. Due to this application we eliminate some drawbacks of the original version of STEM and, moreover, we avoid extra computations connected with sensitivity analysis in every iteration. Specifically, we use the ellipsoid algorithm to minimize the Euclidean norm in the criterion space instead of the Chebyshev norm, which ensures that every solution submitted to the decision maker is efficient. As follows from a computational experiment, in comparison with the application of the simplex method, the proposed modification of STEM shows a smaller increase of the computational effort when the number of criteria increases. However, the absolute computation time becomes worse for problems of larger size.

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Zusammenfassung In dieser Arbeit wird über eine Anwendungsmöglichkeit der Khachiyan-Shor-Algorithmus (Ellipsoid-Algorithmus) im Rahmen des STEM-Verfahrens zur interaktiven Lösung linearer Vektoroptimierungsmodelle berichtet. Auf diese Weise können einige spezifische Nachteile des STEM-Verfahrens in seiner Originalversion vermieden werden. Durch die Verwendung der Euklidischen Norm anstelle der beim STEM-Verfahren üblichen Tschebyscheff-Norm wird garantiert, daß dem Entscheidungsträger nur effiziente Lösungen vorgeschlagen werden. Die numerischen Erfahrungen zeigen, daß der Lösungsaufwand der hier vorgeschlagenen Modifikation des STEM-Verfahrens mit steigender Anzahl von Zielfunktionen weniger stark zunimmt als bei der üblichen Version. Dies gilt jedoch nicht hinsichtlich der allgemeinen Problemgröße.

     

Strukturviskosität von verdünnten Lösungen von Biopolymeren

The importance of the rheological behaviour of solutions of macromolecules is briefly evaluated. The viscosity of the solutions depends on concentration, shear rate and time of shear, this relation being determined by the structure of the dissolved molecules. In dilute solutions shear dependence of viscosity is very frequently caused by the preferential orientation of anisotropic molecules. In such a case the particle dimensions can be calculated from the true limiting viscosity number, an anisotropy factor, the rotational diffusion constant and the effective particle density. These numbers can be derived from the flow curve, which has been extrapolated to zero concentration. It is necessary to measure the flow curve at shear gradients, which are sufficiently low to allow for an extrapolation to vanishing shear rate. By comparing the experimental flow curve with a choice of theoretical ones, the rotational diffusion constant and the anisotropy factor (axial ratio) can be found. From the limiting viscosity number and the axial ratio, the particle density can be calculated.     

Komplexe von 2,6-Dimethylpyridin-1-oxid mit Lanthanidjodiden

Complexes of 2,6-dimethylpyridine 1-oxide with lanthanide iodides of the formulaeLn(2,6-LTNO)₅I₃ whereLn=La, Tb and Yb,Ln(2,6-LTNO)₄I₃ whereLn=Pr and Nd and Er(2,6-LTNO)_4.5I₃ have been prepared and characterised by chemical analysis, infrared and conductance studies. Infrared and conductance data have been interpreted in terms of dimeric (or polymeric) structures involving bridging amine oxide groups.

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