Studies on the Chemistry of Thienoannelated O , N - and S , N -Containing Heterocycles, 28 [1]. Synthesis of Imidazo[1,5- d ]thieno[2,3- b ][1,4]thiazine Derivatives as GABA -Receptor Ligands

Summary.  GABA-receptor-ligands are still very interesting in drug-development. Usually benzodiazepines are used in the treatment but they have serious side-effects. Thus, a recently synthesized quioxaline derivative which showed reduced side-effects in an animal model was used as a model-substance. The cyclus was modified to optimize the pharmacological profile. Accordingly, a series of imidazo-thieno-thiazines was synthesized starting from 5-acetyl-2-chloro-3-nitrothiophene to yield 6-ethyl-2,3-dihydro-1H-thieno[2,3-b][1,4]thiazine-2-one. Reaction with potassium tert-butoxide and diethylchlorophosphate gave an intermediate, which resulted in the desired ring system after adding the corresponding isocyanides and potassium tert-butoxide. Corresponding author. E-mail: thomas.erker@univie.ac.at Received August 6, 2002; accepted August 13, 2002     

The Dyeing of Nylon and Cotton Cloth with Azo Dyes: Kinetics and Mechanism

The mechanism of the dyeing of cotton and nylon cloth by the azo dyes Orange G and Sunset Yellow FCF was investigated using a channel flow cell. The variation in dyeing with flow rate was found to proceed via a mechanism in which the flux of dye entering the cloth relative to the flux of dye to the cloth surfacedecreasedwith increasing flow rate. A mechanism is deduced in which the dye passes from bulk solution, through a porous surface layer within the cloth, before passing into the bulk cloth. Adsorption onto surface sites in this porous layer blocks the passage of further dye into the cloth. Kinetic parameters for such a mechanism are given.     

Beiträge zur Chemie der Pyrrolpigmente, 38. Mitt.: Zur Assoziation von Gallenpigmenten

The long standing problem of solvent dependent absorption spectra of certain bile pigments such as bilirubindimethylester has been solved by measurement of molecular masses by means of vapour pressure osmometry. Using this method and the investigation of the concentration and temperature dependence of the absorption spectra on several model compounds an association equilibrium for pigments of the rubinoid structural type could be confirmed. Moreover the optical properties of the coexisting species and the corresponding equilibrium constants could be deduced by spectroscopic techniques. Verdinoid pigments lacking free carboxylic functions on the other hand tend to be monomeric in solution. A heteroassociated species involving equimolar amounts of a verdinoid and a rubinoid pigment could be verified existing on adsorbents like silicagel.

37. Mitt.:Falk, H., Thirring, K., Tetrahedron, im Druck.     

Synthesen von Heterocyclen, 135. Mitt.: Chinolizine und Indolizine,VI: eine Synthese von 2-Hydroxy-benzo[a] chinolizin-4-onen

Zusammenfassung 2-Hydroxy-6,7-dihydro-4H-benzo[a]chinolizin-4-one (3a—p) werden durch Kondensation von 1-Alkyl-3,4-dihydro-isochinolinen (1a—g) mit Malonsäure-bis-2,4,6-trichlorphenylestern (2a—e) erhalten. Die Ausbeuten sowie die erforderlichen Reaktionszeiten und Temperaturen sind stark von der Art der Substituenten abhängig.

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Syntheses of heterocycles, CXXXV: Quinolizines and indolizines, VI. A synthesis of 2-hydroxy-4H-benzo[a]quinolizin-4-ones

The condensation of 1-alkyl-3.4-dihydro-isoquinolines (1a tog) with 2.4.6-trichlorophenyl malonates (2a—e) yields 2-hydroxy-6,7-dihydro-4H-benzo[a]quinolizin-4-ones (3a—p). Yields, required reaction-periods and temperatures are depending on the nature of the substituents present in the malonyl and isoquinoline residue.

     

Forced lattice vibrations: Part I

This is the First part of a two-part series on forced lattice vibrations in which a semi-infinite lattice of one-dimensional particles {x_n}_n≧1 is driven from one end by a particle x₀. This particle undergoes a given, periodically perturbed, uniform motion, _x0(_t) = _at + _h(_yt), where a and γ are constants and h(·) has period 2π. For a wide variety of restoring forces F (i.e., F′ > 0), numerical calculations indicate the existence of a sequence of thresholds γ₁ = γ₁(a, h, F) > γ₂ = γ₂(a,h,F) > … > γ_k = γ_k(a,h,F) > …, γ_k → 0, as k → ∞. If γ_k > γ > γ_k+1, a k-phase wave that is well described by the wave form, emerges and travels through the lattice. The goal of this series is to describe the emergence and calculate some properties of these wave forms. In Part I the authors first consider the case where F(x) = e^x (i.e., Toda forces) but h is arbitrary, and show how to compute a basic diagnostic (see J(λ), formula (1.26)) for the system in terms of the solution of an associated scalar Riemann-Hilbert problem, once a certain finite set of numbers is known. In another direction, the authors consider the case where F(x) is restoring but arbitrary, and h is small. Here the authors prove a general result, asserting that if there exists a sufficiently ample family of traveling-wave solutions of the doubly infinite lattice, then it is possible to construct time-periodic k-phase wave solutions with asymptotics in n of type (iii) for the driven system (i). In Part II, the authors prove that sufficiently ample families of traveling-wave solutions of the system (iv) exist in the cases γ > γ₁ and γ₁ > γ > γ₂ for general restoring forces F. In the case with Toda forces, F(x) = e^x, the authors prove that sufficiently ample families of traveling-wave solutions.     

Über lineare Unabhängigkeit

It is the aim of the present work to prove, under appropriate conditions, lower estimates for the dimension of w ₁ + ... + w _m over , wherew ₁,...,w _m are given real numbers. In particular, if this dimension ism, i.e. ifw ₁,...,w _m are linearly independent over , we are also interested in a quantitative version of this fact. Our qualitative theorems generalize a result of Nesterenko. Its formulation is quite similar to the axiomatization of methods for algebraic independence, as it became usual during the last decade.

     

Mössbauer studies on the series La1-xSrxFeO3

Mössbauer spectra have been recorded at 4.2 and 300 K on the series La_1–x Sr _x FeO₃, wherex varies from 0 to 1.0 in steps of 0.1. Neutron diffraction experiments have shown that the crystal structure is orthorhombic for 0x<0.3, rhombohedral for 0.4x0.7, and cubic for 0.8<x1.0. Mössbauer spectra at 4.2 K are composed of magnetic sextet components arising from different charge states of iron ions. In the orthorhombic and rhombohedral phases, the charge states Fe³⁺ and Fe⁵⁺ coexist. In the cubic phase, iron is present as Fe³⁺ and Fe⁴⁺ states. At 300 K, the samples are magnetically ordered in the range 0 x0.3 and the coexistence of Fe³⁺ and Fe⁵⁺ remains. For samples 0.4x1.0, the samples are paramagnetic. Fits to these spectra require two components, one corresponding to an Fe⁴⁺ state, the other being best described as an Fe³⁺ ion forx0.7 but forx>0.7 having a mean charge state which increases to 3.5 forx=1.0.