Ergebnisse aus versuchen zur darstellung von bis(trifluormethylsulphanyl)thioketen (CF3S)2C=C=S

The attempted preparation of bis(trifluoromethylsulphanyl)thioketene is described. Mono-and di-(trifluoromethylsulphanyl)-substituted orthothioesters may be prepared fromCH₃C(SC₂H₅)₃ and CF₃SCl in the presence of anhydrous ZnCl₂. The unstable compoundshave been isolated and characterized. The corresponding CF₃Se and CF₃SO₂ derivativesare only formed as intermediates which decompose to ketene diethylmercaptal. Suchmono- and di-substituted products are obtained in good yield from H₂C=C(SC₂H₅)₂ andCF₃ECl (E=S, Se). The reaction of H₂C=C(SC₂H₅)₂ with CF₃SO₂F gave only poor yieldsof (CF₃SO₂)_nCH_2−n=C(SC₂H₅)₂ (n=1, 2) which were only capable of characterizationin etheral solution by spectral means. Attempts to prepare (CF₃S)₂C=C=S by refluxing(CF₃S)₂CHC(O)Cl, (CF₃S)₂CHC(O)OH or (CF₃S)₂C=C=O with P₄S₁₀ in toluene yieldedonly the cyclic dimer and the corresponding 1,3,4-trithiolan.     

Aminomethylphosphine Oxides: Synthesis,dissociation and stability constants, 31P{1H}-NMR-controlled titrations

The title compounds are prepared via Gabriel-synthesis following known or improved procedures. Novel methods using ³¹P{¹H}-NMR controlled titrations of aminomethylphosphine oxides lead to dissociation constants (given as basicity or acidity constants resp.) and to stability constants. Dynamically averaged and ion specific chemical shifts δ_P were derived.     

A new exposure system for the in vitro detection of GHz field effects on neuronal networks

The possible effects of high-frequency electromagnetic fields (EMF) on biological systems are a subject of public concern and scientific discussion. It is generally accepted that the absorption of part of the field energy may cause a temperature rise in biological tissue. Nevertheless, our setup aims to detect possible athermal effects on the electric activity of neuronal in vitro networks. Such networks were formed by primary neurons derived from the murine frontal cortex and cultivated on micro-sensor chips. The action potentials of the neurons were detected in real time by an integrated, electrically passive microelectrode array. For EMF exposure, the chips were introduced into a rectangular wave-guide that could be operated in the propagating or standing wave modes. The drive signals were either continuous waves (1.9-2.2 GHz) or a generic mobile phone signal (UMTS-standard) of up to approximately 8 W. An on-chip sensor allowed the temperature progression to be recorded. In addition, ISFETs and Clark-like electrodes were integrated for the on-chip detection of pH and O(2), respectively.     

Die Kristallstruktur von (PPh4)2[Mo2(O2C?Ph)4Br2] · 2 CH2Br2

Crystal Structure of (PPh₄)₂[Mo₂(O₂C? Ph)₄Br₂] · 2 CH₂Br₂ The title compound, prepared by the reaction of Mo₂(O₂C? Ph)₄ with PPh₄Br and PPh₄N₃, respectively, under the assistance of CH₂Br₂, was characterized by an X-ray structure determination. Space group P2₁/n, Z = 2, R = 0.074 (5261 independent observed reflexions). The lattice dimensions are at ?70°C: a = 1562.9, b = 1406.2, c = 1662.1 pm, β = 94.11°. the compound consists of PPh₄^⊕ ions, CH₂Br₂ molecules, and centrosymmetric anions [Mo₂(O₂C? Ph)₄Br₂]^2?. The axis Br? Mo?Mo–Br is nearly linear (bond angle 175.6°) with bond lengths MoMo = 212.3 pm and Mo? Br = 303 pm, corresponding with a weak electrostatic Mo? Br bond. In the FIR spectrum the Mobr stretching vibration is found at 85 cm^?1, which corresponds with the low value of the force constant of 0.24 N · cm^?1.     

Investigations of the deactivation of inorganic and organic freezing-nuclei

Zusammenfassung Messungen der Konzentration atmosphärischer Gefrierkerne zeigten Fluktuationen in Abhängigkeit von der Konzentration gleichzeitig anwesender Spurengase. Laborversuche mit anorganischen und organischen Testaerosolen wurden vom Verfasser durchgeführt, um den Einfluss von Gasspuren auf die Aktivität der Aerosole als Gefrierkerne zu untersuchen. Ammoniak zeigte eine «vergiftende» Wirkung, während die Wirkung von Schwefeldioxyd, dem verbreitesten atmosphärische Spurengas, vernachlässigbar gering ist. Aus den Versuchen muss die Schlussfolgerung gezogen werden, dass der Einfluss der in dieser Arbeit untersuchten Spurengase auf die Wirksamkeit der Aerosolteilchen als Gefrierkerne erst in Gegenwart von Spurengasmengen, die um Grössenordnungen über den in der Atmosphäre auftretenden Konzentrationen liegen, bemerkenswert wird.

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This paper was presented at the V. International Symposium on atmospheric condensation nuclei and freezing nuclei at Clermont-Ferrand (France) in May 1963. The investigations were carried out at the Department of Cloud Physics, Imperial College of Science and Technology, London.     

SYNTHESIS OF ENANTIOMERICALLY ENRICHED α-AMINOPHOSPHINIC ACID DERIVATIVES VIA ASYMMETRIC HYDROGENATION

Abstract

For the first time, the biological interesting enantiomerically enriched α-aminophosphinic acids and their derivatives were prepared by asymmetric hydrogenation of suitable precursors and saponification of the obtained products. Enantiomeric excesses of up to 99 % were obtained.     

On the role of expectations in a dynamic Keynesian macroeconomic model

A simple Keynesian macroeconomic disequilibrium model with rationing is considered. This paper investigates the influence of different expectations hypotheses (regarding next period's goods prices) on the model's dynamic behavior when intertemporal substitution effects exist. While the bifurcation behavior is not qualitatively influenced when expectations are formed according to adaptive expectations or an unweighted-averages hypothesis, the dynamic behavior of the model can be changed in an essential way when pattern-recognition expectations are assumed. So-called perfect cyclic expectations can turn a previously chaotically moving economy into a system with a low-periodic motion in particular cases.     

On the complexity of simultaneous price-quantity adjustment processes

While the Walrasian price tâtonnement represents the traditional dynamic process in the general equilibrium context with and without production, Walras and other classics designed the process exclusively for pure exchange economies. In productive economies, the short-run output adjustment of existing firms and the entry/exit of firms should be modeled as well. So-called cross-dual processes which represent the classical approach to the dynamics of productive economies are discussed and extended. Complex motion can emerge in a discrete-time version of the original two-dimensional system when the aggregate demand function has a non-standard shape. A simultaneous process of price and short-run quantity adjustment with free entry and exit of competitive firms in a single market with a continuum of firms can generate closed orbits via a Hopf bifurcation when the slope of the demand function is positive at equilibrium. When the continuum economy is replaced by an economy with a finite number of firms, noisy limit cycles and complicated behavior can be observed.     

Die Kristallstrukturen von [ReCl4(PhCCPh)]2 · 2 CH2Cl2 und von PPh4[ReOCl4]

Crystal Structures of [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂ and PPh₄[ReOCl₄] Single crystals of [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂ were obtained by chilling dilute solutions of the solvate [ReCl₄(PhC?CPh)POCl₃] in CH₂Cl₂. PPh₄[ReOCl₄] was formed by the reaction of the diphenyl acetylene complex [ReCl₅(PhC?CPh)] with PPh₄Cl · H₂O in CH₂Cl₂ solution. [ReCl₄(PhC?CPh)]₂ · 2 CH₂Cl₂: space group P2₁/c, Z = 2, 2244 observed independent reflexions, R = 0.038. Lattice parameters (19°C): a = 987.2 pm; b = 1533.9 pm; c = 1193.8 pm; β = 90.17° The compound forms centrosymmetrical dimeric molecules with ReCl₂Re bridges with Re? Cl distances of 241.2 and 267.6 pm. The longer Re? Cl bond is situated in trans-position to the equatorial, side-on coordinated diphenyl acetylene ligand with mean Re? C distances of 200 pm. PPh₄[ReOCl₄]: space group P4/n, Z = 2, 1487 observed, independent reflexions, R = 0.047. Lattice parameters (19°C): a = b = 1272.0 pm; c = 771.3 pm. The compound crystallizes in the AsPh₄[RuNCl₄] type; it consists of [ReOCl₄]^? anions and PPh₄⁺ cations. The anions are tetragonal with C_4v symmetry and bond lengths Re? O = 165.4 pm and Re? Cl = 232.6 pm; the bond angle OReCl is 106.7°.