Über einige neue Pikrate

Ohne Zusammenfassung     

Perhalogenmethylmercapto-heterocyclen, (VII) [1] konkurrenzreaktionen elektronenarmer,substituierter aromaten um die halogenmethylmercapto- BZW. Chlorgruppe von Cl3-nFnCSCl in starken saeuren

Electron-deficient aromatics, such as 2,5-bis(trifluoromethylmercapto)thiophene ($\text{1a}$) or (trifluoromethylmercapto)benzene ($\text{8a}$), react with F₃CSCl in the presence of F₃CSO₃ as a catalyst to give mainly 3-chloro-2,5-bis(trifluoromethylmercapto)thiophen ($\text{3a}$) and 1-chloro-4- or 2-(trifluoromethylmercapto)benzene ($\text{10}$, respectively. This reaction competes with the one expected to result in 2,3,5-tris(trifluoromethylmercapto)thiophene ($\text{2a}$) and 1,4- and 1,2-bis(trifluoromethylmercapto)benzene ($\text{9}$,$\text{9′}$), respectively. Further reactions of deactivated aromatics with Cl_3-nF_nCSCl show that the chlorine substitution is in general catalysed by strong acids. Reaction mechanisms are proposed for both Substitutions. The Cl_3-nF_nCS group in aromatics exerts a -M-effect in the case of an attack of a positive ion, e.g. H^⊕, the well-known +M-effect in the case of reactions with positively polarized molecules, e.g. CF₃S^β+Cl^β-.     

Pseudohalogenverbindungen. XX. Perfluorierte alkan- und phenylsulfonylpseudohalogenide

The pseudohalide CF₃SO₂NCO has been synthesized by means of a new reaction involving trifluoromethanesulphonamide and chlorosulphonylisocyanate. This method may be used for preparing other perfluorinated alkanesulphonyl-, arenesulphonyl- and alkanecarbonyl-amides. Reactions of CF₃SO₂NCO with alcohols, thiols, phenols and amines lead to the corresponding carbonic acid esters, thio-esters, phenyl esters and ureas. Reactions with carbonic acids, aldehydes and dimethylsulphoxide gave CO₂ and the corresponding acid amides, azomethines and imino-dimethylsulphurane. Under pressure at 160°C, CF₃SO₂NCO reacts with phosphorus pentasulphide to give the previously unknown compound CF₃SO₂NCS; with phosphorus pentachloride under the same conditions, CF₃SO₂NCCl₂ is formed.     

Michael additions to trifluoromethylvinyl sulfone

Michael addition reactions of trifluoromethyl vinyl sulfone with organic compounds with labile hydrogen atoms are studied. Such additions can be successfully accomplished using potassium fluoride and 18-crown-6-ether or benzyltrimethylammonium hydroxide (Triton B) as catalysts.     

Synthesis of Carbohydrate Derived α-Methylene-γ-lactones by Diasterecseldctive,Low Temperature Reformatsky-Type Reactions

Hexopyranoside- and hexofuranose uloses with either ethyl 2-(branamethyl)acrylate in the presence of laminar Zn/Ag-graphite or ethyl 2-(trimethylsilylinethyl)acrylate/tetra-n-butylanrnonium fluoride undergo stereoselective branching, mainly with formation of spiro α-methylene-γ-lactones.     

Experimental realization of one-way quantum computing with two-photon four-qubit cluster states

We report an experimental realization of one-way quantum computing on a two-photon four-qubit cluster state. This is accomplished by developing a two-photon cluster state source entangled both in polarization and spatial modes. With this special source, we implemented a highly efficient Grover's search algorithm and high-fidelity two-qubit quantum gates. Our experiment demonstrates that such cluster states could serve as an ideal source and a building block for rapid and precise optical quantum computation.     

Persistent tunneling currents and magnetic-field effects in glasses

Recent experiments on insulating glasses showed an unexpected variation of the dielectric constant with a static magnetic field and, in particular, oscillations with an apparent flux quantum of about 10(-5)h/e. We propose an explanation for these phenomena in terms of a model based on pairs of two-level systems. A weak interaction is shown to give rise to quantum states with a net circular current and a linear field dependence of the energy levels. Under experimental conditions, the dynamic susceptibility shows oscillatory behavior, with an effective flux quantum of the order of 10(-5)h/e.     

Mode-coupling theory for the dynamics of tunnelling systems in dielectrics

A mode-coupling theory (MCT) is presented for the spin-boson model with a spectral density which accounts for a heat bath made up of lattice vibrations of a dielectric solid (superohmic dissipation). A usual decoupling approximation provides a set of non-linear integral equations which are solved both numerically by iteration on a computer and analytically by means of a frequency dependent ansatz for the memory functions. There is a transition to incoherent motion at a temperatureT ^* where the bare two-level energy is equal to the damping rate, in contradiction to results obtained previously from a path integral formulation. The discrepancy arises since in the MCT the relevant self-energy function does not exhibit a 1/z-pole atz=0. For tunnelling systems in dielectrics this yields a new relaxation mechanism due to incoherent tunnelling: the present results might require to modify some of the basic assumptions of the standard tunnelling model for dielectric glasses.