Mono-Aryl/Alkylthio-Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio-Friedel–Crafts/Bradsher Cyclization Reaction

The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (T_decomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S₁ state by molecular oxygen.     

Weakly symmetric spaces in dimension five

We prove that every five-dimensional simply connected naturally reductive space is weakly symmetric in the sense of A.Selberg [11]. (For dimension less than five it was shown in [1] by a different method). We also show that the converse holds for all dimensions not greater than five.Supported by the grant GACR 201/93/0469Supported by a National Research Project of the M. U. R. S. T (Italy).     

Randomization helps to perform independent tasks reliably

This paper is about algorithms that schedule tasks to be performed in a distributed failure‐prone environment, when processors communicate by message‐passing, and when tasks are independent and of unit length. The processors work under synchrony and may fail by crashing. Failure patterns are imposed by adversaries. Linearly‐bounded adversaries may fail up to a constant fraction of the processors. Weakly‐adaptive adversaries have to select, prior to the start of an execution, a subset of processors to be failure‐prone, and then may fail only the selected processors, at arbitrary steps, in the course of the execution. Strongly adaptive adversaries have a total number of failures as the only restriction on failure patterns. The measures of complexity are work, measured as the available processor steps, and communication, measured as the number of point‐to‐point messages. A randomized algorithm is developed, that attains both ??(n log*n) expected work and ??(n log*n) expected communication, against weakly‐adaptive linearly‐bounded adversaries, in the case when the numbers of tasks and processors are both equal to n. This is in contrast with performance of algorithms against strongly‐adaptive linearly‐bounded adversaries, which has to be Ω(n log n/log log n) in terms of work. © 2003 Wiley Periodicals, Inc. Random Struct. Alg., 2004     

Electrostatic potentials of molecules and prediction of the lewis acid-base properties of solvents,part I. General considerations

Summary Electrostatic potentials in the vicinity of isolated molecules of typical nonaqueous solvents were computed in the MNDO approximation. It was found that the calculated dipole moments are in good agreement with experimental values. However, it turned out that in many cases electrostatic interactions of ions with solvent molecules cannot be described in the frame of ion-dipole interactions. Thus, two computable parameters,UN andUP describing short-range electrostatic interactions of a solvent molecule with a cation or an anion of radiusR were proposed. The dependence ofUN andUP uponR is analyzed in the context of ion-solvent interactions.

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Elektrostatische Potentiale von Molekülen und Voraussage von Lewis-Säure-Base-Eigenschaften von Lösungsmitteln, 1. Mitt.: Allgemeine Grundlagen

Zusammenfassung Es wurden die elektrostatischen Potentiale in der Umgebung von isolierten Molekülen typischer nichtwäßriger Lösungsmittel in der MNDO-Näherung berechnet. Die berechneten Dipolmomente waren in guter Übereinstimmung mit den experimentellen Werten. Es wurde jedoch beobachtet, daß in vielen Fällen die elektrostatischen Wechselwirkungen von Ionen mit Lösungsmittelmolekülen nicht im Rahmen von Ionen-Dipol-Wechselwirkungen beschrieben werden können. Dafür wurden zwei berechenbare ParameterUN undUP zur Beschreibung von elektrostatischen Wechselwirkungen im Nahbereich eines Lösungsmittelmoleküls mit einem Kationen- oder AnionenradiusR vorgeschlagen. Die Abhängigkeit vonUN undUP vonR wurde im Zusammenhang von Ionen-Solvens-Wechselwirkungen untersucht.

     

Long time behaviour of a flow in infinite pipe conforming to slip boundary conditions

The paper analyses long time behaviour of solutions of the Navier–Stokes equations in a two‐dimensional pipe‐like domain. The system is studied with perfect slip boundary conditions with arbitrary inflow conditions at infinity. The main results show the existence of global in time solutions and of an attractor for the dynamical system generated by the model. The paper also establishes an upper bound for the Hausdorff dimension of the attractor. Copyright © 2005 John Wiley & Sons, Ltd.     

TLC and HPLC Analysis of the Phenolic Acids in Silphium perfoliatum L. Leaves,Inflorescences and Rhizomes

JPC – Journal of Planar Chromatography – Modern TLC - TLC and HPLC have been used for preliminary evaluation of the phenolic acids occurring in the leaves, inflorescences, and rhizomes...     

Reactions of lithiated 2,5-dimethylazaferrocene with selected electrophiles

Lithiation of 2,5-dimethylazaferrocene 1 with sec-BuLi/TMEDA in THF at −78 °C proceeds (as shown by quenching with D₂O) to comparable extent on the methyl groups and the Cp ring. However, the outcome of the reaction of the lithiated 1 with an electrophile depends on the nature of this electrophile. In the reaction with 4-methoxybenzaldehyde only the product originated from the lateral lithiation is formed, whereas the reaction with 4-methoxyacetophenone and 4,4′-dimethoxybenzophenone afforded mixtures of the products resulting from lateral and ring-lithiation. Similar results were also obtained in the reaction of lithiated 1 with chlorodiphenylphosphine and diphenyl diselenide. On the other hand, the exclusive formation of the Cp-substituted product was observed in the reaction of lithiated 1 with N,N-dimethylformamide. The structures of selected products (oily compounds were transformed into the corresponding crystalline W(CO)₅-complexes) were confirmed by X-ray diffraction. The presented reactions open a novel entry to specifically substituted azaferrocenes (especially those containing heteroatom substituents) with potential applications as ligands for the homogenous catalysis.     

Polymerization of acrylonitrile by catalytic systems consisting of triphenylphosphine and a lewis acid

Polymerization of acrylonitrile in the presence of systems that consisted of triphenylphosphine (PPh₃) and a Lewis acid R_mMX_n (ZnCl₂, Me₃Al, Et₃Al, Et₂AlCl, EtAlCl₂, AlCl₃) was studied. The systems that contained Me₃Al and Et₃Al (i.e., Lewis acid of moderate acidity) were the most efficient catalysts. Conductometric measurements carried out in the polymerization systems showed the presence of ions. The presence of phosphonium cation in the polyacrylonitrile chain formed by the PPh₃–R_mMX_n catalytic systems was determined by IR, ¹H-NMR, and ³¹P-NMR spectroscopy. The average molecular weight measurements and kinetic chain lengths of polyacrylonitrile formed within the reaction time in the presence of PPh₃–Et₃Al showed that transfer reactions occur. According to the results obtained, the polymerization reaction of acrylonitrile by PPh₃–R_mMX_n involved a zwitterion formed by the attack of PPh₃ on acrylonitrile complexed by Lewis acid [Ph₃P^⊕? CH₂? C^?H? C?N → MR_mX_n] and the anion [CH₂?C^?? C?N] formed by the proton abstraction from the monomer.     

The synthesis and characterisation of 1′-ethynyl-2,5-dimethylazaferrocene and derivatives

The synthesis of 1′-ethynyl-2,5-dimethylazaferrocene is reported along with its cyclic voltammetry measurements and the X-ray structure determination of its W(CO)₅-complex. Basic coordination and organic chemistry of 1′-ethynyl-2,5-dimethylazaferrocene is also presented via derivatives incorporating cis-Pt(dppe) and Si(Et)₃ units.