Synthesis of Substituted Hydroxyspiro([1]benzopyran-2,4'(1'H)-pyrimidine)-2'(3'H)thiones and Hydroxyspiro-([1]benzopyran-2,4'(1'H)-pyrimidin)-2'(3'H)ones

We have developed a novel regioselective method for synthesis of substituted spiro([1]benzopyran-2,4'-(1'H)pyrimidine)-2'-(3'H)thiones and spiro([1]benzopyran-2,4'-(1'H)pyrimidin)-2'-(3'H)ones having one or two hydroxyl groups on the benzene ring.     

Application of thermal analysis to the study of the kinetics of two-stage reactions

A method is suggested for studying the kinetic parameters of two-stage reactions from thermoanalytical experimental data. The method allows determination of the kinetic characteristics of the process on the basis of integral thermoanalytical data, without separation of the individual stages. Parallel, independent and successive reactions taking place under isothermal and non-isothermal conditions are considered.

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Zusammenfassung Eine Methode zur Untersuchung der kinetischen Parameter von Zweistufenreaktionen unter Verwendung experimenteller thermoanalytischer Daten wird vorgeschlagen. Die Methode ermöglicht, die kinetischen Kennwerte des Prozesses basierend auf integralen thermoanalytischen Werten ohne Trennung der individuellen Schritte zu bestimmen. Unter isothermen und nichtisothermen Bedingungen parallel, unabhängig voneinander und nacheinander verlaufende Reaktionen werden diskutiert.

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Selective mono-and diamination of polyfluorinated benzenes and pyridines with liquid ammonia

Amination of pentafluoropyridine, 2,3,5,6-tetrafluoropyridine, 4-chlorotetrafluoropyridine, 3,5-dichlorotrifluoropyridine, octafluorotoluene, α,α,α,2,3,5,6-heptafluorotoluene, decafluoro-m-xylene, decafluorobiphenyl, hexafluorobenzene, and pentafluorobenzene with liquid ammonia was investigated. Bis-aminodefluorination temperatures for the majority of substrates were shown to exceed significantly the corresponding temperatures of monoaminodefluorination. The optimal conditions for selective preparation of mono-and diaminopolyfluoro(het)arenes were elucidated. An efficient method for isolation of particular polyfluorophenylenediamines from product mixtures formed in nonselective reactions of pentafluorobenzene and hexafluorobenzene with aqueous ammonia based on complexation with a crown ether is proposed. Dedicated to the memory of Academician N. N. Vorozhtsov on the occasion of his 100th anniversary. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2163–2170, November, 2007.     

Dynamic of the Fluorescence of the Complex Zn++/Bis-N-Carbazolyl-Distyrylbenzene

The discrimination between similar concentrations of the different metal ions is one of the important roles of fluorescent sensors. Here we present the study of the fluorescence dynamic of the chromophore bis-N-carbazolyl-distyrylbenzene (BCDSB) in acetonitrile/water (mmol/L), doped with metal ions such as K+; Ca++; Mg++; Zn++(10 micromol/L). BCDSB has the fluorescence with lambda(max) at 448 nm by excitation at lambda(exc) = 378 nm, lifetime 1.089 ns: quantum yield of the fluorescence is 0.68. With continuation of irradiation fluorescence quenching has been registered for all investigated metal ions. However, in the presence of Zn++ oscillation of the intensity was observed. The energy activation of the oscillation as much as 15 kcal/mol was estimated. We believe, that the specificity of the complex Zn++/BCDSB, is in an asymmetrical structure, formed via binding sites of Zn++ with the electron-enriched binding sites of the BCDSB, excited in n(pi)* state. This asymmetrical complex structure can cause the photoinduced structural fluctuation in the complex coordination.     

Kapitza pendulum effect in a continuously stirred tank reactor

The equations of a continuously stirred tank reactor in a wide range of the parameters have three stationary solutions describing the hot, cold, and intermediate unstable states. Similarity with the equations for one-dimensional motion indicates the possibility of the stabilization of instability by small high-frequency perturbation (Kapitza pendulum effect). This stabilization has been obtained in numerical simulation.     

Existence of a solution of an initial-boundary value difference problem for a linear heat equation with a nonlinear boundary condition

A problem of heat propagation in the ground from a heated pipeline with a partially heat-insulating shell is considered. The possibility is proved to construct a numerical solution of a linear heat equation by using a direct finite-difference method in the case when the thermal radiation on the ground surface is taken into account. On the basis of the theorem about the solvability of a system of linear difference equations by means of the sweep method, the existence and uniqueness of a solution of a corresponding difference problem with nonlinear boundary condition are proved.     

Amination of octafluoronaphthalene in liquid ammonia: 2,6- and 2,7-Diaminohexafluoronaphthalenes selective preparation

Monoamination of octafluoronaphthalene by liquid ammonia affords 2-aminoheptafluoronaphthalene mainly (isolated yield 85-90%). Diamination of octafluoronaphthalene or amination of 2-aminoheptafluoronaphthalene affords a mixture of isomeric 1,6-, 1,7-, 2,6-, and 2,7-diaminohexafluoronaphthalenes with considerable prevalence of the 2,7-isomer (∼70%), thus being the first example of the predominant substitution at position 7 in 2-substituted polyfluoronaphthalenes. The 2,7/2,6 ratio of 2-X-heptafluoronaphthalene (X = ⁻NH, NH₂ and NHAc) amination diminishes with the decrease of electron-donating effect of the substituent; 2,7-diaminohexafluoronaphthalene forms in the reactions of 2-aminoheptafluoronaphthalene or octafluoronaphthalene with excess of NaNH₂ in liquid ammonia and 2,6-diaminohexafluoronaphthalene—in the reaction of 2-acetylamidoheptafluoronaphthalene with liquid ammonia followed by acetylamido group hydrolysis. The method of the selective preparation of these diamines based on the reversible transformation of amino group and a convenient technique of their high purity isolation by complexation with crown ether have been elaborated.     

Crystal associates of 18-crown-6 and polyfluoro(het)arylenediamines: structure,properties, and selectivity of formation

The new group of objects in crystal engineering, namely, 1 : 1 associates of polyfluoro(het)arylenediamines and 18-crown-6, being supramolecular 1D assemblies, is considered. Diamine isomerism is shown to serve as a design tool for control of the supramolecular architecture, and the nature of the aromatic framework and location and volume of substituents determine linear dimensions of the elementary unit in an assembly. A linear dependence of the enthalpy of melting of co-crystals on the length of the assembly unit is observed in the series of the meta-(het)arylenediamine and 18-crown-6 associates. The effect of selective co-crystallization of polyfluoroarylenediamines with crown ether is used in practice for the isolation of high-purity compounds from mixtures of products of the non-selective amination of basic polyfluoroarenes.