A comparison of ring-chain tautomerism in heterocycles derived from 2-aminobenzenesulfonamide and anthranilamide

A number of anthranilamide and 2-aminobenzenesulfonamide derivatives with aromatic aldehydes and 1,3-dicarbonyl compounds were synthesized. Substituted benzaldehyde derivatives of neither aminoamides showed tautomerism in solutions. Reaction products of 2-aminobenzenesulfonamide with p-substituted benzoylacetic aldehydes and p-substituted benzoylacetones undergo ring-chain tautomerism with a good linear correlation between the ring-chain equilibrium constants (log K, where K=[ring]/[chain]) and the Hammett-Brown σ⁺ parameters of the aromatic substituents. The equilibrium constant was measured for the reaction products of 2-aminobenzenesulfonamide with unsubstituted benzoylacetaldehyde at several temperatures which enabled the enthalpy and entropy of this reaction to be evaluated.     

Inclusion of Two PhP(O)(OH) 2 Guest Molecules into the Cavity of Macrocyclic Cavidand Cucurbit[8]uril

A new inclusion compound which is a supramolecular adduct of cucurbit[8]uril with two guest molecules of phenylphosphonic acid, PhP(O)(OH)₂, included into the cavity as ``two guests in host'' is reported. The guests match both size and hydrophilicity/hydrophobicity requirements. Two phenyl groups of molecules of PhP(O)(OH)₂ are directed toward the center of the large hydrophobic cavity whereas the PO(OH)₂ groups are outward-looking and bound with each hydrophilic portal of cucurbit[8]uril by a short hydrogen bond.     

Free radical-scavenging activity of indolic compounds in aqueous and ethanolic media

Indolic compounds are a broad family of substances present in microorganisms, plants and animals. They are mainly related with tryptophan metabolism, and present particularities that depend on their respective chemical structures. The most important members of the family are the plant hormone, indole-3-acetic acid, and the animal hormone, melatonin. An important characteristic of some indolic compounds is that they may be useful as chemical preventive agents against diseases such as cancer, oxidative stress, etc. For this reason, the possible antioxidant activities (free radical-scavenging activity) of several indoles were studied. The2,2'-azino-bis-(3-ethylbenzthiazoline-6-sulfonic acid /H(2)O(2)/HRP decoloration method was applied to determine both hydrophilic (in buffered media) and lipophilic (in organic media) antioxidant properties of the indolic compounds. Also, a study of the hydrophilic antioxidant activities of indoles at different pH values (between 4.5 and 8.5) was made. Finally, their possible role as diet plant antioxidants is discussed.     

Titanium and zirconium chloro, oxo and alkyl derivatives containing silyl-cyclopentadienyl ligands. Synthesis and characterisation

The reaction of the tetramethylcyclopentadiene-silyl substituted derivative C₅Me₄(SiMe₃)(SiMe₂Cl) with MCl₄ afforded the trichloro mono-tetramethylcyclopentadienyl complexes M(η⁵-C₅Me₄SiMe₂Cl)Cl₃ [M=Ti (1), Zr (2)] with selective elimination of SiMe₃Cl. Compound 1 reacts with deoxygenated water in methylene chloride, with the evolution of HCl, to give the dinuclear titanium compound {Ti[μ-(η⁵-C₅Me₄SiMe₂O-κO)]Cl₂}₂ (3), which was converted into the μ-oxo complex {Ti[μ-(η⁵-C₅Me₄SiMe₂O-κO)]Cl}₂(μ-O) (4) by a further hydrolysis reaction which occurred when a solution of 3 in toluene was refluxed for a long period of time in the air. Depending on the size of the alkyl ligand, reactions of the mononuclear compound 1 with an appropriate alkylating reagent rendered the peralkylated Ti(η⁵-C₅Me₄SiMe₂R)R₃ [R=Me (5), CH₂Ph (6)] or partially alkylated {Ti[(η⁵-C₅Me₄SiMe₂(CH₂SiMe₃)]Cl(CH₂SiMe₃)₂} (7) compounds by a salt metathesis route. Attempts to synthesise a partially methylated or benzylated complex were unsuccessful. Treatment of the dinuclear compound 3 with four equivalents of MgClMe yielded the tetramethyl derivative {Ti[μ-(η⁵-C₅Me₄SiMe₂O-κO)]Me₂}₂ (8), while the same reaction carried out with MgCl(CH₂Ph) or Mg(CH₂Ph)₂·2THF gave the chloro-benzyl derivative {Ti[μ-(η⁵-C₅Me₄SiMe₂O-κO)]Cl(CH₂Ph)}₂ (9) as an equimolar mixture of diastereomers, regardless of the molar ratio of the alkylating reagent used. All of the new compounds were characterised by elemental analysis and NMR spectroscopy.     

Plastic deformation and performance of engineering polymer materials

The plastic deformation mechanism operating in polymer glasses is analyzed. The whole process consists of two main stages: nucleation of special shear defects, called PSTs (plastic shear transformations), and their disappearance. The important feature of plastic deformation of glasses is the storage of a large amount of internal energy ΔU_def upon straining. Such energy storage is the critical issue for mechanical performance of polymeric material: if the amount of stored energy is high, the appearance of macroscopic failure is very probable while glassy materials collecting a small amount of stored deformation energy are quite ductile. It is proposed that the rate of disappearance of PSTs is a key factor in dissipation of stored deformation energy. A parameter describing the dissipation ability of material upon deformation is introduced.     

Solid-phase reagent for molecular spectroscopic determination of heavy metal speciation in natural water

A solid-phase reagent based on 1-(4-adamantyl-2-thiasolylazo)-2-naphthol adsorbed onto silica gel was prepared for Co(II) recovery and preconcentration prior to its sorption-spectroscopic detection. The immobilized reagent was applied to the determination of free cobalt ions in natural water. The solid-phase reagent and chemiluminescent method coupled with membrane filtration, gel-permeation and ion-exchange chromatography were applied to the study of the speciation of iron and cobalt in water from the Dnieper reservoirs and lakes of Kyiv City; their predominant forms were complexes of Fe(III) and Co(II) with dissolved organic matter and fulvic acids play a main role in their complexation.     

An unexpected rearrangement of 3-unsubstituted-2-acyl substituted indole phenylhydrazones. A new method for benz[c]β-carboline synthesis

A new type of rearrangement of 3-unsubstituted-2-acyl substituted indole phenylhydrazones with formation of a quinoline ring under acid catalysed conditions was observed.     

Mass displacements in quadrupolar field analysers

The influence of different instrumental parameters on the mass displacements observed in an ion trap and a quadrupole mass filter was investigated. In ion trap measurements it was observed that isolated ions (obtained by both ‘apex’ and ‘two-step’ isolation methods) show the same mass displacements determined in the usual mass spectra; isobaric ions of different structure irradiated with supplementary a.c. fields are ejected at different a.c. voltages, and different cooling times do not affect the mass value. In the quadrupole mass filter, differences in mass were found among isobaric ions of different structure, although to a smaller extent than those observed in the ion trap. All the data obtained are in agreement with the hypothesis of ion–r.f. field interactions originating from the polarizability of the ion.     

Bestimmung von Ascorbinsäure auf Grund ihrer in einem Landolt-System ausgeübten reduzierenden Wirkung

Zusammenfassung Im Bromat-Jodid-Ascorbinsäure-System hängt die Zeit, die bis zur Jodausscheidung vergeht, von der Konzentration der Ascorbinsäure ab. Unter entsprechenden Versuchsbedingungen ist die Reaktionszeit proportional der Ascorbinsäurekonzentration. Danach kann die Ascorbinsäure sowohl mit Hilfe der Simultankomparationsmethode, als auch chronometrisch bestimmt werden. Die Genauigkeit ist ± 3% im Bereich von 5 bis 300g/5 ml. Die Grenzen der Bestimmung sind 1g bzw. 1000g Ascorbinsäure in 5 ml.

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Determination of ascorbic acid on the basis of its reducing action in a landolt system

Summary In the bromate-iodide-ascorbic acid system, the time that elapses until the iodine appears is dependent on the concentration of the ascorbic acid. Under appropriate experimental conditions, the reaction time is proportional to the ascorbic acid concentration. Accordingly, the ascorbic acid may be determined with the aid not only of the simultaneous comparison method but also chronometrically. The precision is ± 3% in the 5–300g/5 ml range. The limits of the determination are 1g and 1000g ascorbic acid in 5 ml respectively.

     

Die katalytischen Reaktionen bei der Spurenanalyse und die Untersuchung ihrer Mechanismen. II Untersuchung der Tiron—H2O2-Reaktion

Zusammenfassung Die Oxydation von Tiron durch H₂O₂ in basischem Milieu wird durch Kobalt stark katalysiert. Die katalysierten Vorgänge sind p_H-abhängig. Im p_H-Bereich 9 bis 11 entsteht ein rotes Oxydationsprodukt unbekannter Struktur; wahrscheinlich handelt es sich um ein o-Chinonderivat. Mit Hilfe der katalytischen Reaktion können 10^–4 g Kobalt/5 ml nachgewiesen werden. In diesem p_H-Bereiche stabilisiert Tiron H₂O₂ bei 100° C, bei 40° C jedoch katalysiert es — in Abhängigkeit von der Konzentration des Tirons — den Zerfall des H₂O₂. Der Effekt spielt im Mechanismus der katalysierten Reaktion wahrscheinlich eine Rolle, doch können die Zusammenhänge an Hand der bisher veröffentlichten Angaben nicht klar gedeutet werden. Der die Reaktion begleitende bzw. ihr folgende Nebenvorgang kann auf den katalytischen Zerfall des H₂O₂ · OOH-Komplexes zurückgeführt werden. Zwischen p_H 7 und 9 entsteht bei der katalysierten Reaktion Semichinon, über p_H 11 oxydiert Tiron das Semichinon unter Ringspaltung und Abspaltung von 1 Mol Sulfat zu Verbindungen, die Säurecharakter tragen.

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Summary The oxidation of Tiron by H₂O₂ in basic milieu is strongly catalyzed by cobalt. The catalyzed reactions are p_H-dependent. A red oxidation product of unknown structure results in the p_H range 9 to 11; probably it is ano-quinone product. As little as 10^–4 g cobalt/5ml can be detected by this catalytic action. In this p_H region, Tiron stabilizes H₂O₂ at 100° C, but at 45° C it catalyzes the decomposition of H₂O₂, in relation to the concentration of the Tiron. The effect probably plays a rôle in the mechanism of the catalyzed reaction, but the up to now published informations are not sufficient to clarify the relationships. The auxiliary process, accompanying or following the reaction, can be attributed to the catalytic decomposition of the H₂O₂-OOH^– complex. Semiquinone is produced by the catalytic reaction between p_H 7 and 9, above p_H 11, the Tiron oxidizes the semiquinone with opening of the ring and splitting off of 1 mol of sulfate yielding compounds which have an acidic character.

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Résumé L'oxydation du Tiron par H₂O₂ en milieu basique est fortement catalysée par le cobalt. Les processus de catalyse dépendent du p_H. Dans le domaine de p_H de 9 à 11, il apparaît un produit d'oxydation rouge, de structure inconnue; il s'agit probablement d'un dérivé de l'o-quinone. La réaction catalytique permet de déceler 10^–4 g cobalt/5 ml. Dans ce domaine de p_H, à 100° C le Tiron stabilise l'eau oxygénée et à 45° C, suivant sa concentration, il catalyse la décomposition de l'eau oxygénée. L'effet joue probablement un rôle sur le mécanisme de la réaction catalysée; on ne peut pourtant pas interpréter clairement ces relations au moyen des indications publiées jusqu'ici. Le processus secondaire qui accompagne la réaction ou qui la suit, peut être ramené à la décomposition catalytique du complexe H₂O₂-OOH^–. Entre p_H 7 et 9, la réaction catalysée donne naissance à une semiquinone; au-dessus de p_H 11, le Tiron oxyde la semi-quinone avec ouverture du cycle et élimination d'une mole de sulfate ce qui donne ensuite des composés qui portent le caractère acide.