Studies of copper(II) chelates ofo-hydroxyacetophenone and its substituted derivatives in dioxane-water mixtures

Summary The interactions of Cu^II witho-hydroxyacetophenone (OHA) and its halogeno- and nitro-substituted derivatives were investigated potentiometrically in dioxane-water mixtures by the Calvin-Bjerrum titration technique at 25° C and ionic strength =0.1 M (NaClO₄). All the ligands form 11 and 12 chelates with Cu^II.The variations of pK with mole fraction of dioxane and 1/D were almost linear. Linearity was observed in the plots of log K₁/logK₂ versus pK, and the magnitudes of slopes led to the conclusion that -donation is: (i) strong in aqueous medium and decreases with the increase in dioxane content in 11 chelates, and (ii) weak and does not change with dioxane, in 12 chelates.     

Solvent dependence of the palladium catalyzed telomerization of isoprene with methanol

The palladium catalyzed telomerization of isoprene with methanol as a nucleophilic agent has been investigated, applying the reaction system Pd-complex, tributylphosphine, sodium methylate, isoprene and methanol in a ratio of 1232002000. Two main products were found: 1-methoxy-3,6-dimethylocta-2,7-diene with a head-head coupling (I) and 1-methoxy-2,6-dimethylocta-2,7-diene with a tail-head-coupling (II). By substituting part of the methanol by different solvents the formation of I and II, respectively, can be controlled to a large extent.     

Oxidizing supported reagents, III. Oxidation of alcohols by new supported K2Cr2O7 reagents

Several new supported K₂Cr₂O₇ reagents are used in the oxidation of secondary alcohols. The influence of the number of active sites and the nature of solid support on the yield is discussed. The influence of the structure of alcohol on the yield of ketone is analyzed.

---

K₂Cr₂O₇ . . .

     

The thermal decomposition of thaumasite from Mothae kimberlite pipe,Lesotho, Southern Africa

The endothermic decomposition of thaumasite from Mothae which has been investigated by DTA and TG shows a peak temperature of 138–203°, and reaction orders of 0.45–1.00, depending on the heating rate employed. The activation energy of the reaction was found to be about 19 kcal/mole; the enthalpy is 246 cal/g.The decomposition seems to be divided into one reaction withn=0.90, immediately followed by one withn=1.59. The first reaction is attributed to the loss of H₂O, the second one to the (partial) release of OH and CO₂.

---

Zusammenfassung Die durch DTA und TG überprüfte endothermische Zersetzung von Thaumasit aus Mothae zeigt in Abhängigkeit der angewandten Aufheizgeschwindigkeiten Spitzentemperaturen zwischen 138 und 203° C, sowie Reaktionsordnungen von 0.45 bis 1.00. Die Aktivierungsenergie der Reaktion ergab sich zu 19 Kcal/Mol, die Enthalpie zu 246 cal/g.Die Zersetzung scheint in eine Reaktion vonn=0.90 und eine sofort darauffolgende vonn=1.59 geteilt zu sein. Die erste Reaktion wird dem Verlust von H₂O, die zweite der (teilweisen) Freisetzung von OH und CO₂ zugeschrieben.

---

Résumé La décomposition endothermique de la thaumasite de Mothae a été étudiée par ATD et TG. Suivant la vitesse de chauffage utilisée la température au sommet du pic varie de 138 à 203° C et l'ordre de réaction de 0.45 à 1.00. On a trouvé que l'énergie d'activation s'élevait à 19 kcal, mol^–1 et l'enthalpie à 246 cal. g^–1.Il semble que la décomposition s'effectue suivant une réaction d'ordren=0.90, immédiatement suivie par une autre oùn=1.59. On attribue la première réaction à la perte d'eau et la seconde à la libération (partielle) d'hydroxyles OH et d'anhydride carbonique CO₂.

---

, , 138–203° 0,45–1,00 . , 19 /, - 246 /. , n=0,90, n=1,59. , - OH CO₂.

---

---

The material used for this study has been kindly supplied by Dr. P. H. Nixon, former chief geologist, Department of Mines, Maseru, Lesotho.     

Reaction of ammonium sulphate with aluminium oxide

The reaction between ammonium sulphate with aluminium oxide was studied. It was confirmed by X-ray diffraction and chemical analysis that three intermediate reaction products, (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ and Al₂(SO₄)₃, are formed. The thermal decompositions of these three compounds were carried out. It has been shown that the same rate law is valid for them. The activation energies for (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ and Al₂(SO₄)₃ are 95.9, 177.9 and 291.0 kj/mol, respectively.

---

Zusammenfassung Die Reaktion von Ammoniumsulfat mit Aluminiumoxid wurde untersucht. Durch Röntgendiffraktion und chemische Analyse wurde bestätigt, daß drei Zwischenprodukte (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ und Al₂(SO₄)₃ gebildet werden. Die thermische Zersetzung der drei Verbindungen wurde durchgeführt. Es wurde gezeigt, daß für alle drei dasselbe Geschwindigkeitsgesetz Gültigkeit hat. Die Aktivierungsenergien für (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ und Al₂(SO₄)₃ sind 95.9, 177.9 und 291.0 kJ/Mol.

---

. - : (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ Al₂(SO₄)₃. , , . (NH₄)₃Al(SO₄)₃, NH₄Al(SO₄)₂ Al₂(SO₄)₃, , 95.9; 177.9 291.0 . ^–1.

---

---

The authors are grateful to Dr. H. Osada and Mr. H. Nakamura, Department of Environmental Engineering, Kyushu Institute of Technology, for their helpful discussions.     

Some effective solvents for rapid and reliable characterization of phenylthiohydantoin-amino acids

Summary One-dimensional chromatography with internal standards permits reliable identification of the phenylthiohydantoins from all the common amino acids with the following TLC systems: silica gel — chloroform/n-butyl acetate (9010), di-isopropylether/ethanol (955), dichloromethane/ethanol/acetic acid (9082) ortrans-dichloroethylene/ethanol/acetic acid (88102); and cellulose with 25% formic acid — heptane/isobutanol/75% fromic acid (40309) or silica gel — chloroform/ ethanol/acetic acid/water (50470.52.5).Abbreviations: PTH=phenylthiohydantoin, TLC=thin-layer chromatography, HPTLC=high-performance TLC; other abbreviations: see end of text. Proportions in solvent mixtures are v/v except where otherwise indicated.     

Catalytic and acidic properties of different metal-zeolite catalysts

Catalytic and acidic properties of bifunctional catalysts containing faujasite, superhigh-silica zeolite and mordenite have been studied in isomerization of C₈-alkylaromatic hydrocarbons.

---

C₈ , , - .

     

Nonisothermal kinetics of zinc oxide nonstoichiometrization

The results obtained by studying zinc oxide non-stoichiometrization are presented. The kinetic parameters values under nonisothermal conditions were calculated too. Both the nonstoichiometric zinc oxide composition and the kinetic parameter values are depending on the generating substances.

---

Zusammenfassung Die Ergebnisse der Untersuchungen der Nichtstöchiometrisierung von Zinkoxid werden vorgeführt.Die Werte der kinetischen Parameter unter nicht-isothermen Bedingungen wurden eben falls berechnet.Sowohl die nichtstöchiometrische Zusammensetzung des Zinkoxids als auch die Werte der kinetischen Parameter hängen von der das Phänomen auslösenden Substanz ab.

---

Résumé On présente les résultats d'une étude sur la formation d'oxyde de zinc non-stchiométrique. Les valeurs des paramètres cinétiques en conditions non-isothermes sont égale ment calculées. La composition de l'oxyde de zinc non-stchiométrique ainsi que les valeurs des paramètres cinétiques dépendent du composé de départ.

---

, , . .

     

Thermal analysis of bitumens from black coal,extracted successively with different solvents

A successive extraction of bitumes from black coal was carried out using the following solvents: petroleum ether, petroleumether-benzene (11), benzene, benzene-ethyl ether (11), ethyl ether, ethyl ether ethanole (11), ethanol. These extract organic products as follows: 0.06, 0.16, 0.11, 0.21, 0.07, 0.29 and 0.70% respectively. The obtained by the above mentioned solvents chujniuds were compounds to the thermal and IR-spectral analysis.

---

Zusammenfassung Mittels folgender Lösungsmittel wurde eine sukzessive Extraktion von Bitumen aus Steinkohle durchgeführt: Petrolether, Petrolether-Benzol (11), Benzol, Benzol-Ethylether (11), Ethylether, Ethylether-Ethanol (11), Ethanol. In dieser Reihenfolge konnten organische Produkte zu 0.06, 0.16, 0.11, 0.21, 0.07, 0.29 bzw. 0.70 % extrahiert werden. Die durch aufgeführte Lösungsmittel erhaltenen Verbindungen wurden einer Thermound einer IR-Analyse unterzogen.

     

Some remarks about butene-1 transformations on NaHY zeolite

Comments are given on the paper Alternative Interpretation of Infrared Spectra of the Zeolite NaHY+Butene-1 System of Forster and Seelemann /2/. Our previous paper /1/ was partly revised but the usefulness of comprehensive studies by infrared and temperature-programmed desorption methods has been emphasized.

---

: NaHY+-1. [2]. [1] , - .

     

Quantitative electron-probe microanalysis of light elements: Determination ofa-Si∶C∶N∶O∶H insulating films

Amorphous SiCNOH films (1–3 m) are studied by EPMA after deposition of gold (1–5 nm) as a conductive coating. Its influence on thek-ratios (X-ray intensity relative to an uncoated standard) of silicon, carbon, nitrogen and oxygen is described as a linear function of the simultaneously determinedk-ratio of gold. Thek-ratios representing the uncoated specimen are obtained by extrapolation and, in combination with the PAP matrix correction model, quantitative EPMA can be performed with an analytical error of 2–5%, as it is demonstrated by samples of SiC, Si₃N₄ and SiO₂. No systematic shift of the concentrations is observed for layers ofa-SiCNOH determined at various electron energies of 5–12.5 keV. Hydrogen is calculated by difference and the concentrations prove to be a useful estimate in agreement with the results of chemical analysis. Si-K/Si-K spectra recorded on organo-silicon films and binary silicon compounds point out significant differences concerning the formation of Si-C, Si-N and Si-O chemical bonds.     

Synthesis of 3′, 4′-dihydronaphth-1′, 2′ ∶ 5, 4-oxazole and its 2-aryl derivatives

From 2-amino-1-keto-1, 2, 3, 4-tetrahydronaphthalene, prepared by reduction of isonitroso--tetralone, a number of N-acyl derivatives are prepared, and these are converted further to 2-substituted 3, 4-dihydronaphth-1, 25, 4-oxazoles,     

Preparation et proprietes physico-chimiques de l'hydrure d'aluminium AlH3γ

Résumé AlH₃ a été synthétisé. La décomposition thermique de cet hydrure ainsi que la désolvatation de Al(AlH₄)₃, (C₂H₅)₂O ont été étudiés par analyse thermogravimétrique. L'analyse thermique différentielle effectuée sur AlH₃ montre un effet exothermique dû au passage à la forme AlH₃ puis endothermique correspondant à la décomposition de la phase formée. Une structure type alanate est proposée pour AlH₃ .

---

Aluminium hydride has been synthetised. Thermogravimetry has been used to investigate the thermal decomposition of this phase and the desolvation of A1(AlH₄)₃· (C₂H₅)₂O. Differential thermal analysis of-AlH₃ shows an exothermic effect due to transformation to -A1H₃, followed by the endotherm of -AlH₃ decomposition. A structure of alanate type is proposed for -AlH₃.

---

Zusammenfassung -AlH₃ wurde synthetisiert. Die thermische Zersetzung dieses Hydrids sowie die Desolvatation von Al(AlH₄)₃·(C₂H₅)₂O wurden mittels Thermogravimetrie untersucht. Die Differentialthermoanalyse von-AlH₃ zeigt einen dem Übergang in die AlH₃ -Form entsprechenden exothermen und mit nachfolgenden endothermen Effekt, welcher der Zersetzung der gebildeten Phase entspricht. Eine Struktur von solvatfreien Alanat-Typ wird für-AlH₃ vorgeschlagen.

---

- . l(l₄)₃. (C₂H₅)₂O . l₃ , l₃. lH₃ .

---

---

Ce travail a été effectué dans le cadre d'un contrat de recherches passé par le Laboratoire de Chimie Minérale avec la Direction des Recherches et Moyen d'Essai. Nous remercions bien vivement cet organisme ainsi que le Centre de Recherches ELF ERAP de Solaize de l'aide qu'ils nous ont apportée.     

Structural studies of nickel-based Raney catalysts

Electron microscopy and Mössbauer spectroscopy studies of nickel-based Raney catalysts have revealed that the catalysts are formed through the successive aggregation of their structural elements. Catalyst particles are covered by a thin layer of nickel oxide.

---

. , . .

     

Thermal properties of thio-and selenocyanatocopper(II) complexes with bipyridine and phenanthroline

The paper deals with the thermal properties of complex compounds of the general formula CuL₂(NCX)₂ (whereL=bipy or phen,X=S or Se). The phenanthroline complexes exhibit a higher thermal stability than those with bipyridine. For the latter complexes thermal decomposition begins with the release of bipyridine molecules, while for the phenanthroline complexes redox reactions of pseudohalogenide ligands with Cu(II) take place. The redox reactions start at a lower temperature for the selenocyanate complexes than for the thiocyanate complexes.

---

Zusammenfassung Vorliegende Arbeit behandelt die thermischen Eigenschaften von Komplexverbindungen der allgemeinen Formel CuL₂(NCX)₂ (mitL=Bipyridin oder Phenanthrolin undX=S oder Se). Die Phenanthrolinkomplexe zeigen eine grössere thermische Stabilität als die Bipyridinkomplexe. Die thermiscne Zersetzung letzterer beginnt mit der Abgabe von Bipyridinmolekülen, während bei den Phenanthrolinkomplexen Redoxreaktionen von Pseudohalogenidliganden·mit Cu(II) stattfinden. Diese Redoxreaktionen beginnen bei den Selenozyanatkomplexen bei niedrigeren Temperaturen als bei den Thiozyanatkomplexen.

---

CuL₂(NCX)₂, L= , X= . . , — . - , .

     

Thermogravimetry of copper and copper oxides (Cu2O-CuO)

The thermogravimetry of mixtures of metallic copper and copper oxides was studied. The experiments were performed by heating the samples in air to 700–800° to transform all the components to copper(II) oxide, and continuing the heating in nitrogen to 1050–1100° when the dissociation of copper(II) oxide to copper(I) oxide is complete. The identification of the components and their quantitative determination were carried out by determining the shape, size, and ratio of the segments of the curves obtained during the heating. The method can be used for quantitative analysis of mixtures of copper and/or copper oxides.

---

Zusammenfassung Gemische von metallischem Kupfer und Kupferoxiden wurden thermogravimetrisch untersucht. Zur Überführung aller Komponenten in Kupfer(II)-oxid erhitzte man sie in Luft auf 700–800°, um daraufhin bis zur vollständigen Dissoziation des Kupfer-(II)-oxids zu Kupfer(I)-oxid unter Stickstoff die Temperatur bis auf 1050–1100° zu steigern. Die Identifizierung der Komponenten und ihre quantitative Bestimmung erfolgten durch die Form, Größe und die Verhältnisse der verschiedenen Abschnitte der erhaltenen Kurven. Diese Methode ist zur quantitativen Bestimmung von Gemischen aus Kupfer und Kupferoxid sowie von Kupferoxiden geeignet.

---

Résumé Étude thermogravimétrique de mélanges du cuivre métallique et d'oxydes de cuivre. Les échantillons sont d'abord chauffés dans l'air jusqu'à 700–800° jusqu'à ce que tous les constituants soient transformés en oxyde de cuivre(II); le chauffage est ensuite poursuivi dans l'azote jusqu'à 1010–1100°, où la dissociation de l'oxyde de cuivre(II) en oxyde de cuivre(I) est complète. Les constituants ont été identifiés et dosés en utilisant la forme, la dimension et les proportions des différentes parties des courbes pendant le chauffage. La méthode peut être utilisée pour l'analyse quantitative de mélanges de cuivre et ou d'oxydes de cuivre.

---

. 700–800: ( (), 1050–1100° [ () (I)]. , , . / .

---

---

The author wishes to acknowledge the financial assistance provided by the Technion — Israel Institute of Technology.The author wishes also to thank Dr. R. F. Tylecote (University of Newcastle Upon Tyne, England) for very helpful comments and useful discussions of this investigation and to Mrs. N. Leder for chemical analyses.     

Studies of Cu?Ni supported catalysts for enantioselective hydrogenation

The effect of support content and composition of supported metal phase on the crystallite size, phase composition and catalytic properties of supported Ni and Cu–Ni catalysts has been investigated. It has been established that with increasing metal content, crystallite sizes and enantioselectivity increase. Copper added to Ni catalysts decreases metal phase dispersity and enantioselectivity.

---

, , - . , . є .

     

Polymeric membrane sodium-selective electrodes based on calix[4]arene ionophores

Six kinds of tetra alkylester type calix[4]arene derivatives, (R₁=R₂=CH₃1, C₂H₅2, C₃H₇3,n-C₄H₉4,t-C₄H₉5,n-C₁₀H₂₁6), a diethyl-didecyl mixed ester type (R₁=C₂H₅, R₂ =C₁₀H₂₁7), and three kinds of lower rim bridged types (R₁=C₂H₅, R₂–R₂=(CH₂)₁₀8, (CH₂)₁₂9, (CH₂)₂(OCH₂CH₂)₃10) were characterized by electrochemical measurement to elucidate the effect of the length of the alkyl group of alkoxycarbonyl substituents on Na⁺ selectivity. To obtain excellent Na⁺ selective ionophores, introduction of short chain alkyl groups rather than long chain ones, such as a decyl group, and maintenance of sufficient solubility of the calix[4]arene derivatives in the membrane solvent are required concurrently. Among the calix[4]arenes tested, 25,26,27,28-tetrakis[(ethoxycarbonyl)methoxy]-p-tert-butylcalix[4]arene2, and the diethyl-didecyl mixed ester type derivative7 are the best ionophores for a Na⁺ selective electrode. On the other hand, sodium selectivity of the bridged type derivative9 is comparable or even superior to that of the known bis(12-crown-4).This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.