Electrocatalytic hydroxylation of aniline on metal oxides

Studies of Mn, Cr, Cu, La, Sb, V, Co and W oxides as catalysts for the electrocatalytic oxidation of aniline to p-aminophenol have revealed the electrocatalytic activity of WO₃. A mathematical model for the kinetics of analine oxidation on WO₃ is suggested that agrees fairly well with the experimental data.

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Mn, Cr, Cu, La, Sb, V, Co, W -. , . , , .

     

Thermal and mechanical behavior of polyethylene film obtained by orientational crystallization

The thermal and mechanical behaviour was measured in the U. S.for a polyethylene that had been prepared and highly drawn in the U. S. S. R. The melting point and percent crystallinity were evaluated in this studies as a function of heating rate and recrystallization. The Young's modulus and tensile stress to break in the orientation direction were 4.1 and 0.15 GPa, respectively.The tensile strain to break was about 8%.

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Zusammenfassung Das thermische und mechanische Verhalten eines in der UdssR hergestellten und stark gezogenen Polyäthylens wurde in den U. S. A. gemessen. Schmelzpunkt und Prozentsatz der Kristallinität wurden als Funktion der Aufheizgeschwindigkeit und Rekristallisation in den Untersuchungen ausgewertet. Der Young-sche Modulus und die Zugspannung zum Reissen in der Orientierungsrichtung betrugen 4.1, bzw. 0.15 GPa. Die Dehnung bis zum Bruch betrug etwa 8 %.

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Résumé On a effectué, aux Etats Unis, l'étude du comportement thermique et mécanique d'un polyéthylène préparé et fortement étiré en URSS. Le point de fusion et le pourcentage de cristallinité ont été évalués en fonction de la vitesse de chauffage et de la recristallisation. Lesvaleurs respectives du module d'Young et de la limite de rupture dans la direction d'orientation s'élèvent respectivement à 4.1 et 0.15 GPa. L'allongement à la rupture est d'environ 8%.

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, . . . 4.1 0.15 . 8%.

     

Über Tetrahydrospiro [cyclohexan-1,4′(1′H)-chinazolin]-2′(3′H)-one

Zusammenfassung Cyclohexanon bzw. Cyclopentanon sowie ihre durch Aldolreaktion entstehenden Dimeren reagieren mit Harnstoff im sauren Medium zu 5,6,7,8-Tetrahydrospiro[cyclohexan-1,4(1H)-chinazolin]-3(2H)-onen (2) bzw. zum Dihydrospiro-(cyclopentan-1,4(1H)-5H-cyclopenta[d]pyrimidin)-2(3H)-on (10). Substituierte Harnsotoffe geben Gemische der isomeren 5,6,7,8-Tetrahydro- und 4a,5,6,7-Tetrahydroverbindungen (2, 3) bzw. 6,7-Dihydro-tH- und 5,6-Dihydro-4aH-verbindungen (10, 11). Charakteristisch für2 (3),10 (11) ist die Reaktivität der Kernstellen 8 bzw. 7 gegenüber elektrophilen Agentien (2f-v, 3f-j, 9 a-i, 10 d-f). Äthylmalonsäurebis-trichlorphenylester bzw. Formaldehyd und prim. Amine führen2 in ein partiell hydriertes 1H-Pyrido[3,2,1-ij]chinazolintrion (6) bzw. 1H-Pyrimido[5,6,1-ij]chinazolinon (7) über. Die 1-Alkylverbindungen (2) geben mit Formaldehyd und primären Aminen Hexahydro-8a-hydroxy-4a,8-propanospiro-(cyclohexan-1,4(1H)-pyrido[4,3-d]pyrimidin)-2(3H)-one (8).

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Heterocycles, XXV: tetrahydrospiro [cyclohexane-1,4(1H)-quinazoline]-2(3H)-ones

Cyclohexanone and cyclopentanone, resp., as well as their dimers (formed by aldol reaction) react with urea in the presence of acids to 5,6,7,8-tetrahydrospiro[cyclohexane-1,4-(1H)-quinazoline]-3(2H)-ones (2) and to the dihydrospiro-(cyclopentane-1,4(2H)-5H-cyclopenta[d]pyrimidine)-2(3H)-one (10), resp. Substituted ureas give the isomeric 5,6,7,8-tetrahydro- and 4a,5,6,7-tetrahydro compounds (2, 3), and 6,7-dihydro-5H- and 5,6-dihydro-4aH-compounds (10, 11), resp. Characteristic for2 (3),10 (11) is the reactivity of the nuclear places 8 and 7 with electrophilic agents (2f-v, 3f-j, 9a-i, 10d-f). Ethylmalonic acid bistrichlorophenylester resp. formaldehyde and primary amines react with2 to the partially-hydrogenated 1H-pyrido[3,2,1-ij]-quinazolinetrione (6) and 1H-pyrimido[5,6,1-ij]-quinazolinone (7), resp. The 1-alkyl compounds (2) give with formaldehyde and primary amines hexahydro-8a-hydroxy-4a, 8-propanospiro(cyclohexane-1,4-(1H)-pyrido[4,3-d]pyrimidine)-2(3H)-ones (8).

     

Etude thermocinetique des phenomenes de dissolution par calorimetrie Calvet a haute temperature dissolution d'alumines dans la cryolithe

Although the thermal curves given by a Calvet calorimeter can be considered representative of the thermogenesis of slow phenomena, this is not the case for the brief thermal effects of dissolution, for example, which need typically no more than twenty minutes. At high temperatures, a numerical method of deconvolution of the recorded signal was applied in order to obtain the proper thermogenesis of the phenomenon. The time constants of the calorimeter were determined from thermal effects due to the dropping into the bath of small quantities of silver and platinum. The method was applied to the dissolution of a-alumina and industrial aluminas in cryolithic baths at 1290 K. The different kinds of alumina could be classified according to their time of dissolution. The dependence of the alumina concentration of the bath on the dissolution rate was also investigated.

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Zusammenfassung Die mittels eines Calvet-Kalorimeters erhaltenen thermischen Kurven sind zwar repräsentativ für langsame Phänomene der Thermogenese, nicht jedoch für kurzzeitige thermische Effekte wie z. B. ein Inlösunggehen, das im allgemeinen nicht mehr als 20 Minuten dauert. In solchen Fällen wurde für hohe Temperaturen eine numerische Methode zur Zerlegung des registrierten Signals angewandt, um die reine Thermogenese der Phänomens zu erhalten. Zeitkonstanten des Kalorimeters wurden aus den thermischen Effekten bestimmt, die beim Einwerfen kleiner Silber- und Platinmengen in das Bad auftraten. Die Methode wurde zur Untersuchung der Auflösung von -Aluminiumoxid und industriellen Aluminiumoxidproben in Kryolithbädern bei 1290 K herangezogen. Die verschiedenen Aluminiumoxidarten konnten nach der zur Auflösung notwendigen Zeit klassifiziert werden. Die Abhängigkeit der Auflösungsgeschwindigkeit von der Aluminiumoxidkonzentration des Bades wurde ebenfalls untersucht.

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, , . , , , , . , . , . - 1290 K. . .

     

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.     

Effect of deuteration on the thermal dehydration of lithium sulfate monohydrate

Effects of deuteration on the thermal stability, enthalpy change and kinetic parameters for the thermal dehydration of Li₂SO₄·H₂O were examined by means of TG and DSC. The enthalpy change for the monohydrate was smaller by 1.63±0.75 kJ/mol than that for the monodeuterate. The rate constant for the monohydrate was a little larger than that for the monodeuterate. However, the thermal stability, activation energy and frequency factor were practically unaffected by deuteration of the hydrate. It is suggested that the activation entropy as well as the activation energy should be considered in explaining the kinetic deuterium isotope effect in the thermal dehydration of Li₂SO₄·H₂O.

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Zusammenfassung Die Wirkung der Deuterisierung auf die Thermostabilität, die Enthalpie-Änderungen und kinetischen Parameter der thermischen Dehydratisierung von Li₂SO₄·H₂O wurden durch TG und DSC untersucht. Die Enthalpie-Änderung für das Monohydrat wurde um 1.63±0.75 kJ/mol niedriger gefunden als für das Monodeuterat. Die Geschwindigkeitskonstante für das Monohydrat war etwas größer als für das Monodeuterat. Die Thermostabilität, die Aktivierungsenergie und der Frequenzfaktor wurden jedoch von der Deuterisierung des Hydrats praktisch nicht beeinflußt. Es wird vorgeschlagen, daß bei der Erklärung des kinetischen Deuterium-Isotop-Effekts bei der thermischen Dehydratisierung von Li₂SO₄·H₂O sowohl die Aktivierungsentropie als auch die Aktivierungsenergie berücksichtigt werden müssen.

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, Li₂SO₄·H₂O. 1.63+0.75 /. , . , , . , Li₂SO₄·H₂O.

     

A new BPO4 catalyst in organic reactions. Dehydration of cycloalkanols

The synthesis of some new and economical BPO₄ catalysts is described. The chemical and textural properties and the thermogravimetric analysis (TGA) of these catalysts is given. The dehydration of cyclohexanol, cycloheptanol and cyclooctanol catalyzed by these new BPO₄ catalysts is studied using the microcatalytic pulse technique.

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BPO₄. , (). , , BPO₄, .

     

Ru(III)-catalyzed oxidation of acetanilide, o-chloroacetanilide, p-chloroacetanilide and p-methylacetanilide by sodium perioda'te at pH 4

The order with respect to [Ru(III)] and [substrate] is unity in each while zero order with respect to [IO ₄ ^– ] has been observed. Variation of solvent composition has no pronounced effect on the rate. A plausible mechanism is suggested.

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[Ru(III)] [] , [IO ₄ ^– ] . . .

     

Synthesis and Structure of a Bis-calix[4]arene with an o-Xylene Linkage

The reaction of p-tert-butyl calix[4]arene 1 with,'-dibromo-o-xylene in basic conditions leads totwo new compounds. One of them is a bis-calix[4]arene, whose crystal structure has been determined.     

Catalytic reduction of NO with CO over CuxCo3?xO4 spinels

The interaction between NO and CO over Cu_xCo_3–xO₄ spinels (0x1) has been studied. It has been found that the two reactions of NO reduction, to N₂O and N₂, respectively, are accelerated by the increase of Cu content (x). With the second reaction acceleration occurs only at x>0.5. This is attributed to the presence of different centers on which N₂O and N₂ are formed.

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NO CO Cu_xCo_3–xO₄ (0x1). , NO N₂O N₂ Cu (x). x>0,5. , N₂O N₂.

     

Changes in activity, selectivity and surface area along an iron-molybdenum catalyst bed after its industrial application

After the industrial use in a combined reactor the surface area of catalysts continuously decreases along the tube. Activity and selectivity of the samples show an extremum as a function of the height (minimum activity corresponds to maximum temperature in the layer). Above and below the hot point, the activities are almost the same but are lower than the initial value. Selectivity is a maximum for samples taken below the hot point. Upwards and downwards from this point the selectivity slightly decreases but remains significantly higher than for the initial catalyst.

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. , , . , . , . , . , , .

     

Cleavage of enantiomers of methano-1H-cyclooct[b]indol-9-ol and their absolute configuration

Chiral [6R and 6S-(6, 9, 10)]methano-1H-cyclooct[b]indol-9-ols were segregated into enantiomers through diastereomeric esters with (R)--trifluoromethylphenylacetic acid. The absolute configuration of the enantiomers was established by the NMR method using the shift reagent Eu(fod)₃ and the circular dichroism spectra.     

Catalytic effect of hydroxy groups on reaction of polyamine with tert-butyl acrylate

The reaction of N-cyclohexyl-1,3-propanediamine with tert-butyl acrylate and the catalytic effect of hydroxy groups on the reaction course was investigated by Near Infrared spectroscopy. The reaction was found to be bimolecular and of second order. The dependence of rate constant on catalyst concentration (diols) is linear and the structure of diol used has no effect.

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N--1,3- -. . . () , .

     

Synthetic studies in the field of chlorobium chlorophyll

By the condensation of -halogenomethyl derivatives of pyrroles with -unsubstituted pyrroles the synthesis of the following unsymmetrical dipyrrolylmethanes has been effected: 5-benzyloxycarbonyl-5-ethoxycarbonyl-3, 3-di(-methoxycarbonylethyl)-4,4-dimethyl-2,2-dipyrrolylmethane (IIIa), 5-benzyloxycarbonyl-5-ethoxycarbonyl-3-(-methoxycarbonylethyl)-4, 4-diniethyl-3-n-propyl-2,2-dipyrrolylmethane(IIIb), 3-acetyl-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIIc), and 3-bromo-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIId). Hydrogenation of the unsymmetrical dipyrrolylmethanes IIIa, b, c, and d has given the corresponding monocarboxylic acids IVa, b, c, and d. The formylation of the dipyrrolylmethanemonocarboxylic acid IVa has given 5-ethoxycarbonyl-5-formyl-3,3-di(-methoxycarbonylethyl)-4, 4-dimethyl-2,2-dipyrrolylmethane (V).For communication II, see [1].Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1045–1047, August, 1970.     

Properties of some catalysts used for the decarbonylation of furfural

Three catalysts containing Mn, Zn, Cd, Sr and K oxides supported on alumina and used for the decarbonylation of furfural are described in this work. The properties of these catalysts such as coefficient and heat of adsorption, specific surface and pore distribution and volume are reported in this work.

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, Mn, Zn, Cd, Sr K, , . , , , .

     

Temperature-programmed reduction and oxidation of bimetallic Pd?Ni/Al2O3 catalysts

Temperature-programmed reduction and oxidation of bimetallic catalysts Pd–Ni/Al₂O₃ seem to indicate phase segregation of palladium and nickel oxides and alloying of palladium and nickel in the process of reduction of oxidized catalysts.

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- Pd–Ni/Al₂O₃ , .

     

Interelectronic angle densities of atoms in momentum space

For the 102 atoms from He to Lr in their ground states, the Hartree–Fock interelectronic angle densities,¯A(¯₁₂), in momentum space are reported, where ¯₁₂ is the angle between the momentum vectorsp₁ and p₂ of two electrons. In the first three atoms, He–Be, ¯A(¯₁₂) is found to be uniform independent of ¯₁₂, while in the remaining 99 atoms,¯A(¯₁₂) is larger for a large ¯₁₂ than for a small ¯₁₂. Accordingly, the average interelectronic angles in momentum space are 90° precisely for the three atoms and greater than 90° for the 99 atoms.     

Comparative studies of the behavior of unsaturated acids and their salts in hydrogenation over platinum

Hydrogenation of unsaturated aliphqtic acids in water and of their unsaturated salts in aqueous metal hydroxide solutions over Pt black has been studied. Kinetic measurements are compared with quantum-chemical calculations.

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Pt-. .

     

Steroid compounds from the Pacific starfishesLuidia quinaria andDistolasterias elegans

One new and four previously known steroid compounds were identified from the Pacific starfishesLuidia quinaria andDistolasterias elegans. The structure of the new steroid was established from spectral data and chemical correlations with other steroids such as 5-cholestane-3,5,6,15,16,26-hexaol 3-sulfate (1). The previously known compounds were identified as 5-cholestane-3,5,6,15,26-pentaol 15-sulfate (2) fromLuidia quinaria and sodium (24S)-O-(-d-giucopyranosyll-5-cholestane-3,6,8,15,24-pentaol 6-sulfate (3), sodium (24S)-5-cholestane-3,6,8,15,24-pentaol 24-sulfate (4), and sodium tornasterol A sulfate (5).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 473–476, February, 1996.     

Kinetic study of the thermal dehydration of layered [Ni2Al(OH)6]2SO4.nH 2O

The kinetics of thermal dehydration of [Ni₂Al(OH)₆]₂SO₄.nH₂O has been studied through the analysis of isothermal weight loss data. The results obtained seem to indicate that the process is governed by a diffusion mechanism up to an value which is dependent on the temperature. An explanation is provided for this behaviour on the basis of the structural properties of the compound and the nature of the water loss.

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Zusammenfassung Die Kinetik der thermischen Dehydratisierung von [Ni₂Al(OH)₆]₂SO₄.nH₂O wurde mittels isothermer TG untersucht. Die Ergebnisse scheinen darauf hinzudeuten, daß der Prozeß bis zu einem von der Temperatur abhängigen -Wert von einem Diffusionsmechanismus bestimmt wird. Für dieses Verhalten wird basierend auf den strukturellen Eigenschaften der Verbindung und der Natur der Wasserabgabe eine Erklärung gegeben.

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, [Ni₂Al(OH)₆]₂SO₄.nH₂O. , , . , .