Effect of ligands on the hydrogenation selectivity in the presence of rhenium catalysts

It has been established that the catalytic activity of rhenium oxohalide complexes with phosphorus- or sulfur-containing ligands in hydroganation of C₆–C₁₀ olefins, nitrobenzene and p-nitrotoluene is primarily determined by the original ligand to rhenium ion bond. Chain length of olefins does not affect their hydrogenation rate.

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- C₆–C₁₀, - - . .

     

Specificity of hydrogen adsorption on chromia-supported platinum group metal catalysts

Hydrogen adsorption on chromia supported Pd, Rh and Pt was studied under various pretreatment conditions. The reduction temperature influences strongly the hydrogen uptake for all these metals. Platinum supported on chromia shows an unusually high hydrogen adsorption stoichiometry.

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Pd, Rh Pt, Cr₂O₃, . , . Cr₂O₃ .

     

Isoquinoline derivatives

1-(3,4-Dimethoxyphenyl)-1-aminomethylcyclopentane (IV) was condensed with substituted phenylacetyl and benzpyl chlorides to synthesize 1-[R,R,R-phenylacet(benz)amidomethyl]-1-(3,4-dimethoxyphenyl)cyclopentanes (VI), which were converted to 1-[R,R,R-phenyl(benzyl)]-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline-4-spirocyclopentanes (IX) by cyclization and subsequent reduction. Reduction of VI yielded the corresponding secondary amines (VII). The compounds obtained were subjected to Chromatographic analysis. The IR spectra were investigated. Compounds VII and IX were subjected to pharmacological testing.See [6] for communication IV.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 637–640, May, 1971.     

Synthesen von 4-Amino-5,6-dihydro-4H-pyrido[3,2,1-j k]-carbazol, 1-Phenyl-4-amino-1,2,3,4-tetrahydrochinolin und deren Derivaten

Zusammenfassung Die Ringschlußreaktion von Carbazol-N-propionsäure ergab 4-Oxo-5,6-dihydro-4H-pyrido[3,2,1-j k]carbazol, dessen Oxim zur 4-Aminoverbindung reduziert wurde. Ähnlich wurden 1-Phenyl-1,2,3,4-tetrahydrochinolin und einige seiner in 4-Stellung substituierten Derivate über das 1-Phenyl-4-oxo-1,2,3,4-tetrahydrochinolin dargestellt: Reduktion gab den Grundkörper, der auch durch Entschwefelung von entsprechenden Heterocyclen erhalten wurde; Nebenreaktionen werden beschrieben. Umsetzung zum Oxim und Reduktion gab 1-Phenyl-4-amino-1,2,3,4-tetrahydrochinolin. Dieses wurde mit Acrylsäuremethylester zu 1-Phenyl-4-(-carbomethoxyäthyl-amino)-1,2,3,4-tetrahydrochinolin, mit -Propiolacton zu 1-Phenyl-4-(-hydroxypropionyl-amino)-1,2,3, 4-tetrahydrochinolin umgesetzt; beide Substanzen wurden durch LiAlH₄ zu 1-Phenyl-4-(-hydroxypropyl-amino)-1,2,3,4-tetrahydrochinolin reduziert.

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Ring closure reaction of carbazole-N-propionic acid gave 4-oxo-5,6-dihydro-4H-pyrido[3,2,1-j k]carbazole, the oxime of which was reduced to the 4-amino compound. Similarly 1-phenyl-1,2,3,4-tetrahydroquinoline and some derivatives thereof (substituted in position 4) were synthesized via 1-phenyl-4-oxo-1,2,3,4-tetrahydroquinoline: reduction gave the tetrahydroquinoline, which also was synthesized by desulfuration of corresponding heterocyclic systems; by-reactions are described. Reduction of the oxime gave 1-phenyl-4-amino-1,2,3,4-tetrahydroquinoline. The latter reacted with methyl acrylate to 1-phenyl-4-(carbomethoxyethyl-amino)-1,2,3,4-tetrahydroquinoline, with -propiolactone to 1-phenyl-4-(-hydroxypropionyl-amino)-1,2,3,4-tetrahydroquinoline, both of which were reduced by LiAlH₄ to 1-phenyl-4-(-hydroxypropylamino)-1,2,3,4-tetrahydro quinoline.

     

51V NMR studies of systems V2O5-KHSO4 and V2O5?K2SO4

Systems V₂O₅–KHSO₄ and V₂O₅–K₂SO₄ have been studied by the⁵¹V NMR method. The first system demonstrates the same states of vanadium as the previously studied V₂O₅–K₂S₂O₇, in this system a compound with an equimolar ratio of components has been found. In V₂O₅–K₂SO₄ the state of vanadium differs from the above systems and the formation of a compound with V/K=4 is observed.

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⁵¹V KHSO₄–V₂O₅ K₂SO₄–V₂O₅. , K₂S₂O₇–V₂O₅, . K₂SO₄–V₂O₅ V/K4.

     

Epoxidation of propylene with tert-butyl hydroperoxide in the presence of heterogeneous polymeric catalysts

A series of heterogeneous polymeric molybdenum containing catalysts on the basis of weak acid cation exchanger Amberlite IRC-84 in an organic and water medium was prepared. The catalysts activity and selectivity in the epoxidation of propylene with tert-butyl hydroperoxide are compared. Data about the chemical structure of catalytically active molybdenum containing centres of the modified cation exchanger were obtained.

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, , IRC-84 . .. , .

     

Infrared study of the interaction of nitric oxide with CuY zeolites

Infrared studies of the interaction of NO with CuY–A zelites have been made over the temperature range from –100°C to 400°C. Several forms of NO adsorption have been found, in particular, a stable cis-dimer at low temperatures.

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- (–100+400°C) NO CuY–A . NO, ë - .

     

Effect of the network structure on the flammability ofcis-1,4-polyisoprene vulcanizates

The combustibilities ofcis-1,4-polyisoprene and its peroxide and sulphur vulcanizates have been investigated by means of the oxygen index method. The temperature distribution in the sample and the molecular weight of the liquid products formed as a result of elastomer destruction in the combustion zone have been measured. It has been found that the combustibility ofcis- 1,4-polyisoprene diminishes as its cross-link density increases. This effect is much stronger for sulphur than for peroxide vulcanizates. The investigations lead to the conclusion that a mechanism of network degradation and volatile sulphur compounds penetrating to the flame are responsible for this difference.

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Zusammenfassung Die Brennbarkeit des unvernetztencis-1,4-Polyisoprens und seiner Peroxid- und Schwefelvulkanisate wurde mit der Sauerstoffindexmethode untersucht. Messungen der Temperaturverteilung im Prüfling wurden ebenfalls ausgeführt und das Molekulargewicht der infolge der Zersetzung der Elastomere in der Verbrennungszone entstehenden flüssigen Produkte mit der Methode der dynamischen Osmometrie bestimmt. Es wurde festgestellt, daß die Brennbarkeit des cis-1,4-Polyisoprens mit zunehmender Vernetzungsdichte abnimmt, und zwar viel ausgeprägter im Falle der Schwefel- als im Falle der Peroxidvulkanisate. Es wurde gefolgert, daß flüchtige, in die Flamme gelangende Schwefelverbindungen als Verbrennungsinhibitoren wirken.

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-1,4- . , . , -1,4- . . , .

     

Influence of rare earth ions on the properties of Pd/SiO2 in CO hydrogenation

Systematic studies of the effect of the lanthanoid (Ln) nature on the activity and selectivity of (Pd+Ln)/SiO₂ catalysts obtained by decomposition of anchored Ln and Pd complexes in methanol synthesis from CO and H₂ have been carried out. It has been established that the highest promoting effect is observed for Pr and Ho ions.

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(Ln) (Pd+Ln)/SiO₂ , Ln Pd, CO H₂. Pr Ho.

     

Dehydroxylation and catalytic activity of dealuminated Y zeolites

Dehydroxylation and catalytic conversion of m-xylene over dealuminated zeolites were studied.

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- .

     

Study of furan compounds

Research on synthesis of polycyclic spirans of the 1, 6-dioxaspiro-[4, 4]nonane group is continued. Electrolysis of methanol solutions of 2-furylcyclopentanol, 2-(5-methyl-furfuryl)cyclopentanol, and 2-furfuryl-1-indanol, gives, by intramolecular alkoxylation, spiro{perhydrocyclopenta[b]furan-2, 2-(5dihydrofuran)}, spiro{perhydrocyclopenta[b]furan-2, 2-(5-methoxy-5-methyl-2, 5-dihydrofuran)}, and spiro{2, 3, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-(5-methoxy-2, 5-dihydrofuran)}, hitherto undescribed in the literature. Depending on the conditions, catalytic hydrogenation of these gives: spiro{perhydiocyclopenta[b]furan-2, 2-(5-methoxytetrahydrofuran)}, spiro{2, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-(5-methoxytetrahydrofuran)}, spiro{perhydrocyclopenta[b]furan-2, 2-tetrahydrofuran}, and spiro{2, 3, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-tetrahydrofuran}.For Part XXXI see [1].     

Kinetics of thermal decomposition of diacyl peroxides in the presence of aerosil

In the presence of aerosil the thermal decomposition of the polymeric peroxide of sebacic acid is enhanced proportionally to the filler weight fraction in the reaction system. This is attributed to the interaction of peroxide groups with acidic groups on the aerosil surface and their decomposition according to a nonradical mechanism unlike the homolytic radical decomposition in solution.

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, , . .

     

Interaction between propene and CoNaX zeolite and exchange of propene hydrogens

Interaction of propene with CoNaX and NaX zeolites and exchange of propene hydrogens with CoNaX zeolite was studied at the temperature of the IR beam and at 300°C by means of IR and MS analysis. In addition, the heats of adsorption were measured. The structure of adsorbed propene complexes was found to be influenced by the presence of Co²⁺ ions. The mechanism of the exchange is discussed and the properties of the OH groups of HY, HX and CoNaX zeolites are compared.

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CoNaX NaX CoNaX 300°C . . , Co²⁺ . OH , CoNaX .

     

Thermal analysis of ferrous sulphate heptahydrate in air

The thermal decomposition of ferrous sulphate heptahydrate was carried out in air under dynamic and isothermal conditions. The intermediate phases were identified by chemical analysis and an X-ray technique. Ferrous sulphate heptahydrate is converted to tetrahydrate and monohydrate, but this conversion is accompanied by oxidation. Fe(OH)SO₄ and Fe₂O(SO₄)₂ are formed as oxidation products, and the latter decomposes to ferric oxide directly and/or through Fe₂(SO₄)₃.

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Zusammenfassung Die thermische Zersetzung von Eisen(II)sulfat Heptahydrat wurde in Luft unter dynamischen und isothermen Bedingungen durchgeführt. Die Intermediärphasen wurden durch chemische Analyse und Röntgentechnik identifiziert. Eisen(II)sulfat Heptahydrat wird in Tetrahydrat und Monohydrat überführt, doch wird diese Umwandlung durch eine Oxidation begleitet. Fe(OH)SO₄ und Fe₂O(SO₄)₂ werden als Oxidationsprodukte gebildet und letzteres wird unmittelbar und/oder über Fe₂(SO₄)₃ zu Eisen(III)oxid zersetzt.

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Résumé La décomposition thermique dans l'air du sulfate de fer(II) heptahydraté a été étudiée en conditions dynamiques et isothermes. Les phases intermédiaires ont été identifiées par analyse chimique et par rayons X. Le sulfate de fer(II) heptahydraté se transforme en tétrahydrate et en monohydrate mais cette conversion s'accompagne d'une oxydation. Il se forme Fe(OH)SO₄ et Fe₂O(SO₄)₂ comme produits d'oxydation et ce dernier se décompose en oxyde de fer(III) directement ou quelquefois avec formation intermédiaire de Fe₂(SO₄)₃.

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(II) . . (II) . Fe(OH)SO₄ Fe₂O(SO₄)₂. (III) Fe₂(SO₄)₃.

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The authors express their grateful thanks to Prof. P. K. Jena, Director, for his keen interest and permission to publish the paper, and to Dr. A. Lakshminarayana for the X-ray measurements. One of us (MSRS) also thanks the Regional Research Laboratory (CSIR) for a fellowship.     

Kinetics and mechanism of the reaction of 1,2-diethoxyethane hydroperoxide with ozone

The kinetics and products of the reaction of 1,2-diethoxyethane hydroperoxide with ozone in CCl₄ solution at 9 and 22°C have been studied. A reaction mechanism is proposed.

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I,I- CCl₄ (9; 22°C). .

     

Studies on the thermal behaviour of detonating fuse and detonators

Investigations of the thermal stability of detonating fuse containing 10 g pentaerythrol tetranitrate (PETN) revealed that the cord burnt under unconfinement at 403 K. Under confinement in a steel pipe or copper tube there was a partial detonation at 403 K. In order to characterize the thermal stability of PETN and pyrotechnic composition used in fuse head of electric detonators differential thermal analysis (DTA) was used.The electric detonators of aluminium cell and copper cell were heated from ambient temperature to 373 K at an average rate of 0.4 deg/min. The rate of heating was increased gradually to 1.5 deg/min till explosion. The detonation temperature varied between 373 K and 375 K.The impact and friction sensitivity of detonating fuse was poor. There was no detonation when a 5 kg hammer was repeatedly hit over the fuse from a height of one metre. There was no detonation when the detonating fuse was rubbed by a blunt edge of steel plate till it was smashed.

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Zusammenfassung Untersuchungen der thermischen Stabilität von Sprengschnuren mit 10 gm^–1 PETN zeigten, daß die Schnur frei bei 403 K verbrennt. Unter Abschluß in einem Stahloder Kupferrohr tritt bei 403 K eine partielle Detonation auf. Zur Charakterisierung der thermischen Stabilität von PETN und von pyrotechnischen Mischungen, die in Zünderköpfen von elektrischen Sprengkapseln verwendet werden, wurde Differentialthermoanalyse (DTA) angewendet. Die elektrischen Sprengkapseln von Aluminium- und Kupferzellen wurden mit einer durchschnittlichen Aufheizgeschwindigkeit von 0.4 Grad/min von Raumtemperatur auf 373 K erhitzt. Die Aufheizgeschwindigkeit wurde bis zur Explosion allmählich auf 1,5 Grad/min erhöht. Die einzelnen Detonationen erfolgten bei einer Temperatur zwischen 373 und 375 K. Die Stoß- und Reibempfindlichkeit der Sprengschnur war gering. Bei einem mehrmaligen Einwirken eines 5 kg-Hammers aus einer Höhe von 1 m erfolgte keine Detonation. Bei Reiben mit der unscharfen Kante einer Stahlplatte bis zur Zerstörung erfolgte keine Detonation.

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, 10 ^–1 PETN, , 403 , 403 . PETN , , . 373 0,4°/. 1,5°/ . 373 375 . . 5 1 . , .

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The authors are indebted to the Director, Central Mining Research Station for giving permission to publish this paper. The views expressed in the paper are those of the authors and not necessarily of the institute which they belong to.     

Shape selectivity and maximum molecular size in methanol to hydrocarbons transformation

The maximum product size obtained during methanol to hydrocarbons transformation on medium and large pore zeolites and amorphous silica-aluminas is not governed by shape selectivity but it is a consequence of operational conditions and other process characteristics such as the occurrence of cracking reactions.

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, , , .

     

Propylene oxidation over tin-molybdenum oxide catalysts

The influence of preparation of tin-molybdenum catalysts on their phase composition and activity has been elucidated. The mutual dissolution of Sn and Mo oxides leads to a considerable increase in their activities and selectivities in the partial oxidation of propylene to acetone.

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. , .