Total synthesis and properties of prostaglandins 34. Synthesis and x-ray structural analysis of (+)4-(carboxymethyloxyiminomethyl)-2-oxabicyclo-[3.3.0]-6-octen-3-one

The reaction of -formyl--lactones with O-substituted hydroxylamines has been investigated. An x-ray structural investigation has been carried out on (+)4-(carboxymethyloxyiminomethyl)-2-oxabicyclo[3.3.0]-6-octen-3-one.For Communication 33, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 737–742, June, 1993.     

Total synthesis and properties of prostaglandins 30. Modification of (1S,5R)-2-oxabicyclo[3.3.0]-6-octen-3-one at the α-carbon atom

Derivatives of -alkyl-, -alkylidene-, and -hydroxymethylene-2-oxabicyclo[3.3.0]-6-octen-3-one were obtained. The possibility of functional substitution of the bicyclic -lactones at the position to the carbonyl group was thereby demonstrated.For Communication 29, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1621–1630, December, 1991.     

Synthesis and chiral-optical properties of (+)-3-methyl-3,4-dihydroisoquinoline-1-thione

(+)-3-Methyl-3,4-dihydroisoquinoline-1-thione was obtained by sulfuration of (+)-3-methyl-3,4-dihydroisoquinolone with phosphorus pentasulfide or by cyclization of (+)--benzylethyl isothiocyante under the influence of polyphosphoric acid. Measurements of the rotatory dispersion and circular dichroism showed the presence of two positive Cotton effects due to n^* and ^* transitions in the thioamide chromophore, as well as Cotton effects apparently due to ^* transitions in the aromatic chromophore.Communication XXXV from the series Stereochemical Investigations. See [11] for communication XXXIV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 94–97, January, 1976.     

Triterpene glycosides ofHedera taurica. XI. Structures of taurosides St-G1, St-H1, and St-H2 from the stems of Crimean ivy

The previously known glycosides 3-O--L-arabinopyranosyl-28-O-[-L-rhamnopyranosyl-(14)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl]hederagenin and 3-O-[-L-rhamnopyranosyl-(12)-O--L-arabinopyranosyl]-28-O-[-L-rhamnopyranosyl-(14)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl]hederagenin and the new triterpene glycoside tauroside St-H₁ — 3-O--D-glucopyransyl-28-O-[-L-rhamnopyranosyl-(14)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl]hederagenin — have been isolated from the stems ofHedera taurica Carr.M. V. Frunze Simferopol' State University. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 571–579, July–August, 1993.     

Prostanoids: LXXXIII. Synthesis of (±)-19-Carboxy-20-norprostaglandin F2α and Its 15β-Epimer

Starting with (±)-7-hydroxy-6-hydroxymethyl-2-oxa-cis-bicyclo[3.3.0]octan-3-one 15,-19-carboxy-20-norprostaglandins F were synthesized.     

Synthesis and 13C NMR spectra of 5-alkyl-1,4-diaza- and 5-alkyl-1-aza-4-oxabicyclo [3.3.0]octan-8-ones

A group of previously unreported 5-alkyl-1,4-diaza- and 5-alkyl-1-aza-4-oxabicyclo[3.3.0]octan-8-ones have been synthesized from the ethyl esters of -ketocarboxylic acids and ethylenediamine or ethanolamine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1405–1408, October, 1987.     

Diazabicycloalkanes with nitrogen atoms in bridgehead positions. 16. Synthesis and properties of benzo[b]-1,4-diazabicyclo[2.2.2]octene and dibenzo[b,e]-1,4-diazabicyclo[2.2.2]octadiene,containing primary aromatic amino acids

4-Aminobenzo[1,2-b]-1,4-diazabicyclo[2.2.2]octene and 4-aminodibenzo[1,2-b, e]-1,4-diazabicyclo[2.2.2]octadiene have been prepared by cyclization reactions of N--chloroethyl derivatives of 1,2,4-triaminobenzene and aminophenazine, and subsequent catalytic hydrogenation of the corresponding 4-nitrobenzo[1,2-b]-1,4-diazabicyclo[2.2.2]octene and 4-benzylaminodibenzo[1,2-b,e]-1,4-diazabicyclo[2.2.2]-octadiene. Using the conversion of these compounds to azides as an example, we have demonstrated the feasibility of applying these primary aromatic amines for the synthesis of derivatives of these heterocycles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 831–837, June, 1988.     

Thermal properties of Jojoba wax

The thermo-oxidative stability of Jojoba wax (Simmondsia chinensis) was studied by differential scanning calorimetry in a dynamic oxygen atmosphere. The thermo-oxidation activation energy (Ea) was calculated by determining the maximum reaction temperature (Tm) at different heating rates (Hr) and using mathematical models previously proposed for dynamic systems. The value obtained was 21.84 Kcal/mol. The oxidation enthalpiesH _ox were also calculated and a lineal relationship was found with the square root of the heating rate and the initial temperature of thermo-oxidation

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Zusammenfassung Die thermooxidative StabilitÄt von Jojoba-Wax (Simmondsia chinensis) wurde durch Differential-Abtastkalorimetrie in dynamischer SauerstoffatmosphÄre untersucht. Die Aktivierungsenergie der Thermooxidation (Ea) wurde durch die Bestimmung der maximalen Reaktionstemperatur (Tm) bei verschiedenen Aufheizgeschwindigkeiten (Hr) unter Anwendung der vorhergehend für dynamische Systeme vorgeschlagenen mathematischen Modelle berechnet. Der erhaltene Wert betrug 21.84 Kcal/Mol. Die OxidationsenthalpienH _ox wurden ebenfalls berechnet und lineare ZusammenhÄnge mit der Quadratwurzel der Aufheizgeschwindigkeit und der Anfangstemperatur der Thermooxidation wurden gefunden.

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Résumé On a étudié, par analyse calorimétrique différentielle dans une atmosphère dynamique d'oxygène, la résistance à l'oxidation thermique de la cire Jojoba (Simmondsia chinensis). On a calculé l'énergie d'activation (Ea) de l'oxydation thermique en déterminant la température maximale (Tm) de la réaction à diverses vitesses de chauffage (Hr) et en utilisant les modèles mathématiques déjà proposés pour des systèmes dynamiques. La valeur obtenue est 21.84 kcal/mole. On a calculé également les enthalpies d'oxydation (H_ox) et on a trouvé des corrélations linéaires entre les racines carrées de la vitesse de chauffage et la température initiale de l'oxydation thermique.

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Jojoba (Simmondsia chinensis) . - (E _a) ( _m) , . 21.84 /. (H _ok) .

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This work has been partially supported by the Consejo Nacional de Ciencia y Technología and the Comisión Nacional de las Zonas Aridas.     

Intramolecular cyclization of N-phthalyl-β-aryl-β-alanine phenylhydrazide

The reaction of N-phthalyl--aryl--alanine N-methyl-N-phenylhydrazides with phosphorus oxychloride (at80 °C) is accompanied by further transformations of the initially formed 2-aminoindole derivatives and leads to isoindolo[1,22,3]-pyrimido[5,6-b]indole derivatives. Intermediate 2-aminoindoles were isolated at lower reaction temperatures. The hydrolysis of the isoindolo[1,22,3]pyrimido [5, 6-b]indole derivatives was studied. The structures of the compounds obtained were established on the basis of the PMR, IR, and UV spectra and the results of elementary analysis.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 926–929, July, 1982.     

Thermal properties of molten sulphur-oxyanionic salts

Lithium, sodium, potassium and ammonium bisulphate have been shown by detailed TG/DTA studies to have limited application as molten solvents. By contrast, the eutectic bisulphate systems, ammonium-potassium bisulphate and sodium-potassium bisulphate, appear to be excellent molten solvents in view of their low melting points, long liquid ranges and prolonged thermal stability at 200°. In contrast to previous studies, potassium pyrosulphate has been found to be an excellent molten solvent, provided rigorous preliminary drying procedures have been applied.

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Zusammenfassung An Hand eingehender TG/DTA-Untersuchungen wurde gezeigt, daß die Bisulfate von Lithium, Natrium, Kalium und Ammonium nur eine begrenzte Anwendung als geschmolzene Lösungsmittel finden können. Die eutektischen Bisulfat-Systeme Ammonium/ Kalium Bisulfat und Natrium/Kalium Bisulfat scheinen wegen ihrer niedrigen Schmelzpunkte, ihres weiten Flüssigkeitsbereichs und ihrer dauerhaften Thermostabilität bei 200° ausgezeichnete geschmolzene Lösungsmittel zu sein. Im Gegensatz zu früheren Untersuchungen erwies sich Kaliumpyrosulfat als ein ausgezeichnetes geschmolzenes Lösungsmittel, vorausgesetzt daß vorangehend strenge Trocknungsverfahren angewandt wurden.

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Résumé On montre par une étude TG/ATD approfondie que les hydrogénosulfates de lithium, de sodium, de potassium et d'ammonium n'ont qu'une application limitée en tant que solvants fondus. Les systèmes eutectiques des hydrogénosulfates ammonium/potassium et sodium/potassium paraissent, au contraire, être des solvants fondus excellents, en raison de leurs points de fusion bas, de leurs larges intervalles d'existence à l'état liquide et de leur stabilité thermique prolongée à 200°. Contrairement à des études antérieures, on a trouvé que le pyrosulfate de potassium est un solvant fondu excellent, à la condition d'appliquer un mode opératoire rigoureux lors du séchage préliminaire.

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/ , , , . , - - , 200°. , , , - .

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The authors would like to thank Dr. C. Barraclough and Mr. M. Beyer of the Physical Chemistry Department, Melbourne University, for assistance with the Raman spectra.     

Effect of dentate number of anchored phosphine ligands on the composition and catalytic properties of their palladium complexes

Mono-, di- and triphosphine ligands anchored by a Si–C bond to the surface of silica have been synthesized. Complexes of Pd(II) and Pd(O) with these ligands have been obtained. On the basis of elemental analysis and UV spectroscopy, structures of the complexes formed are suggested. The catalytic properties of the above complexes in the selective hydrogenation of cyclopentadiene are compared.

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-, - , Si–C . Pd(II) Pd(O) . - . .

     

Influence of alkaline and acidic promoters on the catalytic properties of metallic palladium and rhodium in CO hydrogenation

Influence of alkaline and acidic promoters on the composition of CO hydrogenation products on SiO₂-supported metallic palladium and rhodium has been examined. Alkaline and acidic promoters have been established to increase the yield of methanol and ethanol, respectively.

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, . , , —.

     

Prostanoids: LXXXI. Synthesis of (±)-2-Decarboxy-2-ethyl-19,20-dinor-18-carboxyprostaglandin E1

2-Decarboxy-2-ethyl-19,20-dinor-18-carboxyprostaglandin E₁ was synthesized starting from (±)-7-hydroxy-6-hydroxymethyl-2-oxa-cis-bicyclo[3.3.0]octan-3-one.     

Diazabicycloalkanes with nitrogen atoms in the nodal positions. 21. Heteroatom-promoted lithiation of benzo[b]-1,4-diazabicyclo[2.2.2]octene and introduction of substituents into the annelated benzene ring

The action of n-butyllithium on benzo[b]-1,4-diazabicyclo[2.2.2]octene leads to lithiation in the 3 position of the aromatic ring. The reaction of this lithium derivative with electrophilic reagents was used to synthesize 3- and 3,6-substituted derivatives of benzo[b]-1,4-diazabicyclo[2.2.2]octene.See [1] for Communication 20.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 798–803, June, 1991.     

Dependences between thermal methods for determination of properties of polymer-asphalt composites

Attempts were made to determine correlations between the different thermal methods used for estimating the properties of polymer-asphalt compositions. The compositions containing asphalt, polypropylene and PVC were prepared by mixing the melted components. A number of methods were found usable for estimation of the thermal properties of the compositions, and the possibility of describing the obtained results in terms' of mathematical relationships was demonstrated.

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Zusammenfassung Es wurde versucht, Übereinstimmungen zwischen den verschiedenen Methoden zur Abschätzung der Eigenschaften von Polymer-Asphalt-Gemischen festzustellen. Die Gemische von Asphalt, Polypropylen und PVC wurden durch Mischung der geschmolzenen Komponenten erhalten. Es konnte einerseits eine Anzahl von brauchbaren Methoden zur Abschätzung der thermischen Eigenschaften der Gemische gefunden werden und andererseits eine Möglichkeit zur Fassung der erhaltenen Resultate in mathematische Beziehungen dargestellt werden.

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, - . , , , . , .

     

Flame atomic-absorption spectrometric determination of traces of copper, iron, lead and manganese in nitric acid by injection dosation of concentrated solutions neutralized with ammonia

Summary The dosation system MS-11T working in the solvent-sample-solvent mode was used for the flame atomic-absorption spectrometric determination of copper, lead, iron and manganese in concentrated nitric acid. The acid was neutralized with gaseous ammonia. The resulting concentrated solution of ammonium nitrate (corresponding to 46.4% HNO₃) was thermostatted at 75°C and 250 l-portions were injected into the flame. The effect of the temperature of sample and washing solvent was studied. The precision of the analysis was improved by ensemble summation of the signals. The trace element concentrations, determined by the method of standard addition, were at 0.1 mg/l level.Dedicated to Prof. Dr. Ing. Bernhard Schrader on the occasion of his 60th birthday     

The thermal properties of polysiloxanes poly(dimethyl siloxane) and poly(diethyl siloxane)

New measurements and literature data on polysiloxanes covering heat capacities, transition parameters, enthalpies, entropies and Gibbs energies are presented and critically reviewed. TheATHAS computation method is used to bring heat capacities into agreement with an approximate frequency spectrum. The various crystal and mesophases are discussed. TheATHAS (1990) recommended data are as follows: For poly(dimethyl siloxane) the glass transition is at 146 K with an increase in heat capacity of 29.24 J/(K mol). The completely crystalline sample melts at about 219 K with a heat of fusion of 2.75 kJ/mol. For poly(diethyl siloxane) the glass transition is at 135 K with an increase in heat capacity of 34.48 J/(K mol). The completely crystalline sample changes to a condis crystal at 206.7 K with a heat of disordering of 2.72 kJ/mol. The transition to a poorly characterized viscous crystal with thermodynamic properties close to the melt occurs at 282.7 K with an enthalpy of transition of 1.84 kJ/mol. Final fusion occurs at 308.5 K and a small endotherm of about 231 J/mol. Tables of heat capacities, enthalpies, entropies and Gibbs energies are given from 0 K to 550 K.

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Zusammenfassung Neue Messungen und Literaturangaben von Polysiloxanen über Wärmekapazität, Umwandlungsparameter, Enthalpien, Entropien und Gibbssche Energien werden vorgestellt und kritisch betrachtet. Das Rechenverfahren ATHAS wurde benutzt, um die Wärmekapazitäten mit einem annähernden Frequenzspektrum in Einklang zu bringen. Es wurden die verschiedenen Kristall- und Mesophasen diskutiert. Die von ATHAS (1990) empfohlenen Werte sind wie folgt: Für Poly(dimethylsiloxan) beträgt der Glasumwandlungspunkt 146 K bei Zunahme der Wärmekapazität um 29.24 J/(K.mol). Die vollständing kristalline Probe schmilzt bei etwa 219 K mit einer Schmelzwärme von 2.75 kJ/mol. Für Poly(diethylsiloxan) beträgt der Glasumwandlungspunkt 135 K bei Zunahme der Wärmekapazität um 34.48 J/(K.mol). Die vollständig kristalline Probe wandelt sich bei 206.7 K um, die Fehlordnungswärme beträgt 2.72 kJ/mol. Die Umwandlung in einen wenig verstandenen viskosen Kristall, dessen thermodynamische Eigenschaften denen der Schmelze gleichen, erfolgt bei 282.7 K mit einer Umwandlungsenthalpie von 1.84 kJ/mol. Letztendlich verläuft das Schmelzen bei 308.5 K mit einem kleinen endothermen Effekt von etwa 231 J/mol. Wärmekapazitäten, Enthalpien, Entropien und Gibbssche Energien sind für den Bereich 0 K–550 K tabellarisch angegeben.

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, , , , . ATHAS , - . . ATHAS (1990) : 146 29,24 / ·. 219 2,75 /. 135 34,48 /·. 206,7 2,72 /. « » 282,7 1,84 /. 308,5 231 /. , , 0–550 .

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This work was supported by the National Science Foundation, Polymers Program, Grant #DMR 83-17097 and early work of J.P.W. was supported by the Am. Chem. Soc. Petroleum Research Found, Grant 12431-AC7. In addition at Oak Ridge National Laboratory the work was sponsored by the Division of Materials Sciences, Office of Basic Energy Sciences, U.S. Department of Energy under contract DE-AC05-84OR21400 with Martin Marietta Energy Systems Inc.     

Kinetics and mechanism of the decomposition of pyrite under conventional and quasi-isothermal — quasi-isobaric thermoanalytical conditions

The kinetics and mechanism of the thermal decomposition of pyrite were examined by the method of quasi-isothermal and quasi-isobaric thermogravimetry (Q-TG). It emerged that by means of this technique the overlapping partial processes of the complicated oxidation and decomposition reactions of pyrite can be separated and studied independently from one another. It was found that the partial reactions FeS₂=FeS +S and Fe₂O_3–x(SO₄)_x=Fe₂O₃+SO₃ are endothermic processes taking place quasiisothermally and leading to equilibrium, while the oxidation FeS+O₂=Fe₂O_3–x(SO₄)_x is an exothermic process which takes place in an oscillating manner in a rather broad temperature interval.

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Zusammenfassung Autoren untersuchten die Kinetik und den Mechanismus der thermischen Zersetzung von Pyrit durch quasi-isotherme und quasi-isobare Thermogravimetrie (Q-TG). Es stellte sich heraus, daß sich überlagernde Teilprozesse der komplizierten Oxydations- und Zersetzungsprozesse von Pyrit mit Hilfe dieser Technik absondern und unabhängig voneinander untersuchen lassen. Es wurde festgestellt, daß die Teilreaktionen FeS₂=FeS+S und Fe₂O_3–x(SO₄)_x=Fe₂O₃+SO₃ endotherme Prozesse sind, die quasi-isotherm verlaufen und zu einem Gleichgewicht führen, während die Oxydation FeS+O₂=Fe₂O_3–x(SO₄)_x ein exothermer Prozeß ist, der oszillierend in einem ziemlich breiten Temperaturintervall verläuft.

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(Q-) . . , FeS₂=FeS+S Fe₂O_3–x(S₂O₄)_x=Fe₂O₃+SO₃ , . FeS+O₂ =Fe₂O_3–x(SO₄)_x , .

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The authors thank Prof. E. Pungor for valuable discussions, and Mrs. M. Kiss and Miss I. Fabian for their technical assistance.     

On the problem of predicting the activity of oxide and carbonate catalysts in some reactions of petrochemical synthesis

The problem of predicting the activity of oxide and carbonate catalysts for some reactions of petrochemical synthesis (vapor phase conversion of carboxylic acids, catalytic oxidation of asphaltic tar to bitumen) according to the established dependence of thermal stability variations of intermediates on the formation enthalpy of metal oxides or standard ele.trode potentials is discussed.

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, ( , ) .

     

Triterpene Glycosides of Tetrapanax papyriferum. I. Isolation and Structure of Glycosides St-H2 and St-I2 from Stem Bark

Stem bark ofTetrapanax papyriferumC. Koch., Araliaceae, yielded new triterpene glycosides 28-O--L-rhamnopyranosyl-(14)-O-(6-O-acetyl--D-glucopyranosyl)-(16)-O--D-glucopyranosyl esters of the 3-O-[-D-glucopyranosyl-(13)-[-D-galactopyranosyl-(12)]-O--L-arabinopyranosides of oleanolic and echinocystic acids. The structures of these substances were established using chemical and physicochemical methods