Triterpene glycosides from Pulsatilla chinensis

Four triterpene glycosides were isolated from the roots of Pulsatilla chinensis (Bunge) Regel (Ranunculaceae). Two new glycosides, chinensiosides A (1a) and B (2), were identified as 3-O-[-L-rhamnopyranosyl-(12)--L-arabinopyranosyl]-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid and 3-O-{-L-rhamnopyranosyl-(12)-[-D-glucopyranosyl-(14)]--L-arabinopyranosyl}-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid. The other two glycosides were identified as previously known hederasaponin C (3) from Hedera helix and glycoside III (4) from Pulsatilla cernua.     

Kinetics of Cr(VI) and V(V) oxidation of trans-stilbene and indene

Title reactions are acid catalyzed and strongly dependent on the permittivity of the medium. With Cr(VI) indene reacts faster than trans-stilbene, but with V(V), trans-stilbene reacts faster than indene. The mechanism is discussed.

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. Cr(VI) , -, V(V) - , . , .

     

Transformed steroids. 121. Synthesis of the δ-lactone of 3β-acetoxy-16α-hydroxy-6-oxo-24-nor-5α-chol-17(20)-en-23-oic acid

The synthesis of the ¹⁷⁽²⁰⁾-16 analog of natural chiogralactone is described. Attempts to introduce a 6-oxo group directly into the -lactone proved unsuccessful, since the first stage — saponification — took place with the formation of three products: the 3-hydroxy--lactone, the 3-hydroxy-²⁰⁽²²⁾-lactone, and the 15,17(20)-dienoic acid. The synthesis of the desired compound was effected from the ethyl ester of the 5,16-dienoic acid by the scheme 3-acetate3-tosylate6-hydroxy-3,5-cyclosteroid6-oxo-3,5-cyclosteroid6-oxo-5H--lactone. It has been shown that the cyclopropane ring in the 3,5-cyclosteroid -lactone is extremely stable under the conditions of acid treatments.N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 184–187, March–April, 1981.     

Thermal and some other properties of the complexes crystallizing from the system Ni(II)-en-[Ni(CN)4]2−-H2O

Seven complex compounds exhibiting the compositions Ni(en)₃Ni(CN)₄·H₂O (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄·2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2.5H₂O (VI) and-Ni(en)₂Ni(CN)₄ (VII) were prepared from the system Ni-en-[Ni(CN)₄]^2–-H₂O. These compounds were examined by the methods of infrared spectroscopy, X-ray powder diffractometry, UV-VIS reflectance spectroscopy, and also by the measurement of magnetic moments. The thermal stability, the stoichiometry of thermal decomposition and the mutual transformations were investigated with a derivatograph. The reactions proceeding according to the following schemes were observed if the system was heated to appropriate temperature: (I)(II)(III)(V)(IV) and (VI)(VII)(III)(V)(IV) Process (VII)(III) represents isomerization. The reversibility of the process (V)(IV) is due to the high hygroscopicity of the anhydrous complex. The changes in structure in the course of the individual processes are discussed.

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Zusammenfassung Aus einem System Ni-en-[Ni(CN)₄]^2–-H₂O wurden sieben Komplexe der Formeln Ni(en)₃Ni(CN)₄·H₂O (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄·2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2.5H₂O (VI) und-Ni(en)₂Ni(CN)₄ (VII) hergestellt. Diese Verbindungen wurden mittels IR-Spektroskopie, Röntgenpulverdiffraktometrie, UV-Reflexionsspektroskopie und durch Messungen des magnetischen Momentes untersucht. Die Wärmestabilität, die Stöchiometrie des thermischen Zerfalles und die gegenseitigen Umwandlungen wurden mittels eines Derivatographen untersucht. Wird das System auf geeignete Temperaturen erhitzt, kann der Reaktionsverlauf durch folgendes Schema dargestellt werden: (I)(II)(III)(V)(IV) und (VI)(VII)(III)(V)(IV).Der Prozeß (VII)(III) verkörpert eine Isomerisierung. Die Umkehrbarkeit von Prozeß (V)(IV) ist auf die ausgeprägten Hygroskopieeigenschaften des wasserfreien Komplexes zurückzuführen. Es werden die im Ablaufe der einzelnen Prozesse vorgehenden Strukturveränderungen besprochen.

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Ni- -[No(N)]² -₂ Ni(en)₃Ni(CN)₄ · ₂ (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄-2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2,5H₂O (VI) -Ni(en)₂Ni(CN)₄ (VII). , , - , . , . (I)(II)(III)(V)(IV) (VI)(VII)(III)(V)(IV). (VII)(III) . (V)(IV) . .

     

Steroid glycosides XXI. The structure of polygonatoside E′ and protopolygonatoside E′ from the leaves ofPolygonatum latifolium

Summary The chemical structures of two new steroid glycosides from the leaves ofPolygonatum latifolium have been shown. Polygonatoside E is 3-[0--D-glucopyranosyl-(1 3)-0--D-glucopyranosyl-(1 4)-0--d-galactopyranosyl-(1 3)--D-glucopyranosyloxy]-(25R)-spirost-5-ene, and protopolygonatoside E is 26--D-galactopyranosyl-(1 3)--D-glucopyranosyloxy]-(25R)-furost-5-en-22-ol.Institute of Chemistry, Academy of Sciences of the Moldavian SSR, Kishenev. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 350–354, May–June, 1978.     

γ-Pyrone derivatives

3, 5-Dibromocomanic acid (3, 5-dibromo- -pyrone -2-carboxylic acid) VI and its ethyl ester, hitherto not described in the literature, are synthesized by the following route: diethyl acetonedioxalate (I) diethyl dibromochelidonate (III) (mono) ethyl dibromochelidonate (IV) diethyl 3, 5-dibromocomanate (V) VI. Direct bromination of diethyl bromochelidonate gives the ester III. 6-Bromocomenic acid and its ethyl ester are prepared, as well as 2-bromo-3-hydroxy - -pyrone. Bromocomanic acid (x-bromo--pyrone-2-carboxylic acid) XVI is synthesized by the following route: I (mono) ethyl chelidonate ethyl comanate comanic acid XVI. Oxonium salts are obtained: acid sulfates of comanic acid and ethyl comanate.For Part VII [1].     

Structure of psolusoside a — The main triterpene glycoside from the holothurianPsolus fabricii

The structure of psolusoside A — the main component of the glycosidic fraction from the holothurianPsolus fabricii Duben et Koren — has been determined as 3-0-[0-(3-0-methyl-6-0-sulfato--D-glucopyranosyl)-(1 3)-0-(6-0-sulfato--D-glucopyranosyl)-(1 4)-0--D-quinovopyranosyl-(1 2)--D-xylopyranosyloxy]holosta-9(11),25-dien-16-one.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 212–217, March–April, 1985.     

Zu einigen Besonderheiten des thermischen Zerfalls von Ni(II)-Komplexen mit dreizähnigen Schiffschen Basen

Zusammenfassung Es wurde eine Reihe von Komplexen des zweiwertigen Nickels mit den Schiffbasen H₂L,H₂L der Zusammensetzung NiL·ROH(R=Me, Et, Pr, i-Pr)und NiL ·ROH (R=Me, Et, Pr, i-Pr, Bu) hergestellt und deren thermischer Zerfall untersucht. Es wurde festgestellt, dass bei den Addukten NiL·ROH der Zerfall unter Abspaltung des Alkohols (Zwischenprodukt NiL) verläuft, während bei NiL·ROH sofort nach der Abspaltung des Alkohols zur Massenzunahme auf TG-Kurve durch Oxidation des Stoffes kommt. Das Plateau, das dem Zwischenprodukt NiL entspricht, ist hier nur in der Ineratmosphäre erhaltbar. Es wurden auch die Aktivierungsenergien für die Abspaltung des Alkohols berechnet.

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Ni(II) Schiff base complexes of compositions NiL ROH (R=Me, Et, Pr, i-Pr) and NiL·ROH (R=Me, Et, Pr, i-Pr, Bu) were prepared and investigated by methods of thermal analysis. The thermal decomposition of NiL·ROH led to NiL (plateau in TG curve), whereas NiL·ROH underwent a similar decomposition only in an inert atmosphere (N₂); thermal decomposition in air involved alcohol fragmentation, followed by a mass increase due to oxidation by atmospheric oxygen. The activation energy of alcohol fragmentation was calculated.

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NiL · ROH (R=-, -, - ) NiL-ROH (R=-, -, -, -, ). , NiL ] NiL — . , . .

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Wir möchten uns sehr herzlich bei Doz. RNDr. E. Jóna, CSc. und RNDr. I. Horváth, CSc. für die Messungen in der Stickstoffatmosphäre in SAV Bratislava bedanken.     

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.

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

     

Two new triterpene glycosides from the holothurian Duasmodactyla kurilensis

Two new glycosides have been isolated from the total triterpene glycosides of the holothurianDuasmodactyla kurilensis: kurilosides A (III) and C (IV). It has been established that (III) is 16-acetoxy-3-{[O--D-glucopyranosyl-(1 4)-O--D-quinovopyranosyl-(1 2)]-[O-(3-O-methyl--D-glucopyranosyl)-(1 3)-O-(6-O-(sodium sulfato)--D-glucopyranosyl)-(1 4)]--D-xylopyranosyloxy}-4,4,14-trimethylpregen-9(11)-en-20-one, while the minor glycoside (IV) is 16-acetoxy-3-{O--D-quinovopyranosyl-(1 2)-[O-(3-O-methyl--D-glucopyranosyl-(1 3)-O-(6-O-(sodium sulfato)--D-glucopyranosyl)-(1 4)]--D-xylopyranosyloxy}-4,4,14-trimethylpregn-9(11)-en-20-one.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 221–226, March–April, 1991.     

Studies on the V?Ti?O system obtained by thermal decomposition of vanadyl and titanyl oxalates in argon atmosphere

The V–Ti–O system as a product of thermal decomposition of vanadyl and titanyl oxalates at 873 and 1173 K in argon atmosphere was studied by X-ray diffraction and infrared spectroscopy. The results obtained, the analysis and surface measurement data suggest that a V³⁺–V⁴⁺–Ti⁴⁺–O solid solution is formed. Spectroscopic measurements reveal the presence of a V=O bond in the system obtained at 873 K.

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V–Ti–O, 873 1173 - . , , V⁺³–V⁺⁴–O . V=O , 873 .

     

Kinetics of ammonia decomposition of polycrystalline rhodium at pressures between 0.013 and 103 kPa

The rates of ammonia decomposition on polycrystalline Rh wires between 600 and 1800 K and at pressures between 13.3 Pa and 103 kPa were measured and fitted with a Langmuir-Hinshelwood unimolecular reaction rate expression. At high temperatures and pressures the reaction seems to be mass transfer controlled.

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Rh 600–1800 K 13,3 –103 . , -. .

     

Calculation of thermal effects in DTA

By considering that the temperature of the end of the thermal effect and the return of the thermal curve to the baseline do not coincide new calculation methods for the thermal effect become possible. Both the integral value of the thermal effect and its distribution over temperature may be calculated by processing only that part of the DTA curve which corresponds to the temperature interval of the transformation.It is demonstrated on the examples of non-variant transformation and transformation with an even distribution of the thermal effect over the temperature interval of the transformation that, under certain assumptions, the values of the thermal effect calculated by the suggested method and by the area of the peak are identical.

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Zusammenfassung Bei Berücksichtigung, daß die Temperatur des Endes des thermischen Effekts und die Rückkehr der thermischen Kurve zur Grundlinie nicht zusammenfallen, werden neue Methoden zur Berechnung des thermischen erschlossen. Sowohl der Integralwert des thermischen Effekts, als auch seine Verteilung in dem Temperaturbereich können durch Behandlung ausschließlich desjenigen Teils der DTA-Kurve berechnet werden, welcher dem Temperaturbereich der Umwandlung entspricht.Anhand von Beispielen der nicht-varianten Transformation und der Transformation mit gleichmäßiger Verteilung des thermischen Effekts im Temperaturbereich der Umwandlung wurde gezeigt, daß — unter gewissen Voraussetzungen — die Werte des durch die vorgeschlagene Methode und des aus der Peakfläche berechneten thermischen Effekts identisch sind.

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Résumé En considérant le fait que la température de la fin de l'effet thermique et le retour à la ligne de base de la courbe ATD ne coïncident pas, on a développé de nouvelles méthodes du calcul de l'effet thermique. La valeur intégrale de l'effet thermique ainsi que sa distribution dans l'intervalle de températures peuvent être calculées en ne considérant que la partie de la courbe ATD qui correspond à l'intervalle de température de la transformation.A l'aide d'exemples de transformations invariantes et de transformations à distribution uniforme de l'effet thermique dans l'intervalle de températures de la transformation, on a montré qu'avec certaines hypothèses, les valeurs de l'effet thermique calculées par la méthode proposée et à partir des surfaces des pics, sont identiques.

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. , -, . , , .

     

Steroid saponins and sapogenins ofAllium. XVII. The structure of karatavioside C

A new furostanol glycoside — karatavioside C (I) has been isolated from a methanolic extract of the inflorescences ofAllium karataviense Rgl. (family Liliaceae). By the complete acid hydrolysis, enzymatic hydrolysis, methylation, and reduction of compound (I), and also by the reduction of yuccagenin (II), the structure of the glycoside (I) has been established as 25(R)-furost-5-ene-2, 3, 22, 26-tetrao] 26-0--D-glucopyranoside 3-0-{[0--D-glucopyranosyl-(12)][0--D-xylopyranoside-(13)]-0--D-glucopyranosyl-(14)--D-galactopyranoside.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 355–359, May–June, 1980.     

A simple autonull-type servo-controlled electronic balance for thermogravimetric applications

A simple electronic autonull-type recording balance using a helical quartz spring is described. Deviation from the null position is detected by a pair of photoemissive cells. The error signal generated across the cells as a result of weight change is processed by a servo-system which, in turn, produces an electric current in the balancing coil proportional to the force required to restore the null position. This current, recorded as the potential drop across a standard resistor, is a direct measure of the weight change.The balance has good linear response and can record weight changes up to 150 mg. The performance of the balance was tested in a thermogravimetric set-up, by studying the decomposition in air of the oxalates of copper, nickel and magnesium. The decomposition of nickel oxalate was also studied in flowing hydrogen. The weighing accuracy of the balance, compared against a Mettler model H-15 single-pan balance, was found to be within±1.5%.

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Zusammenfassung Eine einfache elektronische registrierende Quartz-Spiralfeder Kompensationswaage wird beschrieben. Die Abweichung von der Nullposition wird durch zwei Photoemissionszellen angezeigt. Das infolge der Gewichtsänderung durch die Zellen erzeugte Fehlersignal wird durch ein Servosystem empfangen, das seinerseits in der Ausgleichsspirale einen elektrischen Strom erzeugt, der proportional zur für die Wiederherstellung der Null-position benötigten Kraft ist. Dieser Strom, der als Spannungsgefälle in einem Standardwiderstand registriert wird, ist eine direkte Maßzahl der Gewichtsänderung.Die Waage zeigt ein gutes lineares Verhalten und kann Gewichtsänderungen bis zu 150 mg registrieren. Die Leistung der Waage wurde in einer thermogravimetrischen Vorrichtung durch Untersuchungen der Zersetzung der Oxalate von Kupfer, Nickel und Magnesium in Luft geprüft. Die Zersetzung von Nickeloxalat wurde auch in strömendem Stickstoff untersucht. Die Meßgenauigkeit der Waage, vergleichen mit der Einschalenwaage Mettler H-15 wurde im Bereich von±1.5% gefunden.

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Résumé On décrit une balance électronique enregistreuse simple du type auto-zéro, à hélice de quartz. La déviation de la position zéro est décelée par une paire de cellules photoémissives. Le signal de déséquilibre décelé par les photocellules et résultant d'un changement de poids, est reçu par un système asservi qui, à son tour, produit un courant électrique dans la bobine de la balance, proportionnel à la force nécessaire pour rétablir la position zéro. Ce courant, enregistré comme chute de potentiel dans une résistance étalon, est une mesure directe du changement de poids.La balance donne une bonne réponse linéaire et peut enregistrer des changements de poids allant jusqu'à 150 mg. Ses caractéristiques ont été examinées dans un montage thermogravimétrique, en étudiant la décomposition dans l'air des oxalates de cuivre, nickel et magnésium. La décomposition de l'oxalate de nickel a aussi été étudiée sous courant d'hydrogène. L'exactitude de la balance, comparée à celle d'un modèle Mettler monoplateau (type H-15), coïncide à±1.5%.

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, . . , , -, , . , , . 150 . , . . -15 +1.5%.

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The authors wish to express their thanks to Mr. S. P. Sen, Manager. Catalyst Development and Production Department of Fertilizer (Planning and Development) India Limited, for his keen interest and valuable suggestions.     

Toluene disproportionation and coke formation over fluorided alumina and hydrogen-mordenite

Toluene transformation was investigated on a fluorided alumina and a protonic mordenite under hydrogen (0.8, 12 bar) and under nitrogen (12 bar). Hydrogen pressure considerably improves the catalytic stability of H-mordenite by inhibiting the formation of coke. Moreover, hydrogen eliminates part of the coke deposited by reaction under nitrogen, and regenerates the activity of the mordenite. On the contrary, hydrogen has no effect in the case of fluorided alumina. The particular behavior of the mordenite is attributed to its very strong acidity.

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(0,8, 12 ) (12 ). -, . , , , . , - . .

     

A rapid method for catalyst activity measurements by combination of pulse reactor, mass spectrometer and process computer

The combination of a pulse reactor attached directly (without a separation column) to a mass spectrometer/process computer system is described. To obtain a conversion/temperature diagram for the dehydration and dehydrogenation of 2-butanol less than one hour is required. Therefore, the method can be used for rapid characterization or comparison of the activities of various samples.

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, ( ) - . / 2- . .

     

Ein einfacher Zugang zu (R)-γ-Amino-β-hydroxybuttersäure (GABOB) aus natürlichem (2S, 4R)-4-Hydroxyprolin

The oxidative decarboxylation sequence (1a 2a 3a 4a 5a) affording -aminobutanoic acid (5a) is adapted to the synthesis of its hydroxy derivative5b. A facile high yield conversion of (2S, 4R)-4-hydroxyproline-methylester-hydrochloride (7) to (R)-GABOB (5b) on a preparative scale is reported with the hydroxypyrrolidone8 as the intermediate.

     

X-ray diffraction (powder), e.s.r. and other spectral studies oftris[methylenebis(diphenylphosphine oxide)]iron(III) perchlorate

Summary Bifunctional methylenebis(diphenylphosphine oxide) (mdpo) on reaction with iron(III) perchlorate forms the complex, [Fe(mdpo)₃](ClO₄)₃ · H₂O. This has been characterized through elemental analysis, i.r., far-i.r., u.v. and visible spectroscopy and by x-ray diffraction, magnetic moment, molar conductance and e.s.r. data. The e.s.r. spectrum consists of five lines with transitions from: ¦–5/2¦–3/2¦–3/2¦–1/2, ¦–1/2¦+1/2¦+1/2¦+3/2 and ¦+3/2¦+5/2 centred at a g-value of 2.00. On the basis of these studies, a chelated octahedral structure has been assigned to the cation, [Fe(mdpo)₃]³⁺.