Steroid compounds from ophiuroids. I. New steroid sulfate from Ophiura sarsi

The sulfate of a steroid polyol has been isolated from the Far Eastern ophiuroidOphiura sarsi, and its structure has been established by chemical and spectral methods as cholest-5-ene-3,4,21-diol 3-(sodium sulfate). No steroid compounds of such structure from ophiuroids have been described previously.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 375–379, May–June, 1988.     

Application of the vapor phase supporting (VPS) method for preparing SnO2/SiO2 catalysts

Supported SnO₂/SiO₂ catalysts have been prepared by the reaction of the surface hydroxy groups of silica gel and gas phase tin chloride (PS method). The catalytic properties have been examined in the reaction of 2-propanol to show the effect of VPS cycles on the amount and nature of the active sites.

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SnO₂/SiO₂ . 2- VPS .

     

Novel type of oscillatory chemical reactions

Chemical oscillations occur during the uncatalyzed oxidation of a number of phenol and aniline derivatives by acidic bromate.

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.

     

Ausbrennen von Kohlenstoffhaltigen,in den Ziegelrohstoff Eingepressten Stoffen

Zusammenfassung Die Kinetik der Ausbrennung organischer Stoffe im Ziegelscherben wird verfolgt und erläutert. Die Möglichkeiten der Beeinflussung des energetischen Aufwandes unter Nutzung moderner analytischer Methoden sind festzustellen. Bei einem diffusen Ausbrennen ist die Dichte und Durchlässigkeit des Scherbens massgebend. Praktische Anwendungsmöglichkeiten verschiedener auszubrennender Stoffe in unterschiedlichen Rohstoffen der Ziegelindustrie.

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The kinetics of burn-out of organic materials in bricks has been followed and explained. It is to establish that using new analytical methods the energy consumption can be influenced. The diffuse burn-out is determined by the density and permeability of bricks. There is a possibility for practical use of the results in the brick-industry with the different compounds to be burnt out from various raw materials.

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Basic condensation of triphenylsilane. II. Kinetics in anhydrous isopropanol and influence of silanol

Condensation of triphenylsilane with isopropanol in presence of isopropoxide has been studied in anhydrous medium and the activation parameters have been measured. Dehydration of the medium has been obtained by means of a pre-reaction of triphenylsilane with the residual water in the solvent. In this medium the reaction is extremely slow, moreover, it is inhibited by silanol whose effect would lower the actual catalyst concentration.

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. . , .

     

1,4-bis(4′-hydroxy-1′,2′,5′-trimethyl-4-piperidyl)-1,3-butadiyne and its derivatives

1.4-Bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)-1.3-butadiyne has been synthesized from the individual isomers of 4-ethynyl-1,2,5-trimethyl-4-piperidol. Hydrogenation, bromination, and cleavage have given, respectively, 1,4-bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)butane, 1,4-bis(4-nydroxy-1,2,5-trimethyl-4-piperidyl)-1,2,3,4-tetrabromo-1, 3-butadiene, and 4-(1,3-butadiynyl)-1,2,5-trimethyl-4-piperidol.     

Steroids of the furostan and spirostan series from Nolina microcarpa II. structures of nolinospiroside D and nolinofurosides D, E, and F

Proofs are given of the structures of two new glycosides of the furostan series isolated from the leaves of the plantNolina microscarpa S. Wats. (family Dracaenaceae). Nolinofuroside D is (25S)-furost-5-ene-1,3,22,26-tetraol 1-O--D-galactopyranoside 26-O--D-glucopyranoside (I), and nolinofuroside F is (25S)-furost-5-ene-1,3,22,26-tetraol 1-O--D-fucopyranoside 26-O--D-glucopyranoside 3-O--L-rhamnopyranoside (VII). The latter was characterized as its 22-O-methyl ether (VIII). Nolinofuroside E (IV) has the structure of (25S)-furost-5-ene-1,3,22,26-tetraol 26-O--glucopyranoside 1-O-[O--L-rhamnopyranosyl-(12)--D-fucopyranoside], which followed from the structure of the fermentation product (VI). The products of the fermentation of the above-named compounds were present in the plant in only trace amounts. Only one of them — nolinospiroside D (III) — has not been described previously. This monoside of the spirostan series is (25S)-spirost-5-ene-1,3-diol 1-O--D-galactopyranoside.M. V. Frunze Simferopol' State University. Institute of Chemistry of Plant Substances, Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 678–686, September–October, 1991.     

Hexadiene formation during decomposition of 2-propanol over Ca?P?O catalysts

Hexadiene formation from 2-propanol was investigated in view of acid-base properties of Ca–P–O catalysts with the Ca/P atomic ratio varying from 1.5 to 5.0. The catalytic activity in hexadiene formation increased up to a maximum at Ca/P=2.0, having almost the same amount of weak acidic sites as weak basic sites, and decreased with futher increase in Ca/P ratio.

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2- - Ca–P–O Ca/P, 1,5 5,0. , Ca/P=2, , Ca/P.

     

Thermal studies on some complexes of Pd(II)

The formulae suggested for a series of complexes of Pd(II) with various amino acids have been verified by thermal methods using a derivatograph. A correlation of the obtained kinetic parameters with the structures suggested by electronic and IR spectra of the substances has been attempted.

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Zusammenfassung Es wurden Formeln für eine Serie von Komplexverbindungen des Pd(II) mit verschiedenen Aminosäuren vorgeschlagen und thermogravimetrisch bewiesen. Die Übereinstimmung zwischen den erhaltenen kinetischen Parametern und den durch ERS und Infrarotspektroskopie angedeuteten Strukturen wurde geprüft.

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Résumé On a vérifié par thermogravimétrie des formules brutes proposées pour les combinaisons complexes du Pd(II) avec divers acides aminés. On a examiné la correlation entre les paramètres cynétiques obtenus et les structures déduites des spectres IR et electroniques.

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ë , Pd(II) . , , .

     

Reaction of triphenyl phosphite ozonide with thioacetals

Kinetic regularities in the reaction of triphenyl phosphite ozonide with several thioacetals in CH₂Cl₂ solution at –15°C have been studied. The consumption rate of ozonides is described by the kinetic equation W=k₀[(C₆H₅O)₃P·O₃]+k₁[(C₆H₅O)₃P·O₃][R₁R₂C(SR₃)₂] Rate constants k₀ and k₁ for the thioacetals: (CH₃H₇S)₂CH₂, (C₆H₅S)₂CH₂, (C₆H₅CH₂S)₂CH, (n=C₁₂H₂₅–S)₂CH₂, (C₃H₇S)₂C(H)CH₃, (C₃H₇S)₂C(H)C₆H₅, (C₃H₇S)₂C(CH₃)C₆H₅ and (C₃H₇S)₂C(H)C₁₀H₉, increases with increasing the electron-donating power of subtituents R_i.

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CH₂Cl₂ –15°C. : W=k₀[(C₆H₅O)₃P·O₃]+k₁[(C₆H₅O)₃P·O₃][R₁R₂C(SR₃)₂] k₀ k₁ (C₃H₇S)₂CH₂, (C₆H₅S)₂CH₂, (C₆H₅CH₂S)₂CH₂, (n-C₁₂H₂₅S)₂CH₂, (C₃H₇S)₂C(H)CH₃, (C₃H₇S)₂C(H)C₆H₅, (C₃H₇S)₂C(CH₃)C₆H₅, (C₃H₇S)₂C(H)C₁₀H₉. .

     

Veränderung des thermischen Verhaltens von Kaolinit durch mechanische Aktivierung

Zusammenfassung Es ist bekannt, daß die Eigenschaften von Kaolinit nicht nur durch eine Kalzinierung oberhalb 600 °C, sondern auch durch intensive mechanische Beanspruchung stark verändert werden können. Die durch eine Intensivmahlung erzeugte Reaktivitätssteigerung kann durch eine Verbesserung der Säurelösbarkeit des Al₂O₃-Anteiles, das veränderte thermische Verhalten und strukturelle Veränderungen gekennzeichnet werden. In der vorliegenden Arbeit geht es um einen Beitrag zur methodischen Aufklärung der strukturellen und thermischen Veränderungen von Kaolinit, insbesondere durch Einsatz thermoanalytischer und IR-spektroskopischer Methoden. Als intensives Zerkleinerungsaggregat wurde eine Scheibenschwingmühle eingesetzt.

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It is already known that the properties of kaolinite can be changed substantially not only by calcination above 600° but also by intensive mechanical stress.A reactivity increase induced by intensive grinding can be characterized by an increase of acid solubility of the Al₂O₃ content, by changed thermal behaviour and by structural changes. The paper presented contributes to the methodic explanation of structural and thermal changes of kaolinite, especially by the use of thermoanalytical and IR spectroscopic methods. The intensive grinding was performed in a vibration-disc mill.

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Résumé Il est déjà connu que les propriétés de la kaolinite peuvent être profondément modifiées non seulement par calcination au-dessus de 600 °C, mais aussi par contrainte mécanique intense.Une augmentation de la réactivité induite par broyage intense peut être caractérisée par une augmentation de la teneur en Al₂O₃ déterminée par solubilité en milieu acide, par le changement du comportement thermique et par des modifications structurales. Le présent article contribue à l'explication méthodique des changements structuraux et thermiques de la kaolinite, spécialement à l'aide des méthodes d'analyse thermique et de spectroscopie infrarouge. Le broyage intense a été effectué dans un broyeur à disques vibrants.

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, 600°, . l₂₃ , . . .

     

Triterpene Glycosides of Astragalus and Their Genins. LXI. Occurrence of Cycloartane 6-O-Monodesmosides

Cyclosiversigenin 6-O--L-rhamnopyranoside and 6-O--D-glucopyranoside were isolated fromAstragalus coluteocarpusBoiss. (Leguminosae) andAstragalus dissectusB. Fedtsch. et N. Ivanova, respectively. Cyclosiversigenin 5-O--L-rhamnopyranoside was shown to be an artifact forAstragalus coluteocarpus.Thus, the cyclosiversigenin 6-O--D-glucopyranoside that was isolated from certainAstragalusspecies is hypothesized also to be an artifact. Glycosylation of the 6 -hydroxyl group of cycloartanes by D-glucose and D-xylose, in contrast with other substituents, does not change the low-field position of the PMR signal of the 4-CH ₃ group (1.65 2.01 ppm) that is caused by the influence of deuteropyridine directly on the 6 -hydroxyl. Obviously one of the hydroxyls of the -D-glucopyranoside or -D-xylopyranoside residues has the same effect in this instance.     

Effects of tempering time and tempering temperature of caustic mercerization on the spectral and electrical properties of Egyptian cotton fibres

Several samples of Egyptian cotton fabric strips were subjected to various caustic mercerization conditions, varying in temperature and time. On these samples extensive measurements were undertaken, comprising X-ray diffraction, IR absorption spectra and the temperature-dependence of DC-electric conductivity.The phase constitution, % crystallinity, IR band assignment, activation energies for conduction and energy gap were evaluated as a function of caustic mercerization. The results obtained were correlated and discussed in detail, leading to valuable information of use in the cotton fabric strip industries.

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Zusammenfassung Verschiedene Proben von ägyptischen Baumwollstreifen wurden unter verschiedenen Bedingungen (Temperatur, Zeit) einer Laugung unterworfen. Die gelaugten Proben wurden eingehend durch Röntgendiffraktometrie, IR-Absorptionsspektroskopie und Messungen der Temperaturabhängigkeit der elektrischen Gleichstromleitfähigkeit untersucht. Phasenstruktur, Kristallinität, Zuordnung der Banden, Aktivierungsenergien für die Leitfähigkeit und verbotene Bänder wurden in Abhängigkeit von der Laugung ermittelt. Die erhaltenen Ergebnisse wurden miteinander verglichen und in Einzelheiten diskutiert, wobei für die Baumwollverarbeitungsindustrie wertvolle und empfehlenswerte Informationen erhalten wurden.

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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) - , . , .

     

Catalytic properties of plantinized polycyanogens

The effect of various inorganic polymers on the catalytic activity and selectivity of platinum in the hydrogenation of 4-chloronitrobenzene and dinitrotoluene has been studied. Platinized iron-containing polycyanogens are less active but more selective catalysts for the hydrogenation of 4-chloronitrobenzene than Pt/C or Pt/BaSO₄.

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4- . , , , 4-, Pt/C Pt/BaSO₄.

     

Ligand exchange between bis-acetylacetonato cobalt(II) and organotin compounds SnR2Cl2 (R=Ph, Et), II. Mechanism of ligand exchange between acetylacetonate complexes of Co(II)

Ligand exchange between the compounds Co(AA)₂Py₂ and Co(AA)Clpy_x (x=1 or 3) formed in the, system, CO(AA)₂–SnR₂Cl₂(R=Ph, Et) in chloroform with pyridine has been established to be catalyzed by SnR₂Cl₂. An interpretation of the catalytic action of SnR₂Cl₂ is suggested.

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, Co(AA₂py₂ Co(AA)Clpy_x (x=1 3) (Co(AA)₂–SnR₂Cl₂ (R=Ph, Et) , SnR₂Cl₂. SnR₂Cl₂.

     

Determination of the absolute configuration of carbohydrate components of flavonol glycosides of the chestnut

Conclusions On the basis of the rates of their acid hydrolysis, their optical activities, and their IR spectra, it has been established that the glycosides ofAesculus hippocastanum L. are (SK-1) 3--L-arabofuranosyloxy-5,7,4-trihydroxyflavone, (SK-2) 3--L-rhamnofuranosyloxy-5,7,4-trihydroxyflavone, (SK-3) 3--L-arabofuranosyloxy-5,7,3,4-tetrahydroxyflavone, and (SK-4) 3--L-rhamnofuranosyloxy-5,7,3,4-tetrahydroxyflavone.The glycoside SK-3 is identical with avicularin isolated from the leaves ofPsidium quajava [5]. The complete structures of the other three glycosides have been established for the first time.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 1, pp. 5–7, 1969     

Cardiac glycosides of Erysimum crepidifolium

Summary Four cardiac glycosides have been isolated from the leaves ofErysimum crepidifolium Rchb. Three of them have been identified as erysimin, erysimoside, and erycordin. The fourth glycoside, which has been named glucostrophalloside, is new, and it consists of strophanthidin 3-O-[4-O--D-glucopyranosyl--D-allomethylopyranoside].Khar'kov Scientific-Research Institute of Pharmaceutical Chemistry. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 611–614, September–October, 1974.     

Comparison of properties of supported organozirconium catalysts containing zirconium ions in different valence states

A comparison of the properties of supported zirconium catalysts containing zirconium ions in different valence states in ethylene polymerization shows that an increase in the proportion of active centers involving Zr(III) ions results in a decreasing molecular weight of the polymer. The catalyst activity is practically unchanged.

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, , . , , Zr(III) . .