Polyhydroxysteroids from the Far-Eastern starfishCtenodiscus crispatus

Four new polyhydroxysteroids, 5-cholesta-3,5,6,15,16,25,26-heptaol, 24-ethyl-5-cholesta-3,5,6,15,28,29-heptaol-29-sulfate, (22E)-24-methyl-5-cholest-22-ene-3,5,6,15,25,26-hexaol-26-sulfate, 24-propyl-5-cholesta-3,5,6,8,15,28,29-heptaol, and the known 5-cholesta-3,5,6,15,16,26-hexaol, have been isolated from the starfishCtenodiscus crispatus.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1821–1825, October, 1994.     

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.     

Indole derivatives. I.β-(3-indolyl) ketones

A number of -skatyl--substituted acetoacetic esters (ethyl, tert. -butyl, and benzyl) are prepared by treating gramine with sodium derivatives of -substituted acetoacetic esters. When ethyl -alkyl--skatylacetoacetates are heated with dilute alkali, they are split into indole and a substituted acetoacetic ester, while saponification with concentrated alcoholic alkali gives -substituted-(3-indolyl)propionic acids. 3-Skatyl-heptan-2-one can be obtained by pyrolysis of 3-skatyl-3-carbo-tert. -butoxyheptan-2-one, or by hydrogenolysis of 3-skatyl-3-carbobenzoxyheptan-2-one over a palladium catalyst. Alkylation of cycloheptanone and cyclohexanone enamines by gramine gives cyclic-(3-indolyl)ketones, viz., 2-skatylcyclopentanone and 2-skatylcyclohexanone.     

Titrimetrische Mikrobestimmung von Steroid-16α,17α-Diolen mit Blei(IV)-acetat

Zusammenfassung Eine neue maßanalytische Methode zur Bestimmung von 16, 17-Dihydroxysteroiden wurde beschrieben. Die Titration wird mit Blei(IV)-acetat-Maßlösungen (0,01-n bzw. 0,001-n) in einer Lösung von Kaliumacetat in 0,25-n Essigsäure durchgeführt. Die Endpunktermittlung erfolgt potentiometrisch. Das Äquivalentverhältnis beträgt 12. Die beschriebene Methode ist zur Bestimmung von Zehntelprozenten 16,17-Dihydroxysteroid als Verunreinigung in deren Acetoniden geeignet.

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Micro-titration of 16,17-Dihydroxy-steroids with standard lead tetraacetate solution

Summary A new volumetric method is described for the determination of 16,17-dihydroxy steroids. The titration is carried out using standard lead tetraacetate solution as the titrant (0.01N and 0.001N, resp.), while the solvent for the titration is the solution of potassium acetate in acetic acid (0.25N). The end point i s determined potentiometrically. The equivalent ratio is 1 2. The described method enables the determination of 0.1% of 16,17-dihydroxy steroid impurities in their acetonide derivatives.

     

Deutung der K α-satelliten bei leichten Elementen

Zusammenfassung Ausgehend von der KL-Ionisation wurden die K -Satelliten(, , ₃, ₃, ₄) der Elemente Z=8 bis Z=12 den entsprechenden Übergängen zugeordnet. Die Berechnung der Übergänge wurde nach der Z-Dependence-Theorie bis einschließlich zweiter Näherung durchgeführt.

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Interpretation of the K -satellites of the light elements

Starting from the KL-ionisation the K -satellites(, , ₃, ₃, ₄) of the elements Z=8 to Z=12 have been assigned to the corresponding transitions. The transitions have been calculated by the Z-dependence-theory including the second approximation.

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Résumé Les satellites K (, , ₃,₃, ₄) des éléments Z= 8 à Z=12 ont été attribués aux transitions correspondantes à partir de l'ionisation KL. Les transitions ont été calculées par la théorie dépendant de Z en tenant compte de l'approximation seconde.

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Herrn Prof. Timm in dankbarer Würdigung der Hilfen, die die BASF für den Aufbau unserer theoretisch-chemischen Arbeitsgruppe geleistet hat, zum 60. Geburtstag gewidmet.

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Der Deutschen Forschungsgemeinschaft dankt D. H. für die finanzielle Unterstützung, die die Dunchführung dieser Arbeit wesentlich erleichterte.     

Zusammenhang zwischen den K α-Satelliten-Linien und den Röntgenübergängen vom Typ K 1 L 1→L 2 bei den Elementen Neon,Natrium, Magnesium,Aluminium und Silizium

Zusammenfassung Für die Elemente Neon, Natrium, Magnesium, Aluminium und Silizium werden mit einem quantenmechanischen Variationsverfahren unter Verwendung einer minimalen STF-Funktionenbasis Röntgenübergänge vom Typ K ¹L¹L² berechnet und den K -Satellit-Linien , , ₃, ₃ and ₄ zugeordnet.

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Relation between K -Satellits and X-ray-transitions of the type K ¹ L ¹L ² for Ne, Na, Mg, Al and Si

STF-Calculations are reported for X-ray-transitions of the type K ¹L¹L² for Ne, Na, Mg, Al and Si. It is shown that these transitions are correlated with the K -satellits , , ₃, ₃ and ₄.

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Die Wellenfunktionen können auf Anfrage zur Verfügung gestellt werden.     

Mechanism of the Low-Temperature Interaction of Hydrogen with α-Oxygen on FeZSM-5 Zeolite

The mechanism of a low-temperature reaction of hydrogen with the radical anion surface oxygen species (-oxygen, ) formed by decomposing N₂O over FeZSM-5 zeolite was studied using kinetic and isotope techniques. It was found that the reaction is of first order with respect to hydrogen and the rate of the reaction is proportional to the concentration of . The activation energy of the reaction, which was measured for ₂ or D₂ over a temperature range from +20 to –;;100°, is equal to 3.2 or 5.3 kcal/mol, respectively. The reaction occurs with a considerable kinetic isotope effect (k /k _D), which varies over the range of 3.4–;;41 depending on the temperature. This fact indicates that the rate-limiting step of the reaction includes the dissociation of the hydrogen molecule. The temperature dependence of the isotope effect gave a value of 2.1 kcal/mol, which is close to the difference between the zero bond energies in the molecules of ₂ and D₂; this fact suggests that a tunnel effect does not significantly contribute to the reaction. The dissociative mechanism is consistent with data obtained by in situ IR spectroscopy. The interaction of hydrogen with -oxygen is accompanied by the formation of new hydroxyl groups (absorption bands at 3635 and 3674 cm^–;;1) at the surface of the zeolite. The identification of these groups was supported by an isotope shift either on the replacement of ₂ by D₂ or on the replacement of ¹⁶ by ¹⁸. The stoichiometric ratio ₂ : is consistent with the previously drawn conclusion on the paired arrangement of -sites.     

The identification of small amounts of sugars by means of X-ray diffraction patterns

Summary The identification of small amounts of sugars by their X-ray powder diagrams is suggested as a most simple and practical method in routine analysis.It is especially valuable in working with minute amounts of material, and has proved very useful for the final identification of chromatographically-separated sugars.The characteristics of the powder diagrams of a number of monosaccharides of special interest to the physiological chemist are reported in detail. The substances thus investigated are- and-D-glucose and-glucose monohydrate,- and-D-galactose,- and-D-mannose,D-fructose,D-glucuronolactone,- and-D-glucosamine hydrochloride,- and-D-galactosamine (chondrosamine) hydrochloride,-L-fucose, andD-ribose. For various reasons arabinose, lyxose, and xylose have also been included.It is clear from the powder diagrams of the galactoses that the crystalstructure earlier ascribed to-galactose is that of-galactose.A single-crystal study of-glucosamine hydrochloride was carried out by theWeissenberg technique. The crystal-dimensions obtained agree with those earlier found byCox et al^{5, 7}.The optical rotation of chondrosamine hydrochloride was found to be [] _D ^20° = - 135° - 93° - 39°, the first value being considerably higher than that given for the-form byLevene. A method for the preparation of-mannose is described.

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Zusammenfassung Die Identifizierung kleiner Mengen verschiedener Zuckerarten mit Hilfe ihrer Röntgen-Pulverdiagramme wird als einfache und praktische Routinemethode vorgeschlagen.Diese Methode ist besonders wertvoll, wenn nur kleine Substanzmengen zur Verfügung stehen, und hat sich für die endgültige Identifizierung von chromatographisch getrennten Zuckern als sehr geeignet erwiesen.Die Einzelheiten der Pulverdiagramme folgender physiologisch-chemisch bedeutungsvoller Monosaccharide werden mitgeteilt:- und-D-Glukose und Glukosehydrat,- und-D-Galaktose,- und-D-Mannose,D-Fruktose,D-Glukuronolakton,- und-D-Glukosaminhydrochlorid,- und-D-Galaktosamin-(Chondrosamin)-hydrochlorid,-L-Fukose, dieD-Pentosen Arabinose, Lyxose, Ribose und Xylose.Aus den Pulverdiagrammen der Galaktosen geht deutlich hervor, daß die Krystallstruktur, die früher der-Galaktose zugeschrieben wurde, tatsächlich diejenige der-Form ist.Die Untersuchung eines Einzelkristalles von-Glukosaminhydrochlorid wurde nach derWeissenberg-Technik ausgeführt. Die erhaltenen Werte stimmen mit den früher vonCox und Mitarbeitern gefundenen überein.Die optische Drehung des Chondrosaminhydrochlorids wurde zu [] _D ^20° = + 135° + 93° + 39° gefunden. Der erstgenannte Wert ist größer als der entsprechende, vonLevene angegebene Drehungswert.Eine Methode zur Darstellung von-Mannose wird beschrieben.

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Résumé On propose une méthode de routine simple et pratique pour l'identification de petites quantités de divers sucres au moyen de leur diagramme de poudres aux rayons X. Cette méthode est particulièrement précieuse quand on n'a que de petites quantités de matière à sa disposition et elle s'est montrée très convenable pour l'identification finale de sucres séparés par chromatographie. Des particularités des diagrammes de poudres des monosaccharides suivants intéressent le chimiste physiologiste: et-D-glucose et hydrate de glucose, et-D-galactose, et-D-mannose, D-fructose,D-glucuronolactone, chlorhydrate d' et-D-glucosamine, chlorhydrate d' et-D-galactosamine (chondrosamine), l'-L-fucose, lesD-pentoses, l'arabinose, le lyxose, le ribose, le xylose. Des diagrammes de poudres des galactoses découle clairement le fait que la structure cristalline qui fut attribuée précédemment à l'-galactose est celle de la forme. L'expérience sur un cristal unique de chlorhydrate d'-glucosamine a été effectuée d'après la technique deWeissenberg. Les valeurs obtenues concordent avec celles trouvées précédemment parCox et ses collaborateurs. Le pouvoir rotatoire du chlorhydrate de chondrosamine a été trouvé égal à _D ²⁰ = + 135° + 93° + 39°. La première valeur est plus grande que celle donnée parLevene. On décrit une préparation de l'-mannose.

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With 3 figures.     

Einwirkung von Schwefel und Ammoniak auf Propiophenon,n-Butyrophenon und i-Butyrophenon

Zusammenfassung Bei der Einwirkung von Schwefel und Ammoniak auf Propiophenon,n-Butyrophenon undi-Butyrophenon entstehen die entsprechenden Thiazoline-(3), deren saure Hydrolyse zu -Mercaptopropiophenon, -Mercapto-n-butyrophenon bzw. -Mercapto-i-butyrophenon führt. Die Dehydrierung dieser -Mercaptoketone mit Schwefel zu Di- bzw. Trisulfiden wird beschrieben. Die Kondensation der -Mercaptoketone mit Ammoniak und einer Oxokomponente führt zu neuen Thiazolinen-(3), von denen die in 2- und 5-Stellung monosubstituierten Vertreter sich mittels Schwefel zu Thiazolen dehydrieren lassen.

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The interaction of sulfur and ammonia with propiophenone,n-butyrophenone andi-butyrophenone leads to the corresponding thiazolines-(3). On acid hydrolysis of the latter -mercaptopropiophenone, -mercapto-n-butyrophenone and -mercapto-i-butyrophenone respectively are formed. The dehydrogenation of these -mercaptoketones with sulfur to di- and trisulfides respectively is described. The condensation of the -mercaptoketones with ammonia and oxo-components yields new thiazolines-(3) of which the 2- and 5-monosubstituted compounds can be dehydrogenated to thiazols with elementary sulfur.

     

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     

Novel dioximato-bridged chromium(III)-copper(II)-chromium(III) trinuclear complexes with ferromagnetic exchange interactions

Summary Two new dioximato-bridged trinuclear Cr^II-Cu^II-Cr^III complexes, [Cr(salen)-Cu(-BD)₂-Cr(salen)] (1) and [Cr(salen)-Cu(-FD)₂-Cr(salen)]-H₂O (2), have been prepared and characterized [salen^2– = N,N-ethylene- bis (salicylideneiminate), (-BD)^2– = -benzyldioximato and (-FD)^2– = -furildioximato]. Magnetic susceptibility measurements in the 4.2–300 K range demonstrated the operation of a ferromagnetic interaction between the adjacent Cr^III and Cu^II ions through oximato bridges in both (1) and (2). Based on spin Hamiltonians =–2J(₁₂+₂₃)(S₁=S₃=3/2,S₂=1/2) the exchange integrals (J) were evaluated as 3.19 and 5.38 cm^–1 for (1) and (2), respectively.     

Synthesis of α-alkyl- and α,α-dialkyl-β-phenyltryptamines

A new method was developed for the synthesis of -alkyl- and ,-dialkyl--phenyltryptamines based on alkylation of nitroalkanes with -phenyl-nor-gramine.     

Triterpene glycosides ofHedera canariensis. I. Structures of glycosides L-A,L-B1, L-B2, L-C,L-D,L-E1 1, L-G1, L-G2, L-G3, L-G4, L-H1, L-H2, AND L-I1 from the leaves ofHedera canariensis

From the leaves of Algerian ivyHedera canariensis Willd. (fam. Aralaceae) we have isolated 13 triterpene glycosides: the 3-O--L-arabinopyranosides of oleanolic acid (A), of echinocystic acid (B₁), and of hederagenin (B₂); the 3-O-[O--L-rhamnopyranosyl-(2)--L-arabinopyranoside]s of oleanolic acid (C), of echinocystic acid (D), and of hederagenin (E₁); the 3-O--L-rhamnopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--gentiobioside of hederagenin (G₁); the 3-O-[O--L-rhamnopyranosyl-(12)--L-arabinopyranoside] 28-O--gentiobioside of hederagenin (G3); the 3-O-[O--L-rhamnopyranosyl-(12)--L-arabinopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--gentiobioside]s of oleanolic acid (G₂), of echinocystic acid (H₁), and of hederagenin (H₂); the 3-O-[O--L-rhanmopyranosyl-(12)--D-glucopyranoside] 28-O-(O--L-rhamno-pyranosyl-(14)--gentiobioside] of hederagenin (H₂); and the 3-O-(O--L-rhamnopyranosyl-(12)-O-gentiobiosyl)-O-(14)--L-rhamnopyranosyl-(12)-a-L-arabinopyranoside] of hederagenin (G₄). The structures of the substances isolated have been established on the basis of chemical transformations and¹³C NMR spectroscopy.Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 377–383, May–June, 1996. Original article submitted December 3, 1995.     

On the electrophoretic mobility and zeta potential of montmorillonite in non-aqueous media

Experimental results on the electrophoretic velocity and mobility of Ca-montmorillonite in 2-propanol are reported. The variation of the electrophoretic velocity with the externally applied electric field and the particle size range, at constant volume fraction and temperature, is considered. Given the difficulties for determining the types and concentrations of ions present in these liquid media, two methods are discussed for the estimation of the double layer thickness and hence the product, necessary for the determination of the zeta potential () of the interface. Although both methods of calculation yield different values of, the results for the zeta potential are very similar in the regions of and characteristic of our systems. The application to the experimental data of three theoretical relations between electrophoretic mobility and zeta potential is also discussed.     

Simultaneous vibrational relaxation and thermal dissociation of diatomic molecules

A model of a truncated harmonic oscillator with equidistant levels and one-quantum transitions is applied. The balance equations for O₂ have been solved numerically with 26 levels, with the transition probabilities taken as P _k,k +1k exp (k) P ₁₀, in which k is the number of the level and is an adjustable parameter that takes account of the anharmonicity. A Boltzmann distribution is obtained up to level 19 with =0, but for 0 there are deviations from that distribution in lower levels. Levels with k=1, 2, 3 are populated with relaxation times substantially less than the relaxation time for the vibrational energy. Dissociation depletes levels with k 19.     

Über halogen- und stickstoffhaltige Derivate aliphatischer Carbonsäuren, 6. Mitt.: Über die Gewinnung von α-Oximino- und α-Nitrodicarbonsäureestern

Zusammenfassung Aus den entsprechenden -Bromestern werden durch Umsetzung mit Natriumnitrit die -Oximinodicarbonsäuredimethylester C₇ und C₉ und der , -Dioximinoazelainsäuredimethylester erhalten. -Methyladipinsäure wird zum Gemisch aus -Bromund -Bromester umgesetzt. Mit Natriumnitrit wird -Nitro-und -Oximino--methyladipinsäuredimethylester erhalten.

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The -oximino dicarboxylic dimethyl esters of C₇ and C₉ and the , -dioximino azelaic acid dimethyl ester are received from the corresponding -bromo esters by reaction with sodium nitrite. -Methyladipic acid is reacted with bromine to a mixture of the -bromo and -bromo ester. Reaction with sodium nitrite gives the -nitro ester and the -oximino ester of -methyl adipic acid.

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5. Mitt.:H. Reinheckel, Mh. Chem.98, 1217 (1967).     

Synthesis of pyrimidyl-N1-α-amino acids

-(5-Fluoro-N₁-uracilyl)--alanine, -(5-bromo-N₁-uracilyl)--alanine, -(5-chloro-N₁-uracilyl)--alanine, -(N₁-thyminyl)--alanine, -(N₁-cytosinyl)--alanine, -(2-oxo-4-carboxymethylamino-1, 2-dihydro-N₁-pyrimidyl)--alanine, -(N₁-uracilyl)--aminobutyric acid, -(N₁-thyminyl)--aminobutyric acid, and -(N₁-cytosinyl)--aminobutyric acid were synthesized by the reactions involving the cyanohydrin synthesis and other transformations. In addition, a number of substituted N₁-pyrimidylacetaldehydes and N₁pyrimidylpropionaldehydes and their diethylacetals were synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 530–534, April, 1971.     

Analogs of pyrimidine nucleosides

N₁-(-Tetrahydrofuranyl)- and N₁-(-tetrahydropyranyl)uracils and the corresponding 6-azauracils have been obtained by the condensation of bistrimethylsilyl derivatives of uracils and 6-azauracils with-chlorotetrahydrofuran and-chlorotetrahydropyran. The superiority of the silyl method over the mercury method used previously has been demonstrated.For part III, see [9].     

On the maximum reaction rate and inflexion points on the DTG curve

The authors present some theoretical considerations concerning the influence of the form of the conversion functionf() on the values of the degree of conversion corresponding to the maximum value of the reaction rate (_max) as well as on the inflexion points (_inf) of the DTG curve. The obtained equations are characterized by a general validity no matter the form off().

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Zusammenfassung Es werden einige theoretische Überlegungen bezüglich des Einflusses der Form der Konversionsfunktionf() auf die Werte der Konversionsrate bei maximalen Reaktionsgeschwindigkeiten (_max) sowie auf Inflexionspunkte () der DTG-Kurve angestellt. Die erhaltenen Gleichungen sind unabhängig von der Form vonf() durch eine all-gemeine Gültigkeit charakterisiert.