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.     

Chemical transformations of 3-methyl ethers of 14β-hydroxy-8α, 9β-D-homoestrone and 14α-hydroxy-9β-D-homoestrone

Conclusions Starting with the 3-methyl ether of 14-hydroxy-8,9-D-homoestrone (I) we synthesized the 3-methyl ethers of 8, 14-D-homoestrone (V) and 8, 9-D-homoestrone (III).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2625–2627, November, 1972.     

Synthesis and transformations of the 20-substituted derivatives of 16α,17α-epoxy-5α-pregnane-3Β,21-diol-20-ones

A new and more effective sequence of reactions is proposed for the production of 16,17-isopropylidenedioxy-5-pregnane-3,21-diol-20-one. It uses methods previously unused for 5-H-steroids and involves 21-hydroxylation of 16,17-epoxy-5-pregnan-3-ol-20-one with diacetoxyiodobenzene and cis-opening of the obtained 21-hydroxy-16,17-epoxy-5-pregnane-3,21-diol-20-one by acetic acid in the presence of epoxycarbonylhydrazine, followed by condensation of the obtained product with acetone.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1185–1188, May, 1991.     

Triterpene glycosides ofCauliphyllum robustum. The structures of caulosides B and C

Summary Two triterpene glycosides — caulosides b and c — have been isolated from a methanolic extract of the leaves ofCaulophyllum robustum maxim. Cauloside b has been identified as hederagenin 3--L-rhamnopyranosyl-(12)--L-arabinopyranoside, while cauloside c has the structure of hederagenin 3-0--L-arabinopyranosyl(13)--L-pyranosyl-(12)--L-arabinopyranoside.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center of the Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 174–176, March–April, 1979.     

Membrane transport of dicarboxylic and α-hydroxy carboxylic acids induced by α-amino phosphonates

New -amino phosphonates containing different alkyl and aryl substituents at the -carbon atom were synthesized in high yields by the Kabachnik—Fields and Pudovik reactions. These compounds were studied as carriers of several -hydroxy carboxylic and dicarboxylic acids through liquid impregnated membranes. These -amino phosphonates studied are capable of molecular recognition of oxalic acid among structurally similar -hydroxy carboxylic and dicarboxylic acids. The efficiency and selectivity of mass transfer of oxalic acid increase with an increase in the lipophilicity of the -amino phosphonate.     

Formation of Supramolecular Polymers Constructed by Cyclodextrins with Cinnamamide

-Cyclodextrin having cinnamamide at 6- or 3-positions (6-CiNH--CD, 3-CiNH--CD) and -cyclodextrin with cinnamamide on 6-position (6-CiNH--CD) have been prepared. Supramolecular structures were formed in the solid state or aqueous solutions and characterized by measurements of NMR and vapor pressure osmometry (VPO). The results indicate that 6-CiNH--CD formed insoluble supramolecular polymers in the solid state, while 6-CiNH--CD and 3-CiNH--CD formed supramolecular complexes in aqueous solutions. 6-CiNH--CD was found to form a dimer in an aqueous solution. 3-CiNH--CD formed intermolecular complexes to give supramolecular polymers. The differences of the position of guest part on cyclodextrins caused to give a variety of supramolecular structures in aqueous solutions.     

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.     

Interaction of super-finely dispersed Al powders with water

Interaction of super-finely dispersed Al powders (SFDP) with water is characterized by the presence of a considerable section on the kinetic curves, where the conversion rate is maximum and its degree is as high as =0.5–0.7. It is suggested that the essential factor accounting for the conversion kinetics and the phase composition of its products is the self-heating of Al particles.

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() , , () 0,5–0,7. , .

     

New cardenolides from the leaves ofGomphocarpus fruticosus

Two new glycosides, gomphotin (1) and gomphotoxin (13), and also the known gomphoside (9) have been isolated from the leaves ofGomophocarpus fruticosus. Compounds (1) and (9) contain a 4,6-dideoxyhexosulose residue as the sugar component, and (13) a 6-deoxyhexosulose, which are attached to glycolic OH groups of the aglycons by 3-O-1,2-O-2 (9, 13) and 3-O-1,4-O-2 (1) acetal-ketal bonds. The structures of the new compounds are represented by the names (3-O-1,4-O-2)-(2,3-dihydroxy-4, 6dideoxyhexulosido)-14-hydroxy-5-card-20(22)-enolide* (1) and (3-O-1,2-O-2)-(2,3,4-trihydroxy-6-deoxyhexulosido)-14-hydroxy-5-card-20(22)-enolide* (13).State Scientific Center for Drugs of the Ministry of Health and the National Academy of Sciences of the Ukraine, Kharkov, fax 441118. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 824–832, November–December, 1995. Original article submitted May 22, 1995.     

Preparation of n-oxides of α− and α′-A minonicotines

Summary All possible N-oxides of -benzamidonicotine were prepared and were hydrolyzed with hydrochloric acid to N-oxides of the corresponding -aminonicotines.     

Steroid compounds from the starfish Lysastrosoma anthosticta collected in the Sea of Japan

Six polyhydroxylated steroids and their derivatives were isolated from the starfish Lysastrosoma anthosticta collected in the Posyet Bay, Sea of Japan. These include a new glycoside of the steroid polyol, lysastroside A (1), which was identified as (25S)-26-O--d-xylopyranosyl-5-cholestane-3,6,8,15,16,26-hexaol, and the previously known pycnopodioside C monoglycoside (2), marthasterone sulfate (3), (25S)-5-cholestane-3,6,8,15,16,26-hexaol (4), (25S)-5-cholestane-3,6,7,8,15,16,26-heptaol (5), and (25S)-5-cholestane-3,6,7,8,15,16,26-heptaol (6). The compounds were tested for the haemolytic activity and the action on the embryogenesis of the sea urchin Strongylocentrotus intermedius.     

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.     

Steroid compounds of marine sponges. VII. Preparation of derivatives of sokotrasterol and halistanol sulfates and structure-activity interrelationships among these compounds

Five new sulfated derivatives of sokotrasterol and halistanol have been obtained: 24-nor-5-cholane-2,3,6,23-tetraol 2,3,6-tri(sodium sulfate); 24-nor-5-cholane-2,3,6,23-tetraol 2,3,6-tri(sodium sulfate) 23-palmitate; 24,25-dimethyl-5-cholestane-2,3,6-triol 3-(sodium sulfate); 24,25-dimethyl-5-cholestane-2,3,6-triol 6-(sodium sulfate); and 24,25-dimethyl-5-cholestane-2,3,6-triol 2,6-di(sodium sulfate). The inhibiting and membranolytic properties of the polysulfated steroids from sponges and their derivatives have been studied. It has been shown that physiological activity in this series of compounds depends on biphilicity.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 441–445, July–August, 1986.     

Triterpene glycosides ofLeontice eversmannii

Conclusions The structure of leontoside D-a hederagenin pentaoside-has been established. The O-glycosidic moiety of leontoside D is O--D-glucopyranosido-(1 4)-O--L-arabopyranose, and the O-acyl moiety is O--L-rhamnopyranosido-(1 4)-O--D-glucopyranosido-(1 6)-O--D-glucopyranose.Khimiya Prirodnykh Soedinenii, Vol. 4, No. 3, pp. 153–158, 1968     

<Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR spectra of some drimanic sesquiterpenoids

One- and two-dimensional homo- and heteronuclear correlation proton, carbon, proton—proton, and proton—carbon NMR spectra of fifteen drimanic sesquiterpenoids: 11,12-dibromodrima-5,8-dien-7-one, drim-8-en-7-one, 11-hydroxydrim-8-en-7-one, 11,12-dihydroxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 8,9-epoxydriman-7-one, 8,9-epoxydriman-7-ol, 11,12-diacetoxydrim-8-en-7-ol, drimane-7,8,11-triol, 7,8-isopropylidenedioxydriman-11-al, 9, 11-dihydroxydrim-7-en-6-one, drimane-7,8,9-triol, drimane-7,8,11-triol, and drim-8-ene-7,11,12-triol were studied. The proton and carbon chemical shifts were assigned.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2589–2594, December, 2004.     

Control of the synthesis of some biologically active substances by thin-layer chromatography

Summary The aim of this investigation was the synthesis of -aryl propionic acids which might be expected to have antiinflammatory activity. The total synthesis of -(4-benzoylphenyl)--methyl propionic acid was monitored by thin-layer chromatography. The adsorption of the compounds of interest was found to be dependent upon the polarity of the eluting solvents. The observed retentions were mathematicaly analysed, and the system that showed the best separation of reactants evaluated. A least squares method was used to determine the best geometric curve expressing the relationship between values for R_f and eluent composition.Presented at the 14th International Symposium on Chromatography London, September, 1982     

Heterogeneous reactions of solid nickel(II) complexes,XII

The possibilities of correlating the structures and the stepwise thermal decomposition reactions of solid coordination compounds are discussed. The starting compounds were Ni(NCS)₂(py)₄, (py=pyridine), CuSO₄ · 5 H₂O and NiSO₄ · 7 H₂O, for which correlations of the above type were studied. It was found that the structural data on the initial compound alone are not sufficient to predict the stepwise course of the thermal decompositions of coordination compounds.

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Zusammenfassung Die Möglichkeiten der Korrelierung der Struktur und der stufenweisen thermischen Zersetzungsreaktionen fester Koordinationsverbindungen werden erörtert. Die Ausgangssubstanzen waren Ni(NCS)₂(py)₄, (py=Pyridin), CuSO₄·5 H₂O und NiSO₄·7 H₂O, für welche Korrelationsberechnungen des untersuchten Typs durchgeführt wurden. Es wurde festgestellt, daß die Strukturangaben der Ausgangsverbindung allein nicht ausreichen, um den stufenweisen Verlauf der thermischen Zersetzung von Koordinationsverbindungen zu beschreiben.

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Résumé On discute les possibilités d'établir une corrélation entre la structure et les réactions de décomposition thermique graduelle de composés de coordination solides. Les composés de départ étaient les suivants: Ni(SCN)₂(py)₄, (py=pyridine), CuSO₄·5 H₂O et NiSO₄·7 H₂O pour lesquels on a effectué le calcul des corrélations du type étudié. On a trouvé que les données relatives à la structure du composé de départ ne suffisaient pas pour prédire les étapes de la décomposition thermique des composés de coordination.

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, . Ni(NH₃)₂Pt(CN)₄ · 2₆₅ Ni(en)₂Pt(CN)₂· 0,14₆₅. , . : —Ni(NH₃)₂Pt(CN)₄·2₆₅, «» — Ni(en)₂Pt(CN)₄·0.14₆₅. . -« »-NiPt(CN)₄ · 6₂ Ni(en)₃Pt(CN)₄·₂. Ni(NH₃)₂Pt(CN)₄·2₆₅ 55–244°, Ni(en)₂Pt(CN)₄·0.14₆₅ - 139– 284°.

     

Transformed steroids. 189. Synthesis and transformations of 21-hydroxy-5α-H-pregnane 2′,2′-dimethyl-[16α,17α-d]-thioxalanes

In a continuation of the research on use of 20-keto-16,17-epoxysteroid 20-hydrazones for synthesis of 17-thio analogs of 20-ketosteroid 16,17-acetonides [2, 3], we synthesized 5-H-pregnane-3,16,21-trihydroxy-17-thiol-20-one 16,17-acetonide and found methods for its microbiological dehydrogenation and hydroxylation into ⁴-3-keto-and 9-hydroxy-⁴-3-keto derivatives.See [1] for Communication 188.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1182–1186, May, 1992.     

Reactivity of alkylperoxyl radicals in reactions with aromatic nitrons

Interaction of tetradecylperoxyl radicals with two aromatic nitrons has been studied.

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