Fluorine containing β-lactones

Summary Ring opening of -trifluoromethyl- -methyl- -propiolactone is unidirectional and leads to derivatives of -trifluoromethyl- -hydroxybutyric acid.     

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.     

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.     

Reduction of some D-homosteroids with an aromatic a ring with alkali metals under the conditions of Birch's reaction. II.

Summary 1. The reduction of 3-methoxy-D-homoestra-1, 3, 5(10), 8-tetraen-17a-ol (IV) with alkali metals in the presence of ammonium chloride or alcohol gives, in addition to 8, 9-dihydro derivatives, the 8, 9 and 8, 9-epimers, the structure of which has been shown partly by independent synthesis and partly on the basis of chemical reactions and NMR spectra.2. Hydrolysis of the reduction products has given 19-nor-D-homotestosterone (III) and its 8- and 9, 10-epimers (V) and (VI). The ketols (III) and (V) readily form hydroperoxides in air.3. The reduction of the ethylene ketal of 3-methoxy-D-homoestra-1, 3, 5(10), 8-tetraen-17a-one (XIX) takes place stereodirectively and gives only 8, 9-dihydro derivatives.Khimiya Prirodnykh Soedinenii, Vol. 1, No. 2, pp. 90–100, 1965     

Tripenoid glycosides of alfalfa. VII. Medicosides E and F

Two hederagenin glycosides — medicosides E and F — have been isolated from the roots ofMedicago sativa L. (Leguminosae). Medicoside E has the structure of hederagenin 28-O--D-glucopyranoside 3-O-[O--G-glucopyranosyl-(13)--D-xylopyranoside]. Medicoside F has the structure of hederagenin 28-O--D-glucopyranoside 3-O-[O--D-glucopyranosyl-(12)--L-arabinopyranoside].Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent. Institute of Organic Chemistry, Russian Academy of Sciences, Moscow. Translated from Khimiya Prirodnykh Soedinenii. No. 5, pp. 701–705, September–October, 1993.     

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     

Temperature dependence of the X-ray induced adsorption of oxygen and methane on ZnO

The capacity of ZnO with respect to the photo- and X-ray adsorbed, as well as postadsorbed oxygen is shown to depend on the temperature. It is suggested that this dependence cannot be attributed to either the thermal annealing of the induced sites or the thermal desorption of the adsorbed molecules.

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O , - , , , . , .

     

Oxygen sorption and thermal regeneration of sorption centers on catalysts of ammonia synthesis in helium and hydrogen flow

The interaction of oxygen with catalysts for ammonia synthesis in helium and hydrogen flow has been studied. Various catalysts sorb from 7 to 12 oxygen layers. 2 to 4 layers can be removed by thermal activation in helium, the rest only by hydrogenation in hydrogen.

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. , 7–12 . 2–4 , .

     

Glycosides of marine invertebrates. X. The structure of stichoposides A and B from the holothurianStichopus cloronotus

The structures of two triterpene oligosides from the holothurianStichopus cloronotus (Brandt) have been established; they are: 23-acetoxy-3-[O--D-quinovopyranosyl-(12)--D-xylopyranosyloxy]holost-7(8)-ene and 23-acetoxy-3-[O--D-glucopyranosyl-(12)--D-xylopyranosyloxy]holost-7(8)-ene.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. 181–184, March–April, 1981.     

Thermoanalytische und Kalorimetrische Untersuchung von CoOOH und CoOOD

Zusammenfassung CoOOH und CoOOD wurden definiert hydrothermal synthetisiert, chemischanalytisch und röntgenographisch charakterisiert sowie thermoanalytisch untersucht.Nach den Ergebnissen verläuft der thermische Abbau zu CO₃O₄, H₂O_(g) bzw. D₂O_(g) und O₂ in einer für Hydroxide typischen Einstufenreaktion. Ihre Temperaturlage ist vom Partialdruck der Reaktionsgase abhängig.Die hochtemperaturkalorimetrische Untersuchung erbrachte Werte für die Standardbildungsenthalpien _B H ₂₉₈ (CoOOH: –456±3; CoOOD: –455±3 kJ mol^–1) sowie die Standardreaktionsenthalpien ihrer Zersetzungsreaktionen.

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Hydrothermally synthesized CoOOH and CoOOD were characterized by chemical, X-ray and thermal analysis. The thermal decomposition leads to CO₃O₄, H₂O_(g) or D₂O_(g) and O₂ in a one-step reaction typical for hydroxides. The decomposition temperature depends on the partial pressure of the gaseous reaction products. High-temperature calorimetric studies allowed determination of the standard enthalpy of formation _B H ₂₉₈ (CoOOH: – 456±3; CoOOD: –455±3 kJ mol^–1) and the standard enthalpy of the decomposition reactions.

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CoOOD , . , , Co₃O₄, ₂ D₂ O₂. . . _BH ₂₉₈ (: –456±3; CoOOD: – 455±3 kJ ml^{– 1}.

     

A DSC study of thermally treated and UV-treated low-density polyethylene

The melting behaviour of thermally and UV-treated polymer film was studied using DSC. The melting profiles was registered after periods of 24 hours of exposure. The melting profiles after the UV-exposure resembled those observed after heating at 60°. A weak shoulder was first recorded at about 50° and was observed to shift to higher temperatures with increasing exposure time. At the end of the experiments the shoulder was registered around 80°. The changes are compared with results from mechanical tensile tests.

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Zusammenfassung Das Schmelzverhalten eines thermisch und UV-behandelten Polymer-films wurde unter Anwendung der DSC untersucht. Das Schmelzprofil wurde nach 24-stündiger Behandlung registriert. Die Schmelzprofile nach UV-Behandlung ähnelten jeden, die nach Erwärmung auf 60° erhalten worden waren. Eine schwache Schulter wurde zuerst bei etwa 50° beobachtet, welche bei steigender Behandlungszeit in Richtung der höheren Temperaturen verschoben wurde. Am Ende der Versuche wurde die Schulter bei etwa 80° registriert. Die Änderungen wurden mit den Ergebnissen mechanischer Dehnteste verglichen.

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Résumé On a étudié par analyse calorimétrique différentielle (DSC) le comportement pendant la fusion d'un polymère en film soumis à un traitement thermique et par UV. Les profils de fusion ont été enregistrés après des périodes d'exposition de 24 h. Les profils de fusion après traitement UV ressemblent à ceux obtenus après chauffage à 60 °C. Un faible épaulement vers 50° est d'abord enregistré puis il se déplace vers les températures plus élevées, quand la durée d'exposition augmente. En fin d'expérience l'épaulement se situe vers 80°. Ces modifications sont comparées avec les résultats obtenus à partir des essais mécaniques de traction.

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, . , 60°. 50°, . 80°. .

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Valuable assistance from Mrs. E.-L. Svahn is greatefully acknowledged. This work was supported by the Neste Oy Foundation and the Foundation of Technology in Finland.     

Triterpene glycosides ofAstragalus and their genins. LVI. Cyclopycnanthoside— A new cycloartane glycoside

The stems ofAstragalus pycnanthus Boriss. (Leguminosae) contain a number of low-molecular-mass substances, of which -sitosterol, cyclosieversioside F, and D-3-O-methyl-chiro-inositol have been identified, and also a new cycloartane diglycoside — 24R-cycloartane-3, 6, 16, 24,25-pentaol 16-O--D-glucopyranoside 3-O--D-xylopyranoside.Throughout this paper the given Russian name of the compound concerned would correspond to an English pycanthoside. Pycnanthoside agreees better with the name of the source plant — Translator.The materials of this paper were presented at the Second International Symposium on the Chemistry of Natural Compounds (SCNC, Eskiehir, Turkey, October 22–24, 1996).Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 40 64 75. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 194–200, March–April, 1998.     

Cardiac glycosides of Cheiranthus allioni. IX

Summary From the seends ofCheiranthus allioni hort. another three cardiac glycosides have been isolated. One of them has been identified as cheirotoxin. It has been established that in cheirotoxin the D-glucose is attached to C₄ of the D-gulomethylose and this glycoside therefore has the structure of strophanthidin 3-O-[4-O--D-glucopyranosyl--D-gulomethylopyranoside]. The two other glycosides, which have been named sarmentogulomethyloside and gulosarmentoglucoside are new and are, respectively, sarmentogenin-3-O--D-gulomethylopyranoside and sarmentogenin 3-O-[4-O--D-glucopyranosyl--D-gulomethylopyranoside].For Communication VIII see [1].Khar'kov Scientific-Research Institute of Pharmaceutical Chemistry. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 607–611, September–October, 1974.     

Triterpene glycosides of Astragalus and their genins. XXIV. Cycloorbicoside G from Astragalus orbiculatus

A bisdesmosidic glycoside — cycloorbicoside G — has been isolated from the epigeal parts of the plantAstragalus orbiculatus Ledeb. (Leguminosae), and on the basis of chemical transformations and spectral characteristics its structure has been established as (23R,24S)-16,23;16,24-diepoxycycloartane-3,7,25-triol 25-O--D-glucopyranoside 3-O--D-xylopyranoside.Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 837–842, November–December, 1987.     

Triterpene glycosides of Astragalus and their genins XLII. Cycloartanes of Astragalus tragacantha

Another six components ofAstragalus tragacantha Habl. have been identified on the basis of spectral characteristics and chemical transformations. We have previously described cyclocanthagenin and its 3-0--D-xylopyranoside — cyclocanthoside A — as products of the acid hydrolysis of cyclocanthoside D. Cyclocanthosides B, C, E, and G are here described for the first time and are (24S)-cycloartane-3,6,16,24,25-pentol 3-O-(4-O-acetyl--D-xylopyranoside) 6-O--D-glucopyranoside, (24S)-cycloartane-3,6,16,24,25-pentol 6-O-(6-O-acetyl--D-glucopyranoside) 3-O--D-xylopyranoside, (24S)-cycloartane-3,6, 16,24,25-pentol 6-O--D-glucopyranoside, and (24S)-cycloartane-3, 6, 16, 24, 25-pentol 6-O--D-glucopyranoside 3-O-[O--D-glucopyranosyl-(12)--D-xylopyranoside], respectively.Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Institute of Ecological Genetics, Moldavian Academy of Sciences, Kishenev. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 360–367, May–August, 1992.     

Cardiac glycosides of Cheiranthus allioni. XI

Summary Another three cardiac glycosides have been isolated from the seeds ofCheiranthus allioni hort. One of them has been identified as digifucocellobioside (digitoxigenin 3 -O-[O--D-glycopyranosyl(1 4)-O--D-glucopyranosyl(1 4)-O--D-fucopyranoside]). The two other glycosides, called digitoxigenin gulomethyloside and glucodigigulomethyloside are, respectively, digitoxigenin 3 -O--D-gulomethyloside and digitoxigenin 3 -O-(4-O--D-glucosyl--D-gulomethyloside).For Communication X, see [1].Khar'kov Scientific-Research Institute of Pharmaceutical Chemistry. All-Union Scientific-Research Institute of Medicinal Plants. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 754–758, November–December, 1975.     

Phytoecdysteroids ofSilene nutans. III. Nusilsterone

A new ecdysteroid — nusilsterone — has been insolated from the whole plantSilene nutans L. It has been shown that it is 1,2,3,14,20R,22R,24,25-octahydroxy-5--cholest-7-en-6-one.Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii. No. 4, pp. 522–525, July–August, 1985.     

Evaluation of the Compression Behavior of Paracetamol Tablets Produced by Dispersion in β-Cyclodextrin. Part I: Scanning Electron Microscopic Study of Tablets

The compression behaviour of three powder products of Paracetamol–-cyclodextrin solid dispersions (PAR--CD SD) and PAR alone were evaluated using the method of scanning electron microscopy (SEM). The four powder products were: PAR, PAR–-CD physical mixture, kneaded solid dispersion of PAR–-CD and spray dried solid dispersion of PAR–-CD (PAR–-CD ratio of 1 : 1 w/w). By observing the surface, side and broken surface of each tablet sample under different magnifications the compression behaviour, mechanism of consolidation and deformability of particles were evaluated. PAR alone and the PAR–-CD physical mixture were compressed by the brittle fracture mechanism; the PAR–-CD kneaded solid dispersion showed a good plastical deformation. With PAR–-CD spray dried solid dispersion a good plastic deformation and mechanism of cool sintering were postulated. The influence of -CD on the compression behavior of the PAR was proved. The results obtained by the SEM method are well correlated with physicopharmaceutical parameters (crushing strength, disintegration time, friability, elastic recovery and tensile strength) of the tablets.     

Dimerization of N-methylanabasine in the presence of metallic sodium

In a study of the dimerization of N-methylanabasine in the presence of metallic sodium under conditions for the dimerization of pyridine, it was found that the reaction does not take place at room temperature while at 50–70° C it leads to the formation of,-di(1-methylpiperid-2-yl)-,-bipyridyl. Oxidation of the latter yielded 4,4-bipyridyl-5, 5-dicarboxylic acid, the decarboxylation of which gave,-bipyridyl.