Mono- and sesquiterpenoids of the oleoresin ofAbies nephrolepis. Crystal structure of (+)-β-cedrol

The composition of the mono- and sesquiterpenoids from the oleoresin of the Khingan fir has been studied. Thirteen monoterpenoids have been identified — bornyl acetate, -terpenyl acetate, geranyl acetate, citronellyl acetate, -fenchyl acetate, linalool, geraniol, terpineol-4, -terpineol, -fenchol, borneol, sabinene hydrate and thymol methyl ether; and 19 sesquiterpenoids — -longipinene, longicyclene, longifolene, -copaene, -ylangene, sibirene, -and -selinenes, - and -cadinenes, -muurolene, caryophyllene, -humulene, - and -bisabolenes, ar-curcumene, nerolidol, bisabolol, and -cedrol. The crystal structure of -cedrol has been investigated by x-ray structural analysis.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 41–45, January–February, 1985.     

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.     

Sorption behavior and inventory of alpha-emitters on the surfaces of spent nuclear fuel cladding

Alpha-emitters on the surfaces of Zircaloy-4 cladding of PWR spent nuclear fuel have been examined at fuel burnup of 6900, 29,400 and 38,100 MWd/t. The amount of -emitter on the inner and outer surfaces of cladding increased with fuel burnup, whereas the amount of plutonium on the outer surface remained roughly constant. The distribution of -activity in the cladding varied with fuel burnup. The ratio of -activity on the outer surface to total -activity of the cladding decreased from about 50% at fuel burnup of 6900 MWd/t to 3% at fuel burnup of 38,100 MWd/t. The inventory of the -activity in unit weight of cladding was found to be 4.75·10² and 4.35·10⁴ Bq/g-cladding at fuel burnup of 6900 and 38,100 MWd/t, respectively. Adsorptive ability of the outersurface of irradiated cladding was about one order of magnitude greater than that of unirradiated Zircaloy-4 for -emitters and some of the fission products except ruthenium.     

Determination of the half-lives of transactinium isotopes by relative activity method

Relative activity method offers the potentiality of providing half-life values over a wide range in a short time for different -emitting transactinium isotopes. The method involves the preparation of a synthetic mixture using another isotope of the same element followed by the determination of atom ratio and -activity ratio by thermal ionization mass spectrometry and -spectrometry, respectively. A double dilution technique is described which helps in maintaining the atom ratios as well as -activity ratios close to unity so that these could be determined with high precision and accuracy. Results obtained on the half-lives of²³²U,²³⁸Pu,²⁴²Pu and²⁴³Am using double dilution technique in relative activity method are summarized. Requirements, advantages and applications of this technique for determining the half-lives of other transactinium isotopes are presented.     

Synthesis of α, α, ω-trihydropolyfluoroalkyl chlorophosphates by the reaction between α,α,ω-trihydropolyfluoroalkyl phosphites and sulfuryl chloride

Conclusions An efficient method for the synthesis of ,,-trihydropolyfluoroalkyl chlorophosphates is by reacting ,,-trihydropolyfluoroalkyl dichlorophosphites and bis-(,,-trihydropolyfluoroalkyl) phosphites with sulfuryl chloride. It has been found that in three-coordinated polyfluoroalkyl phosphites, the high electronegativity of the polyfluoroalkyl groups hinders cleavage of the latter on reaction with sulfuryl chloride, thereby facilitating the formation of oxidation products.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 146–149, January, 1988.     

Excess enthalpies of aqueous solutions of small peptides at 25°C

Heats of dilution of aqueous solutions of the following di-and tripeptides were determined at 25°C over a wide concentration range: -alanyl-glycine, -alanyl--alanine, DL--alanyl-glycine, glycyl-DL--alanine, L--alanyl-L-alanine, DL--alanyl-DL--alanine, DL--alanyl-DL-valine, DL--alanyl--alanine, glycyl--aminobutyric acid, glycyl-L-leucine and DL--alanyl-glycylglycine. The excess enthalpies H^ex and partial molar relative enthalpies L₂ were calculated and enthalpy coefficients of intermolecular interaction were analysed using the additivity principle of Savage and Wood. The concentration dependence of the enthalpic characteristics of peptide-peptide interactions is discussed based on of their hydrophobicity and hydrophilicity. The three-stage model of peptide association is described using enthalpic coefficients of intermolecular interactions.     

Studies on the Colloidization and Stability of Layered M(IV) Phosphates in Aqueous Amine Solutions

For the purpose of preparing pillared materials and multifunctional films,the colloidization and hydrolysis of -Zr(HPO4)2·H2O(-ZrP), -Sn(HPO4)2·H2O (-SnP)and -Ti(HPO4)2·H2O (-TiP) in alkylamineand alcohol amine solutions were investigated. The phosphates colloidizeat a low level of amine intercalation but recrystallize at high levels ofamine uptake. Alcohol amines are more efficient in colloidization ofphosphates than alkylamines, and in the same amine solution -ZrPand -SnP colloidize more readily than -TiP. Thehydrolytic reaction of the phosphates following the course of intercalationin different amine solutions were studied. The dissolution of the metal ionsaccompanying the hydrolysis of HPO42- leads to the destruction ofthe sheet structure. The strong hydrolytic reaction of -TiP causesit to colloidize with difficulty. The phase transformations of the wet amineintercalates during air drying were detected by XRD. The interlayer aminemolecules may arrange in monolayer, bilayer or intermediate orientation,depending on the nature and content of the amines.     

3-Äthyl-3-phenylpiperidindion-(2,4) und 3-Äthyl-3-phenylpyrrolidindion-(2,4) aus α-Phenylacetessigester

Zusammenfassung -Äthyl--phenylacetessigester (I) wurde bromiert, der resultierende -Bromacetylphenylbuttersäureester (II) mit NaBH₄ zum Bromhydrin (III) reduziert. Umsetzung mit KCN lieferte den -Cyan--hydroxy--phenyl--äthylbuttersäureester (IV), der in Gegenwart vonRaney-Ni zu den beiden stereoisomeren 3-Äthyl-3-phenyl-4-hydroxypiperidonen-(2) (Va) und (Vb) reduziert wurde. Oxydation von (Vb) mit CrO₃ lieferte das 3-Äthyl-3-phenylpiperidindion-(2,4) (VI).     

Total synthesis and properties of prostaglandins 30. Modification of (1S,5R)-2-oxabicyclo[3.3.0]-6-octen-3-one at the α-carbon atom

Derivatives of -alkyl-, -alkylidene-, and -hydroxymethylene-2-oxabicyclo[3.3.0]-6-octen-3-one were obtained. The possibility of functional substitution of the bicyclic -lactones at the position to the carbonyl group was thereby demonstrated.For Communication 29, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1621–1630, December, 1991.     

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.     

Top soil environmental radioactivity in Akwa Ibom State of Nigeria

A survey of top soil environmental radioactivity in Akwa Ibom State of Nigeria has bean investigated. The results vary considerably from one environment to another ranging between a minimum of 161 mBq·g^–1 and a maximum value of 648 mBq·g^–1 -activity. The work reveals that hospitals and health centres lead in top soil radioactivity with the highest mean values of (378 mBq·g^–1) and (294 mBq·g^–1) followed closely by industrial areas with mean values of (372 mBq·g^–1) and (283 mBq· g^–1) trailing beaches and recreation centres having average values of (364 mBq·g^–1) and (273 mBq·g^–1). Lower levels of top soil radioactivity were observed mostly in environments with high level human interaction activity such as schools, offices, environments and recreation centres. An overall top soil mean of 342 mBq·g^–1 -activity, 271 mBq·g^–1 -activity and 71 mBq·g^–1 -activity were observed in the State.     

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.     

Steroid glycosides from the starfishEchinaster sepositus

Two new steroid glycosides, which have been called echinasterosides B₁ and B₂ have been isolated from the starfishEchinaster sepositus. Using chemical transformations (methylation, hydrolysis) and also spectral methods (¹H and¹³C NMR spectroscopy and GLC-MS) the complete chemical structure of B₁ has been established as 15-acetoxy-5-cholestane-3,4,6,8,24-pentaol 24-O[O-(2)O÷ methyl--D-xylopyranosyl)-(13)--L-arabinofuranoside] (I) and that of glycoside B₂ as 5-cholestane-3,4,6,8,15,24-hexaol 24-O-[O÷(2-O-methyl--D-xylopyranosyl)-(13)--L-arabinofuranoside] (II).Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Pirodnykh Soedinenii, No. 2, pp. 246–249, March–April, 1987.     

Molar cotton-mouton constants and anisotropy of magnetic susceptibility of benzyl chlorides and benzyl bromides

Conclusions Due to thearom^–gsC-Hal* interaction, the magnetic susceptibility ellipsoids of -haloalkylbenzenes, with the exception of ,'-p-xylylidene bromide, undergo rearrangement of the semimajor axes with a decrease in the diamagnetic component in direction 1, 4 and along the axis of symmetry of the electrons in the ring.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No No. 7, pp. 1552–1557, July, 1986.     

Bestimmung von Thorium-230 und Thorium-232 in Uranerzen

Zusammenfassung Ein Analysenverfahren für uranhaltige Erze wird beschrieben. Das ²³⁰Th wird durch Messung der -AktivitÄt bestimmt, das ²³²Th durch Aktivierungsanalyse und Messung des ²³³Pa. Zur Bestimmung der Ausbeute bei der chemischen Trennung wird ²³⁴Th zugegeben. Die AktivitÄt der Radionuklide wird im - und -Plateau eines Methandurchflu\zÄhlers gemessen. Die Auswertung der AktivitÄtsmessungen wird erlÄutert.

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Summary An analytical method for uranium ores is described. ²³⁰Th is determined by measuring the -activity, ²³²Th by activation analysis and measuring the activity of ²³³Pa. In order to estimate the yield of the chemical separation ²³⁴Th is added. The activity of the radionuclides is measured in the - and the -plateau of a methane flow counter. The evaluation of the activity measurements is described.

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An der Ausführung der Analysen war Frl. L. Ulrich beteiligt.     

Über die Darstellung von 3β, 16α-und 3β, 16β-Diacetoxy-5α-pregnan-20-on

Zusammenfassung Die Synthese von 3, 16-Diacetoxy-5 -pregnan-20-on (VI) aus 3-Acetoxy-5 -pregn-16-en-20-on und eine verbesserte Darstellung von 3, 16-Diacetoxy-5 -pregnan-20-on (III) aus 3-Acetoxy-pregna-5, 16-dien-20-on werden beschrieben.     

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.     

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.     

Synthesis and chiral-optical properties of (+)-3-methyl-3,4-dihydroisoquinoline-1-thione

(+)-3-Methyl-3,4-dihydroisoquinoline-1-thione was obtained by sulfuration of (+)-3-methyl-3,4-dihydroisoquinolone with phosphorus pentasulfide or by cyclization of (+)--benzylethyl isothiocyante under the influence of polyphosphoric acid. Measurements of the rotatory dispersion and circular dichroism showed the presence of two positive Cotton effects due to n^* and ^* transitions in the thioamide chromophore, as well as Cotton effects apparently due to ^* transitions in the aromatic chromophore.Communication XXXV from the series Stereochemical Investigations. See [11] for communication XXXIV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 94–97, January, 1976.     

The problem of identifying an adequate kinetic equation for a chemical transformation in thermal analysis

Additional criteria are suggested for the selection of an adequate functiong() describing the mechanism of a chemical transformation using the Satava method.

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Zusammenfassung Zusätzliche Kriterien werden zur Auswahl der geeigneten Funktion g() zur Beschreibung des Mechanismus der chemischen Umwandlung mit der Satava-Methode vorgeschlagen.

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g() .