Triterpene glycosides of Pulsatilla dahurica structures of glycosides A,B, C,and D

The isolation of four triterpene glycosides from the roots of the dahurian anemonePulsatilla dahurica (Fisch. ex DC) Spreng, is described together with their identification, on the basis of chemical transformations, spectral characteristics, and literature analogies, as hederagenin 3-O--L-arabinoside, hederagenin 3-O-[O--D-glucopyranosyl-(12)--L-arabinopyranoside], hederagenin 3-O--L-arabinopyranoside 28-O-[O--L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranoside], and hederagenin 3-O-[O--D-glucopyranosyl-(14)--L-arabinopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranoside].Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 349–356, May–August, 1992.     

Metabolic Studies of Clostebol Acetate in Horses

Clostebol acetate (4-chlorotestosterone acetate) is a synthetic anabolic steroid which may be used to enhance performance in racehorses. Studies on the in vitro biotransformation of clostebol acetate with horse liver microsomes were carried out. Six metabolites (C1 – C6) were detected. They were 4-chlorotestosterone (C1), 4-chloroandrost-4-en-3-ol-17-one (C2), 4-chloroandrost-4-ene-3,17-diol (C3), 4-chloroandrost-4-ene-3,17-dione (C4), 4-chloroandrost-4-en-6-ol-3,17-dione (C5) and 6-hydroxy-4-chlorotestosterone (C6). Clostebol acetate (350 mg) was administered orally to 2 thoroughbred geldings. The parent drug was not detected in post-administration urine, and only three metabolites C1, C3, and 4-chloroandrostane-3,17-diol (C7) were observed. The metabolic pathway for clostebol acetate is postulated. These studies have shown that metabolites C3 and C7 could be used as potential screening targets for controlling the abuse or misuse of clostebol acetate in racehorses.     

Thermodynamics of Binding of α:-Cyclodextrin to Straight-Chain Alkyl Derivatives in Aqueous Solution

Apparent standard Gibbs energy, enthalpy, entropy, and heatcapacity data of the interactions of -cyclodextrin (CD) to some n-carboxylatesH(CH₂)_nCOO^- (n = 4–6), are determined by isothermal titration microcalorimetryat different temperatures in phosphate buffer, pH 9.0, assuming a 1 : 1 model indilute solution. Modelling of contributions of the thermodynamic properties of the solutionindicates that CD undergoes conformational change upon binding to homologousseries of n-carboxylates, n-alcohols, ,-alkane dicarboxylates and ,-alkane diols.     

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.     

Porphyrins. 9. New data on the polyformylation of metal complexes of etioporphyrin I

The structures of the products of the polyformylation of Cu, Ni, and Co complexes of etioporphyrin (EP) as monoformyl-, ,-diformyl-, ,-diformyl-, and ,,-triformyl-EP were established by electronic, IR, and PMR spectroscopy and mass spectrometry. -Formyl--(N-methylformaldimine)-EP and porphyrins that contain a cyclopentane ring can be formed by alkaline treatment of the Vilsmeier formylation products.See [1] for communication 8.See [2] for our preliminary communication.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 767–775, June, 1979.     

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.     

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.     

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.     

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.     

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.     

Transformed steroids. 190. Influence of Co-complexation on the epoxide ring opening of 17β-ethynyl-16α,17α-epoxyandrost-4-en-3-one on reacting with pyridine hydrofluoride,pyridine hydrochloride,and pyridine thiocyanate

The epoxide ring opening of 16,17-epoxy-17-ethynylandrost-4-en-3-one and its dicobalt hexacarbonyl complex on reacting with Py·HF, Py·HCl, and Py·HSCN was studied. The results of these reactions and the structure of the end products depend not only on the complexation of the acetylene bond, but also on the nucleophilic reagent used. On the basis of the reaction of a Co-coordinated 16,17-epoxy-17-ethynylandrost-4-en-3-one there has been developed a preparative method for the synthesis of pregn-4-ene-3,20-dione-[17,16-d]-1,3-oxazolidin-2-one.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2661–2666, November, 1992.     

Isomer yield ratios and cross sections for110(4.9 h)In/110(69 min)In and108(58 min) In/108(39.6 min)In produced by alpha reactions on silver

This paper reports the determination of absolute excitation functions and cross section ratios for the production of 110(4.9 h)/110(69 min) In and^{108(58 min)/108(39.6 min)}In in reactions of -particles with natural silver. Target stack foils of silver were bombarded with the 55.0 MeV -particle, beam available at the Buenos Aires synchrocyclotron. The -spectrometry was used for the identification and for the determination of the absolute activity of^{110(4.9 h)}In and^{110(69 min)}In from¹⁰⁷Ag/, n/ and¹⁰⁹Ag/, 3n/ reactions and of^{108(58 min)}In and^{108(39.6 min)}In from¹⁰⁷Ag/, 3n/ and¹⁰⁹Ag/, 5n/ reactions by means of Ge intrinsic detector.This work has been sponsored by the Subsecretaria de Ciencia y Tecnología Argentina.     

13C NMR spectra and stereoisomerism in series of androstano-and estrano-D′-pentaranes

Conclusions The stereoisomerism in series of androstano- and estrano-D-pentaranes in solution has been investigated by¹³C NMR. The orientation of the D ring in the 15,16-, 15,16-, and 15,16-isomers relative to the steroid skeleton, as well as the boat conformation of the D ring, were determined from the¹³C chemical shifts.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1038–1045, May, 1984.     

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.     

Aggregations or crystals of Acridine Orange in various synthetic-polymer fibres

Summary The visible absorption spectra of the cross-sections of the dyed various synthetic-polymer fibres were measured by means of a microspectrophotometer. We found that the spectra of Acridine Orange hydrochloride in the crosssections of fibres showed a maximum of -band and band, and the spectra of Acridine Orange (free base), indicated a maximum of -band, -band and the crystal peak of the dye. These results suggest that the monomeric state, the aggregate as well as the crystal of the dye exist in these dyed synthetic-polymer fibres.

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Zusammenfassung Die sichtbaren Absorptionsspektren der Querschnitte der verschiedenen gefärbten synthetischen Polymerfasern wurden mit einem Mikrospektrophotometer gemessen. Dabei wurde herausgefunden, daß die Spektra der Acridinorange Hydrochloride in den Querschnitten ein Maximum beim -Band und beim -Band und die Spektra der Acridinorange (freie Base) ein Maximum beim -Band, -Band und beim Kristallpik der Farbstoffe zeigen. Diese Resultate deuten darauf hin, daß sowohl der monomere Status, als auch Aggregate und die Kristalle der Farbstoffe in diesen synthetischen Polymerfasern existieren.

     

Polarographic behavior of 2,2′-bifuryl and 2,2′-furoin

In aqueous and aqueous-ethanolic buffer solutions at pH<9, 2, 2-bifuryl and 2, 2-furoin give two-electron polarographic electroreduction waves, the half-wave potentials of which depend on the pH. The primary product of the electroreduction of 2, 2-bifuryl is trans-1,2-dihydroxy-1,2-bis(, -furyl)ethylene, which then rearranges into 2, 2-furoin. The anode-cathode wave of 2,2-bifuryl has been studied by means of a Kalousek commutator. It has been shown that the polarographic behavior of 2,2-bifuryl and 2, 2-furoin is similar to that of benzil and benzoin, but differs from the behavior of analogs of the pyridine series.     

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.     

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.     

Untersuchungen über Phenthiazinderivate. 10. Mitteilung

Zusammenfassung Es wurde ein allgemein anwendbarer Weg zur Herstellung von in -Stellung basisch substituierten 4,10-Trimethylenphenthiazinen durch Umsetzung der aus den -Hydroxyverbindungen erhaltenen -Bromverbindungen mit sekundären Aminen angegeben. Für das in der Literatur bekannte -Amino-4,10-Trimethylen-phenthiazin wurden neue Darstellungen beschrieben.     

Charge-transfer Interaction: A Driving Force for Cyclodextrin Inclusion Complexation

PM3 calculations were performed on the complexation of -cyclodextrin (-CD) with nitrobenzene, benzoic acid, benzoate anion, 4-nitrophenol, and 4-nitrophenolate anion. The results, in agreement with the experimental observations, indicated that the complex -CD-benzoic acid was more stable than -CD-nitrobenzene, and -CD-4-nitrophenolate was more stable than -CD-4-nitrophenol. Frontier orbital analysis suggested that charge-transfer interaction led to such behaviors, and hence constituted a nontrivial driving force in the molecular recognition of -CD.