Triterpene glycosides of alfalfa. II. Medicosides C

The roots of the plantMedicago sativa (family Fabaceae) have yielded, in addition to the medicoside G described previously, two more triterpeneglycosides, caulosaponin B and the new glycoside medicoside C. The latter has the structure of hederagenin 3-O-[-L-arabinoyranosyl-(1 2)--D-glucopyranosyl-(1 2)--L-arabinpyranoside].Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 805–808, November–December, 1985.     

Saponins of dioscorea XV. Caucasosaponin and caucasoprosapogenin fromD. caucasica

Summary Two new saponins have been isolated from the rhizomes ofD. caucasica: the water-soluble caucasosaponin—a rhamnosotriglucoside of 25 D-22-spirost-22-en-3-ol—and the water insoluble caucasoprosapogenin—a glucosotrioside of 25 D-22-spirost-5-en-3-ol-, and also the previously known rhamnosidodiglucoside of 25 D-22-spirost-5-en-3-ol—gracillin.Khimiya Prirodnykh Soedinenii, Vol. 3, No. 4, pp. 237–241, 1967     

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.     

Alkaloids ofRhinopetalum stenantherum. II. The structure of stenanthine and stenanthidine

From a methanolic extract of the epigeal part ofRhinopetalum stenantherum have been isolated -chaconine (I) and the new glucoalkaloids stenanthine with mp 262–264°C []_D 46.5°, C₄₅H₇₃NO₁₅ (II), and stenanthidine with mp 269–271°C, []_D –47.5°, C₃₉H₆₃NO₁₁ (III). On the basis of the facts that partial hydrolysis of the trioside (II) formed the biosides (I) and (III), and that on the hydrolysis of the latter the monoside -chaconine was found, it may be assumed that stenanthine has the structure of solanidine 3-0-{[0--D-glucosyl-(1 6)]-[0--L-rhamnosyl-(1 4)]-D-glucoside}, and stenanthidine that of solanidine 3-0-[0--D-glucosyl-(1 6)-D-glucoside].Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 349–356, May–June, 1981.     

Cardenolides of the pods ofOrnithogalum magnum Krasch. et Schischk

Summary Steroid glycosides of the cardenolide group have been found inOrnithogalum magnum.Three glycosides, provisionally called substances a, b, and c, have been isolated by adsorption chromatography on alumina.Substance a is 3-(O--L-rhamnopyranosyl)-11, 14-dihydroxy-5-card-20(22)-enolide (rohdexin A).Khimiya Prirodnykh Soedinenii, Vol. 1, No. 3, pp. 156–160, 1965     

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.     

Reaction of α-polynitroalkyl derivatives of sulfur and selenium with hydrogen halides and halide ions

Hydrogen halides (HCl and HF) react with -polynitroalkylsulfides and -polynitroalkylselenides as electrophilic or as nucleophilic reagents depending on the conditons, forming accordingly products of electrophilic or nucleophilic substitution at the -carbon atom. In contrast to this, halogen ions (Cl^–, F^–) always bond to the -carbon. The use of dipolar aprotic solvents and activators (Lewis acids or strong mineral acids) facilitates the formation of products of nucleophilic substitution at the -carbon.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2106–2111, September, 1989.     

Steroids of the spirostan and furostan series of plants of the Allium genus. XXIII. Structure of cepagenin and of alliospirosides C and D from Allium cepa

Two new steroid glycosides of the spirostan series have been isolated from the fruit ofAllium cepa L. (family Liliaceae): alliospirosides C and D. On the basis of chemical transformations and spectral characteristics it has been established that the aglycon of both glycosides is a new steroid sapogenin — cepagenin — having the structure of (24S,25R)-spirost-5-ene-1,3,24-triol. Alliospirosides C and D are cepagenin 1-O-[O--L-rhamnopyranosyl-(12)-L-arabinopyranoside] and 1-O-[O--L-rhamnopyranosyl-(12)-O--D-galactopyranoside], respectively.Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 843–849, November–December, 1987.     

Phytoecdysteroids of Rhaponticum carthamoides. II. Rhapisterone B

A new ecdysteroid (rhapisterone B) has been isolated from the seeds ofRhaponticum cathamoides (Willd.) Iljin. (familyCompositae). It has been shown that it is 2, 3, 11, 14, 20R, 24-hexahydroxy-5-cholest-7-en-6-one.Institute of the Chemistry of Plant Substances, Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 806–808, November–December, 1991.     

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.     

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.     

Structure of haplosidine

A new glycoalkaloid, haplosidine, has been isolated from the epigeal part of the plantHaplophyllum perforatum, and its structure has been established as 7-[O--D-glucopyranosyl-(1 3)-2-O-acetyl--L-rhamnopyranosyloxy]-4,8-dimethoxyfuranoquinoline.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 94–97, January–February, 1988.     

Iriterpene glycosides of Astragalus and their genins XLIII. Cycloaraloside B from Astragalus amarus

The structure of a new cycloartane glycoside, cycloaraloside B, isolated from the roots ofAstragalus amarus Pall. (Leguminosae) has been established on the basis of chemical transformations and spectral characteristics: it is 20R,24S-epoxycycloartane-3,6,16,25-tetraol 3-O-[O--L-rhamnopyranosyl-(12)-(6-O-acetyl--D-glucopyranoside)].Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 528–531, September–October, 1992.     

Steroids of the spirostan and furostan series from plants of the genus Allium. Structure of anzurogenin A from Allium suvorovii and A. stipitatum

The collective fruit of the cocultivatedAllium suvorovii Rgl. andA. stipitatum Rgl. (familyLiliaceae) has yielded a new genin of the spirostan series — anzurogenin A, which is 2,3,5-trihydroxy-(25R)-spirostan-6-one.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 68–73, January–February, 1988.     

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.     

HCN synthesis from NH3 and CH4 on Rh and Ir

The synthesis of hydrocyanic acid from methane and ammonia on Rh and Ir wires was studied at temperatures varying between 1200 and 1500 K at one atmosphere. Activation energies and preexponential factors are reported.

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1200–1500K . .

     

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.     

Flavonone biosides ofAcinos thymoides

Summary It has been established by a chemical and spectroscopic study of the flavonoid biosides isolated from the hypogeal part ofAcinos thymoides that bioside A is 5,7-dihydroxy-4-methoxyflavan-7-one -(D-glucopyranosyl-2--L-rhamnopyranoside), or poncirin, and bioside B is 5,7-dihydroxy-4-methoxyflavan-7-one -(D-glucopyranosyl-4--L-rhamnopyranoside), which we have called acinoside.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 3, pp. 166–172, 1966     

Polyhydroxylated steroids from the starfishPatiria pectinifera

By chromatography on Polikhrom-1, silica gel, and Florisil, an ethanolic extract of the digestive organs of the starfishPatiria pectinifera has yielded the steroid polyols 5-cholestan-3,6,8,15,16,26-hexaol and 5-cholestan-3,4,6,7,8,15,16,26-octaol 6-(sodium sulfate). The structures of the compounds have been shown by spectral characteristics and chemical transformations.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 738–741, November–December, 1984.