Steroids of the spirostan and furostan series from plants of the genus Allium. XXVII. Alliosterol and allosides A and B from Allium suvorovii and Allium stipitatum — Structural analogs of furostanols

Two new glycosides of the cholestane series (allosides A and B) have been isolated from the fruit of the cocultivatedAllium suvorovii Rgi. andAllium stipitatum Rgl. (family Liliaceae, local name anzur). The acid hydrolysis of both compounds gave a sterol not previously described, which has been called alliosterol and has the structure of (22S)-cholest-5-ene-1, 3, 16, 22-tetraol, and the product of its dehvdration, which is (16S, 22S)-furost-5-ene-1, 3-diol. Alloside A is the 16-O--D-galactopyranoside, and alloside B the 16-O--D-galactopyranoside 1-O--D-glucopyranoside of alliosterol.Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 231–241, March–April, 1991.     

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.     

Crystal and molecular structures of the sesquiterpene lactone ajafinin

An x-ray structural analysis has been made with the aim of reliably determining the spatial structure of the sesquiterpene lactone ajafinin. It has been established that it has the structure and configuration of 1,2--epoxy-3,4,10-trihydroxy-5,6(H),7(H)-guai-11(13)-en-6,12-olide.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 291–295, May–June, 1986.     

Radiation-induced reactions of cholesterol in an aqueous medium

⁶⁰Co -ray radiolysis of cholesterol /3-hydroxy-5-cholestene/ /I/ in the two-phase system /water-ethyl acetate/ and in the presence of air has been studied using TLC and GC methods. The following products were observed in the irradiated mixture: 3, 7-dihydroxy-5-cholestene /II/, G O. 36, 3-hydroxy-7-keto-5-cholestene /III/, G 1.48, 3-hydroxy-7-keto-5-cholestane /IV/, G 0.22, 3,5,6-trihydroxy-5-cholestane /V/, G 0.83, 5,6-epoxy-3-hydroxy-5-cholestane /VIa/, G 0.26, 5,6-epoxy-3-hydroxy-5-cholestane /VIb/, G 0.24, and 2, 3-dihydroxy-5-cholestene /VII/, G 0.22. The dose dependence of the formation of these products shows that the cholesterol derivatives substituted in the position 7 /II–IV/ are formed from a common precursor — the radical Ia. On the other hand, the products of the 5–C=C double bond reactions /V and VI/ are formed independently. Also the product VII is formed independently. A reaction scheme that is in agreement with these results is proposed.     

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.     

New polyhydroxysteroids from the far-eastern starfish Henricia sp.

From the far-eastern starfishHenricia sp. we have isolated and characterized the new polyhydroxysteroid (24S)-5-cholestane-3,4,6,8,15,24-hexaol and three new glycosides: (24S)-5-cholestane-3,4,6,8,15,24-hexaol 3-O-(2,4-di-O-methyl--D-xylopyranoside) (henricioside H₁), 24-methyl-5-cholesta-4,22E-diene-3,6,8,15,16,26-hexaol 3-O-(2,3-di-O-methyl--D-xylopyranoside) (henricioside H₂), and the 22,23-dihydro derivative of henricioside H₂ (henricioside H₃).Pacific Ocean Institute of Bioorganic Chemistry, Far-Eastern Scientific Center, Russian Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 249–253, March–April, 1993.     

Triterpene Glycosides from Tragacantha stipulosa and Their Genins. Structure of Cyclostipuloside E

The known compound trojanoside A (1) and a new cycloartane glycoside cyclostipuloside E (2) were isolated from the aerial parts of Tragacantha stipulosa Boriss. The structure of cyclostipuloside E was proposed as 24R-cycloartan-3,6,16,24,25-pentaol 6,16,25-tri-O--D-glucopyranoside 3-O--D-xylopyranoside based.     

Gitoxigenin glycosides

Summary Three cardiac glycosides have been synthesized from gitoxigenin and D-glucose: gitoxigenin 3-O--D-glucopyranoside, gitoxigenin 16 -O- -D-glucopyranoside, and gitoxigenin 3, 16-di-O- -D-glucoside. The first glycoside, obtained with a yield of 49% on the weight of the initial aglycone, possesses a fairly high biological activity (0.25 mg/kg), while the other two, formed in a yield of about 0.3%, do not possess the action on the heart that is specific for the cardenolides.Khar'kov Chemical and Pharmaceutical Scientific-Research Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 45–49, January, 1971.     

Steroid saponins and sapogenins ofAllium IX. The structure of aginoside

Summary From a methanolic extract of the skins of the bulbs ofAllium giganteum Rgl, a new steroid glycoside has been isolated — aginoside, which is (25R)-5-spirostan-2, 3, 6-triol 3-0-{[0--D-xylopyranosyl-(13)-]-[0--D-glucopyranosyl-(12)]-0--D-glucopyranosyl-(14)-0--D-galactopyranoside}.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 480–486, July–August, 1976.     

Triterpene glycosides of Astragalus and their genins XXXIX. Cycloaraloside D from Astragalus amarus

The structure of a triterpene glycoside of the cycloartane series — cycloaraloside D, isolated from the roots ofAstragalus amarus Pall. (Leguminosae) — has been established on the basis of chemical transformations and spectral characteristics. Cycloaraloside D is 20R, 24S-epoxycycloartane-3, 6, 16, 25-tetraol 3-0-[0--L-rhamnopyranosyl-(1 2)--D-glucopyranoside].Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 526–528, July–August, 1991.     

Triterpene Glycosides of Fatsia japonica. VI. Structures of Glycosides D3a and D3b

Seeds of Fatsia japonica (Araliaceae) yielded the new glycosides of gypsogenin: 3-O--D-glucopyranosyl-(12)-O--D-glucopyranoside and 3-O--D-galactopyranosyl-(12)-O--D-glucopyranoside. The structures of these compounds were established by chemical methods and NMR spectroscopy.     

Ultrasonic study of the molecular encapsulation and the micellization processes of dodecylethyldimethylammonium bromide-water solutions in the presence of β-cyclodextrin or 2,6-di-o-methyl-β-cyclodextrin

Aqueous solutions of -cyclodextrin (-CD) or 2,6-di-o-methyl--cyclodextrin (DM--CD) and dodecylethyldimethylammonium bromide (D₁₂EDMAB) have been studied from speed of sound (u) data at 298.15 K, using a pulse-echo-overlap technique. The molecular encapsulation process of the surfactant monomer into the cyclodextrin cavity and its effect in the micellization process of the surfactant have been analyzed from theu measurements: I) as a function of [D₁₂EDMAB] in the presence of several initial cyclodextrin concentrations (-CD or.DM--CD); II) as a function of [cyclodextrin] (-CD or DM--CD), for an initial micellar solution of D₁₂EDMAB and; III) as a function of the [cyclodextrin]/[surfactant] stoichiometric concentrations. Both inclusion complexes formed (-CDD₁₂EDMAB) and (DM--CDD₁₂EDMAB) have stoichiometries of 11, and their association constantK have been determined using a model proposed in this work, based on the additivity of the different contributions of the involved species to the speed of sound. The apparent critical micellar concentration, cmc^*, of D₁₂EDMAB is found to increase linearly upon the addition of cyclodextrin (-CD or DM--CD). The free surfactant concentration in the micellar region, [D₁₂EDMAB]_f, decreases in the presence of -CD and slightly increases in the presence of DM--CD. The influence of the parcial methylation of the -cyclodextrin (-CDDM--CD) and of the polar head of the surfactant (D₁₂TAB D₁₂EDMAB) on the complextion and micellar parameters are also discussed.Supplementary material available: Tables of speed of sound (14 pages) are available from the authors.     

Oxidative transformations of labdane diols. III. Preparation of acids with a strobane skeleton from larixol

It has been shown that the oxidation of larixol with chromic acid mixture forms methyl 6-oxo-8,13-epoxystroban-14-oate, methyl 6-oxo-8,13-epoxystroban-14-oate, and 6,13-dioxo-14,15-bisnorlabd-7-en-17-oate.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 697–703, November–December, 1986.     

Thermal decomposition of phosphorylated hemimercaptals

Conclusions The reaction of diphenylchlorophosphine with ,,-trichloro--hydroxyethyl ethyl sulfide in the presence of triethylamine leads to the formation of -ethylthio-,,-trichloroethyl diphenylphosphonite. The reaction of diphenylchlorophosphine with dimethyl -hydroxy--propylthiophosphonate in the presence of triethylamine gives -propylthio--dimethylphosphonoethyl diphenylphosphonite. The phosphorylated hemimercaptals obtained are thermally unstable and decompose to S-alkyl diphenylthiophosphonites and the corresponding carbonyl compounds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2619–2621, November, 1985.     

Experimental study of particle-to-liquid mass transfer in two-phase fixed and fluidized beds

Primary experimental results for local particle-to-liquid mass transfer in two-phase fixed and fluidized beds and in free flows are reported. A hypothesis on the mechanism of the effect of turbulent pulsations is suggested.

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Chemistry and Structure of Diterpene Compounds of the Kaurane Series: IV.1 Acylation of Reduction Products of the Isosteviol Keto Group

Acetylation with acetic anhydride of (4,8,13)-16-hydroxy-13-methyl-17-norkaurane-18-carboxylic acid and its methyl ester, obtained by reduction of isosteviol and (4,8,13)-18-methoxycarbonyl-13-methyl-16-oxo-17-norkaurane, respectively, gives rise to (4,8,13)-16-acetoxy-13-methyl-17-norkaurane-18-carboxylic acid and (4,8,13)-16-acetoxy-18-methoxycarbonyl-13-methyl-17-norkaurane. The molecular and crystal structures of the compounds were established by X-ray diffraction.     

Transformed steroids. Communication 148. 1,3-Cycloaddition of diazomethane and diazoacetate to Δ15-17-ketoandrostane at normal and high pressures

Conclusions 1,3-Cycloaddition of diazomethane and ethyl diazoacetate to ¹⁵-17-ketoandrostane proceeds regio- and stereospecifically from the -region of the steroid molecule, The pyrazolinoandrostanes obtained were converted into the corresponding 15,16-cyclopropane derivatives.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1893–1898, August, 1985.     

Rearrangement ofα -trifluoromethyl-β-dialkylamino-β-fluoroacrylic acid N.N-dialkylamides

Conclusions When heated in the presence of a catalytic amount of BF₃ etherate,-trifluoromethyl--diethylamino--fluoroacrylic acid N, N-dimethylamide is reversibly isomerized to-trifluoromethyl--dimethylamino--fluoroacrylic acid N, N-diethylamide. The methyl esters of-trifluoromethyl--diethylammo--fluoroacrylic acid and-trifluoromethyl--phenoxy--fluoroacrylic acid N,N-dimethylamide are not isomerized under the same conditions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No.1, pp.137–141, January, 1976.     

Steroid saponins and sapogenins ofAllium. XVII. The structure of karatavioside C

A new furostanol glycoside — karatavioside C (I) has been isolated from a methanolic extract of the inflorescences ofAllium karataviense Rgl. (family Liliaceae). By the complete acid hydrolysis, enzymatic hydrolysis, methylation, and reduction of compound (I), and also by the reduction of yuccagenin (II), the structure of the glycoside (I) has been established as 25(R)-furost-5-ene-2, 3, 22, 26-tetrao] 26-0--D-glucopyranoside 3-0-{[0--D-glucopyranosyl-(12)][0--D-xylopyranoside-(13)]-0--D-glucopyranosyl-(14)--D-galactopyranoside.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 355–359, May–June, 1980.     

Effect of the medium on the oxidation of aliphatic monocarboxylic acids

Oxidation rates and k₂/k₆ ratios are given for some acids from propionic to lauric. The k₂/k₆ ratio is shown to be influenced by the electrostatic effect of the solvent. A linear dependence between the isodielectric values of k₂/k₆ and the number of methylene groups in the acid molecules is described.

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k₂/k₆ . k₂/k₆ k₂/k₆ .