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.     

Structural Studies on Host + Guest Recognition Sensory Systems

Rhodamine B-ethylenediamine--cyclodextrins (RhB--CDen) and rhodamine B--cyclodextrins (RhB--CD) can form inclusive complexes with many guest molecules, a reaction which can be used as a nucleic acid probe. In this paper, the most stable conformations of RhB--CDen and RhB--CD have been determined by fluorescence experiments and analyzed by molecular modeling simulation. The interaction between RhB--CDen and two guest molecules, 1-borneol and cyclohexanol, has also been investigated. The results showed that RhB--CDen has a stronger interaction with 1-borneol than with cyclohexanol. Borneol could push the three aromatic-rings of rhodamine B out of the CD cavity, while the cyclohexanol could not. The interactive sites of host and guest are also presented.     

Die γ-Bestrahlung von synthetischem β-Carotin

Zusammenfassung Das feste -Carotin ist gegen -Strahlung ziemlich stabil. Bei Bestrahlung unter Sauerstoffbegasung treten deutliche -Carotin-Verluste erst bei der hohen Dosis von 12 Mrad auf; bei Bestrahlung an der Luft werden ähnliche Radiolyseerscheinungen erst durch wesentlich höhere Strahlendosen ausgelöst. Spaltungsprodukte, die bei 12 Mrad und Sauerstoffbegasung auftraten und dünnschichtchromatographisch aufgetrennt werden konnten, waren Isozeaxanthin, -Carotin-5,6-5, 6-diepoxid, -Carotin-5,8-5,8-diepoxid, -Apo-12-carotinal, -Apo-10-carotinal, 3,3,6-Trihydroxy--carotin-5,8-epoxid und Vitamin-A-Alkohol. Es ist bemerkenswert, daß ein Teil der Radiolyseprodukte (z. B. Vitamin-A₁-Alkohol, -Apo-12-carotinal und -Apo-10-carotinal) Vitamin-A-Wirksamkeit besitzt.

---

The -Irradiation of synthetic -carotene. Some physico-chemical and thin-layer chromatographic studies of radiolysis products

Solid -carotene is remarkably stable to -irradiation. In an oxygen atmosphere doses as high as 12 Mrad were required to bring about significant losses of -carotene, whereas in air even larger doses had to be applied in order to effect a comparable degree of radiolysis. Cleavage products which arose in O₂ at a dose of 12 Mrad and which could be separated from each other by thin-layer chromatography were isozeaxanthin, -carotene-5,5-5,6-diepoxide, -apo-12-carotenal, -apo-10-carotenal, 3, 3, 6-trihydroxy--carotene-5,8-epoxide and vitamin A₁. It is notable that some of the radiolysis products (e.g., vitamin A₁, -apo-12-carotenal and -apo-10-carotenal) possess vitamin A activity.

---

---

Herrn Prof. Dr.O. Hromatka zum 65. Geburtstag gewidmet.     

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.     

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.     

Steroids of the spirostan and furostan series from Nolina microcarpa IV. Structures of nolinogenin,nolinospiroside B,and nolinofuroside B

A glycoside has been isolated from the plantNolina microcarpa S. Wats. (family Dracaenaceae) which has been called nolinofuroside B and has the structure of 6-methoxy-3,5-cyclo-(25S)-furostan-1,22,26-triol 1-O--D-fucopyranoside 26-O--D-glucopyranoside (I). Enzymatic hydrolysis of the bioside (I) yielded nolinospiroside B (III) and nolinogenin (IV). The latter is 6-methoxy-3,5-cyclo-(25S)-spirostan-6-ol, and glycoside (III) is its 1-O--D-fucopyranoside.M. V. Frunze Simferopol' State University. Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 218–224, March–April, 1992.     

Triterpeneglycosides of Astragalus and their genins. XXV. Cyclocanthoside D from Astragalus tragacantha

The epigeal part of the plant ofAstragalus tragacantha Habl. (Leguminosae) has yielded, together with cyclosieversigenin 3-O--D-xylopyranoside, a new glycoside of the cycloartane series — cyclocanthoside D, the structure of which has been established on the basis of chemical transformations and spectral characteristics as 24S-cycloartane-3,6,16,24,25-pentaol 16-O--D-glucopyranoside 3-O--D-xylopyranoside.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 73–76, January–February, 1988.     

Arjunolic acid derivative glycoside from the stems of <Emphasis Type="Italic">Hedera colchica</Emphasis>

Five triterpenoid saponins were isolated from the stems of Hedera colchica K. Koch, Araliaceae. Two of them are new natural substances. HCSt-A (1): 3-O--D-arabinopyranoside; 28-O--L-rhamnopyranosyl-(1 4)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl-arjunolic acid. HCSt-B (2): 3-O--D-xylopyranoside; 28-O--L-rhamnopyranosyl-(14)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl-hederagenin. The derivative of arjunolic acid is described for the first time in Araliaceae family. The chemical structures of isolated compounds were established on the base of chemical and 1D and 2D NMR experiments.Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 461–463, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

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.     

Steroids of the furostan and spirostan series from Nolina microcarpa II. structures of nolinospiroside D and nolinofurosides D, E, and F

Proofs are given of the structures of two new glycosides of the furostan series isolated from the leaves of the plantNolina microscarpa S. Wats. (family Dracaenaceae). Nolinofuroside D is (25S)-furost-5-ene-1,3,22,26-tetraol 1-O--D-galactopyranoside 26-O--D-glucopyranoside (I), and nolinofuroside F is (25S)-furost-5-ene-1,3,22,26-tetraol 1-O--D-fucopyranoside 26-O--D-glucopyranoside 3-O--L-rhamnopyranoside (VII). The latter was characterized as its 22-O-methyl ether (VIII). Nolinofuroside E (IV) has the structure of (25S)-furost-5-ene-1,3,22,26-tetraol 26-O--glucopyranoside 1-O-[O--L-rhamnopyranosyl-(12)--D-fucopyranoside], which followed from the structure of the fermentation product (VI). The products of the fermentation of the above-named compounds were present in the plant in only trace amounts. Only one of them — nolinospiroside D (III) — has not been described previously. This monoside of the spirostan series is (25S)-spirost-5-ene-1,3-diol 1-O--D-galactopyranoside.M. V. Frunze Simferopol' State University. Institute of Chemistry of Plant Substances, Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 678–686, September–October, 1991.     

Hydrogenation of xylenes over supported Pt catalysts. Influence of different variables on their catalytic activity

In this work we studied and compared the catalytic activity of various supported Pt systems on the gas-phase hydrogenation of o-, m- and p-xylene. We analyzed the influence of different catalyst preparation variables (solvent, precursor, salt, support and catalyst reduction temperature used) on the catalytic activity and selectivity towards the corresponding cis-and trans-dimethylcyclohexanes.

---

- o-, m- -. (, , ) - -.

     

Temperature programmed reduction and oxidation of Ir/Al2O3 catalysts

3 % Ir/Al₂O₃ catalysts have been studied by means of temperature programmed reduction and oxidation. With growing degree of metal oxidation (higher T_ox) reducibility of the catalysts at low temperatures decreases.

---

3% Ir/Al₂O₃ . ( ) .

     

New cardenolides from the seeds ofCoronilla hyrcana

Summary Four substances have been isolated from the seeds ofCoronilla hyrcana: hyrcanoside, deglucohyrcanoside, hyrcanogenin, and substance E.It has been established that hyrcanoside (I) has the structure 3-(O--D-xylopyranosyl- <4 1 > -O--D-glycopyranosyl)-14-hydroxy-19-oxocard-4, 20 (22)-dienolide; deglucohyrcanoside (VII) is 3-(O--D-xylopyranosyl)-14-hydroxy-19-oxocard-4, 20 (22)-dienolide; and hyrcanogenin (V) is 3, 14-dihydroxy-19-oxocard-4, 20 (22)-dienolide. Both the aglycone hycanogenin (V) and its glycosides (I) and (VII) are new compounds.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 4, pp. 251–257, 1966     

Alkaloids of the Monolian flora. IV. Turcosine — A new alkaloid from Aconitum turczaninowi

As the result of a further study of the total alkaloids from the epigeal part ofAconitum turczaninowi we have isolated beiwutine and delcaroline and also a new alkaloid, which has been called turcosine. The structure of turcosine as 6,16-dimethoxy-4-methoxymethyl-1,7,8,10,14-pentahydroxy-N-ethylaconitane has been shown from a study of the IR, mass, PMR, and¹³C NMR spectra of the alkaloid and of the triacetate obtained from it.Institute of Chemistry, Mongolian People's Republic Academy of Sciences. Institute of the Chemistry of Plant Substances, Uzbekistan Republic Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedeninii, No. 1, pp. 60–62, January–February, 1993.     

Triterpene glycosides of Astragalus and their genins XXX. Cycloaraloside A from Astragalus amarus

In addition to -sitosterol, cyclosieversigenin, and -sitosterol -D-glucopyranoside, the roots of the plantAstragalus amarus Pall. (Leguminosae) have yielded a new triterpene glycoside of the cycloartane series — cycloaraloside A, which has the structure of 2OR,24S-epoxycycloartane-3,6,16,25-tetraol 3-O--D-glucopyranoside.Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 806–809, November–December, 1989.     

Minor polyhydroxysteroids from the starfish Crossaster papposus

Minor polyhydroxysteroids from the starfishCrossaster papposus have been isolated and characterized: 5-cholestane-3,6,8,15,16,26-hexanol and 24-methyl-5-cholesta-14,22E-diene-3,6,8,26-tetraol 26-O-(3-O-methyl--D-glucopyranoside) (crossasteroside P₃). The structures of the compounds were established on the basis of spectral methods.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, p. 218–221, March–April, 1990.     

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.     

Coronillobiosidol — A cardenolide glycoside from seeds of Coronilla scorpioides

The seeds ofCoronilla scorpioides have yielded a new cardenolidic bioside, which has been called coronillobiosidol and has the structure of 3-O-[O--D-glucopyranosyl-(1 4)--D-glucopyranosyl]-14, 19-dihydroxy-5-card-20(22)-enolide.Khar'kov State Pharmaceutical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 726–728, September–October, 1988.