Phytoecdysones ofRhaponticum integrifolium II. Integristerone A

Summary A new phytoecdysone — integristerone A — has been isolated from the flower heads ofRhaponticum integrifolium. It has been shown that it is 1,2,3,14,20R,22R,25-heptahydroxy-5-cholest-7-en-6-one.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 813–819, November–December, 1977.     

New terpenoid coumarins from Ferula tadshikorum

Summary Two new terpenoid coumarins — tadzhiferin (I) and tadzhikorin (II) — have been isolated from the fruit ofFerula tadshikorum M. Pimen.On the basis of physicochemical and spectral investigations, the structure of 7-(9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyloxy)coumarin is proposed for (I) and that of 7-(4-acetoxy-9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyloxy)coumarin for (II).All-Union Scientific-Research Institute of Medicinal Plants, Moscow. M. V. Lomonosov State University. Botanical Garden, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 593–599, September–October, 1976.     

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.     

Phytoecdysteroids ofSilene nutans. III. Nusilsterone

A new ecdysteroid — nusilsterone — has been insolated from the whole plantSilene nutans L. It has been shown that it is 1,2,3,14,20R,22R,24,25-octahydroxy-5--cholest-7-en-6-one.Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii. No. 4, pp. 522–525, July–August, 1985.     

Triterpene glycosides of Astragalus and their genins. XXIV. Cycloorbicoside G from Astragalus orbiculatus

A bisdesmosidic glycoside — cycloorbicoside G — has been isolated from the epigeal parts of the plantAstragalus orbiculatus Ledeb. (Leguminosae), and on the basis of chemical transformations and spectral characteristics its structure has been established as (23R,24S)-16,23;16,24-diepoxycycloartane-3,7,25-triol 25-O--D-glucopyranoside 3-O--D-xylopyranoside.Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 837–842, November–December, 1987.     

Steroid saponins and sapogenins ofAllium XI. Neoalliogenin fromAllium turcomanicum

Summary In addition to the known spirostans neoagigenin and alliogenin, we have isolated from the skins of the bulbs ofAllium turcomanicum Rgl. a new steroid sapogenin — neoalliogenin, which is (25S)-5-spirostan-2, 3, 5, 6-tetraol.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 823–826, November–December, 1977.     

2,3-Dihydroxypyridine Loaded Amberlite XAD-2 (AXAD-2-DHP): Preparation, Sorption–Desorption Equilibria with Metal Ions, and Applications in Quantitative Metal Ion Enrichment from Water, Milk and Vitamin Samples

2,3-Dihydroxypyridine loaded (via –N=N–linker) Amberlite XAD-2 (AXAD-2-DHP) was prepared and characterized by elemental analyses, TGA and FT-IR spectra. It (1g packed in a column of 1cm diameter; surface area 135.5m²g^–1) was found to be an effective solid phase sorbent for enriching Zn²⁺, Mn²⁺, Ni²⁺, Pb²⁺, Cd²⁺, Cu²⁺, Fe³⁺ and Co²⁺ at pH 3.5 to 7.0 using flow rates between 1.0–5.0mLmin^–1. For desorption (recovery 97.0–99.8%) of the metal ions, 8 to 10mL of 2.0molL^–1 HCl or 1.5molL^–1 HNO₃ at a flow rate of between 2.0 and 4.0mLmin^–1 were found most suitable. The t_1/2 (time for 50% sorption) is between 2 and 10min when a 50mL solution (containing a total amount of metal of 2mg) was equilibrated with 0.5g of resin. Sorption of all metal ions except Pb²⁺ follows the Langmuir model, whereas for Pb the data fits with the Freundlich model. The sorption capacity is between 60.7 (for Cd) and 406.7 (for Cu) µmolg^–1. The resin can withstand an acid concentration of 6molL^–1 and can be reused for thirty cycles of sorption–desorption. The preconcentration factor varies between 100 and 300. For Cd, Ni and Cu the sorption capacity of 2,3-dihydroxypyridine loaded cellulose is lower than that of the present resin. The tolerance limits of electrolytes, humic acid, complexing agents, Ca²⁺ and Mg²⁺ in the enrichment of all metal ions are reported. The limits of detection are 3.88, 5.37, 8.72, 13.88, 4.71, 1.24, 0.59 and 0.30µgL^–1 for Zn²⁺, Mn²⁺, Ni²⁺, Pb²⁺, Cd²⁺, Cu²⁺, Fe³⁺ and Co²⁺, respectively. The calibration curves for flame AAS determination were linear in the ranges 0.018–1.0, 0.067–5.0, 0.2–5.0, 0.9–20, 0.028–2.0, 0.077–5.0, 0.19–10 and 0.1–3.5µgmL^–1, respectively. All the eight metal ions in river and synthetic water samples, Co in vitamin tablets and Zn in milk samples have been quantitatively enriched with Amberlite XAD-2-DHP and determined by flame atomic absorption spectrometry.     

Triterpene glycosides ofAstragalus and their genins. XIV. Askendoside A fromAstragalus taschkendicus

A new glycoside of the cycloartane series — askendoside A — has been isolated from the roots ofAstragalus taschkendicus Bge. (family Leguminosae), and on the basis of chemical transformation and spectral characteristics its structure has been established as 3-[O--L-arabinopyranosyl-(12) -(3-O-acetyl--D-xylopyranosyl)-oxy]-24R-cycloartane-6, 16, 24, 25-tetraol.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 587–592, September–October, 1983.     

Proanthocyanidins ofPolygonum coriarium. IV. Structures of proanthocyanidins T3 and T4

Two oligomeric proanthocyanidins have been isolated from the roots ofPolygonum coriarium. By a study of their physical properties and spectral characteristics and analysis of the results of chemical transformations, the chemical structures of these compounds have been established as: (–)-epicatechin-77[O--D-glucopyranosyl]₃ O-⊃-D-glucopyranosyl (m-trigallolyl)-[(4-6)-(–)-epigallocatechin]₂-(4-6)-(–)-epigallocatechin—T3; and (–)-epicatechin-3-O-galloyl-7-[O--D-glucopyranosyl]₃O--D-glucopyranosyl galloyl-[(4-6)-(–)-epicatechin]₄-(4-6)-(–)-epigallocatechin — T4.The materials of this paper were presented at the IInd International Symposium on the Chemistry of Natural Compounds (SCNC), Eskiehir, Turkey, October 22–24, 1966).Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 707–713, September–October, 1997.     

Structure of 2,4,4,5,5‐pentamethyl‐2‐imidazoline‐1‐oxyl‐3‐oxide

The crystal and molecular structures of the stable nitroxide radical 2,4,4,5,5pentamethyl2imidazoline1oxyl3oxide was determined. The N—O bond lengths are 1.279(2) and 1.280(2), respectively. The O^-—N⁺=C—N— O fragment is nearly planar with carbon atoms of the ethyl fragment that deviated from the O—N⁺=C—N—O plane by –0.204(5) and +0.176(5). The minimum intermolecular distance between the oxygen atoms of NO groups is 4.094.     

Triterpene glycosides of Hedera taurica. III. Structures of hederosides A3, B,E2 and F from the berries of Crimean ivy

Four triterpene glycosides — hederoside A₃, B, E₂, and F — have been isolated from the berries ofHedera taurica Carr. (Crimean ivy), family Araliaceae. On the basis of the results of acid hydrolysis and physiochemical methods of investigation the following structures have been suggested: A₃ — 3-O-(-L-arabinopyranosyl)hederagenin; B — 3-O-(-D-glucopyranosyl)hederagenin; E₂ — 3-O-[O--D-glucopyranosyl-(1 2)--D-glucopyranosyl]oleanolic acid; and F — 3-O-[O--D-glucopyranosyl-(1 2)--D-glucopuranosyl]hederagenin. Hederoside E₂ is a new glycoside of oleanolic aid.M. V. Frunze Simferopol' State University. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 721–726, September–October, 1988.     

Adsorptive Catalytic Voltammetry of Physcion in the Presence of Dissolved Oxygen at a Carbon Paste Electrode

A novel electroanalytical method for the determination of physcion is described for the first time. Physcion yields an adsorption catalytic voltammetric peak at –0.74V (vs. SCE) in 0.4molL^–1 NH₄Cl–NH₃·H₂O buffer solution (pH 10.5) at a carbon paste electrode (CPE). The experimental results indicated that physcion is efficiently accumulated at a CPE by adsorption. In the subsequent potential scan, physcion was reduced to a homologous anthrahydroquinone compound. The compound was then immediately oxidized to physcion by the dissolved oxygen in the solution, and then physcion was again reduced at the CPE. As a result, a cyclic catalytic reaction was established. The second-order derivative peak current is proportional to the physcion concentration in the ranges of 2.0×10^–104.0×10^–9molL^–1 (accumulation 90s) and 4.0×10^–92.0×10^–8molL^–1 (accumulation 60s). The limit of detection is 8×10^–11molL^–1 (S/N=3) for a 120s accumulation time. The method was applied to the direct determination of physcion in the medicinal plant polygonum multiflorum Thumb with satisfactory results.     

Retro-michael reaction of 28-methoxy-18,19-secolupane-18,19-dione derivatives

The interactions with KOH in boiling diethyleneglycol of 3,28-dimethoxy- and 3-acetoxy-28-methoxy-18,19-secolupane-18,19-diones have been studied. In the first case, 3-methoxy-19,20,21,22,29,30-hexanor-18,19-seco(17H)lupan-18-one and the corresponding 18-ol were isolated from the mixture of products, and in the second case 3-hydroxy-19,20,21,22,29,30-hexanor-18,19-seco(17H)lupan-18-one — which was also obtained by an analogous reaction from 3-acetoxy-18,19-secolupan-18,19-dione — and 3-hydroxy-19,20,21,22,28,29,30-heptanor-18,19-secolupan-18-one. Thus, it has been found that in this case the retro-Michael reaction is accompanied by 28-demethoxylation and partially by 28-demethoxy-methylation.Pacific Ocean Institute of Bioorganic Chemistry, Far-Eastern Branch, Russian Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 210–215, March–April, 1992.     

Oligomeric proanthocyanidin glycosides ofClementsia semenovii. II

The structures of proanthocyanidins CS-3 and CS-4, isolated from the roots ofClementsia semenovii have been established on the basis of chemical and spectral studies. CS-3 is 7-O-(6-O-galloyl--D-Glcp O--D-Glcp O--D-Glcp O--D-Glcp O--D-Glcp)-(+)-catechin-(4—8)-(–)-epigallocatechin-(4—8)-(+)-catechin-(4—8)-(–)-epigaLLocatechin-(4—8)-(–)-epigallocatechin-(4—8)-(–)-epigallocatechin, and CS-4 is 3-O-galloyl-7-O-[6-O-galloyl--D-Glcp O--D-Glcp O--D-Glcp-(+)-gallocatechin-(4—8)-[(+)-catechin-(4—8)-(3-O-galloyl-(–)-epigallocatechin]₂-(4—8)-(–)-epicatechin.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 50–58, January–February, 1999.     

Cardiac glycosides of theCheiranthus allioni. XII

The seeds ofCheiranthus allioni hort. have yielded three new cardenolides the structures of which have been established and which have been named as 4-dehydrosarmentogenin (II), 4-dehydrosarmentogenin rhamnoside (I), and 4-dehydrosarmentogenin rhamnoglucoside (IV). (II) — C₂₃H₃₂O₅. m.p. 296–302°, [] _D ²⁰ +26.2±3° (in pyridine) is 3,11,14-trihydroxy-14-card-4,20(22)-dienolide. (I) C₂₉-H₄₂O₉, m.p. 268–275°, [] _D ²⁰ –38.2±3° (chloroform-ethanol) is 11,14-dihydroxy-3--L-rhamnopyranosyloxy-14-card-4,20(22)-dienolide.(IV) C₃₅H₅₂O₁₄, [] _D ^20D –44.1±3° (methanol), is 3-(4-O--D-glucopyranosyl--L-rhamnopyranosyloxy)-14-card-4, 20(22)-dienolide. An independent synthesis of 4-dehydrosarmentogenin (II) has been carried out, starting from 3,5,11,14-tetrahydroxy-5,14-card-20(22)-enolide, which has confirmed its structure.For Communication XI, see [1].All-Union Scientific-Research Drug Institute, Kharkov. Kharkov State Pharmaceutical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 119–125, January–February, 1987.     

Tripenoid glycosides of alfalfa. VII. Medicosides E and F

Two hederagenin glycosides — medicosides E and F — have been isolated from the roots ofMedicago sativa L. (Leguminosae). Medicoside E has the structure of hederagenin 28-O--D-glucopyranoside 3-O-[O--G-glucopyranosyl-(13)--D-xylopyranoside]. Medicoside F has the structure of hederagenin 28-O--D-glucopyranoside 3-O-[O--D-glucopyranosyl-(12)--L-arabinopyranoside].Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent. Institute of Organic Chemistry, Russian Academy of Sciences, Moscow. Translated from Khimiya Prirodnykh Soedinenii. No. 5, pp. 701–705, September–October, 1993.     

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.