Triterpene glycosides of the holothurian Eupentacta pseudoquinquisemita

The holothurianEupentacta pseudoquinquisemita Deichmann collected in Kraternaya Bay, Ushishir Islands has yielded two triterpene pentaosides — the previously known cucumarioside C₂, and cucumarioside H, which is a new glycoside. With the aid of¹³C NMR spectroscopy and solvolytic desulfation its structure has been determined as 6-acetoxy-3-([3-O-methyl--D-xylopyranosyl-(1 3)--D-glucopyranosyl-(1 4)] [-D-xylopyranosyl-(1 4)] [-D-xylopyranosyl-(1 2)]--D-quinovopy-ranosyl-(1 2)-(4-O-sulfato--D-xylopyranosyloxy)holosta-7,22,24(trans)-triene. Cucumarioside H was also identified inEupentacta (=Cucumaria)fraudatrix from Posyet Bay, Sea of Japan.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 221–225, March–April, 1988.     

Triterpene glycosides ofHedera canariensis IV. Structures of glycosides L-F3, L-G0, and L-Gla from the leaves of Algerian ivy

Three minor partially acetylated glycosides have been isolated from the leaves of Algerian ivy, Hedera canariensis Willd. (Araliaceae) — the previously known {3-O-[-L-rhamnopyranosyl-(12)-O--L-arabinopyranoside] 28-O-[-L-rhamnopyranosyl-(14)-O-(6-acetyl--D-glucopyranosyl)-(16)-O--D-glucopyranoside}s of oleanolic acid and of hederagenin (ciwujianoside C₄ and kizuta saponin K₁₁) and the new 3-O-[-L-rhamnopyranosyl-(12)--O-L-arabinopyranoside] 28-O-[-L-rhamnopyranosyl-(14)-O-(6-O-acetyl--D-glucopyranosyl)-(16)-O--D-glucopyranoside of echinocystic acid (glycoside L-G₀). The structures of the glycosides isolated have been established on the basis of chemical transformations and¹H and¹³C NMR spectroscopy.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 81–86, January–February, 1999.     

Triterpene glycosides from Pulsatilla chinensis

Four triterpene glycosides were isolated from the roots of Pulsatilla chinensis (Bunge) Regel (Ranunculaceae). Two new glycosides, chinensiosides A (1a) and B (2), were identified as 3-O-[-L-rhamnopyranosyl-(12)--L-arabinopyranosyl]-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid and 3-O-{-L-rhamnopyranosyl-(12)-[-D-glucopyranosyl-(14)]--L-arabinopyranosyl}-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid. The other two glycosides were identified as previously known hederasaponin C (3) from Hedera helix and glycoside III (4) from Pulsatilla cernua.     

Triterpene glycosides of Hedera taurica. IV. Structure of hederosides A1, A2, D1, and D2 from the berries of Crimean ivy

New triterpene glycosides have been isolated from the berries of Crimean ivyHedera taurica Carr. (family Araliaceae) — hederoside A₁ (methyl ester of 3-O--D-glucopyranosylhederagenin) and hederoside D₁ 3-O-[O--D-glucopyranosyl]-(12)--D-glucopyranosyl]hederagenin and also the known glycosides 3-O--D-glucopyranosyloleanolic acid and 3-O-[O--D-glucopyranosyl-(12)--L-arabinopyranosyl]hederagenin. The structures of these compounds were established on the basis of the results of chemical methods and¹H and¹³C NMR spectroscopy.M. V. Frunze Simferopol' State University. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 228–230, March–April, 1990.     

Coumarin glycosides ofHaplophyllum performatum. structures of haploperosides C,D, and E

New coumarin glycosides — haploperosides C, D, and E — have been isolated from the epigeal part of theHaplophyllum performatum (MB) Kar et Kir. On the basis of chemical transformations and spectral characteristics, haploperoside D has the structure of 6-methoxy-7-[0--L-rhamnopyranosyl-(1 2)--D-glucopyranosyloxy]-2H-benzopyran-2-one, and haploperoside C that of 6-methoxy-7-[0--L-rhamnopyranosyl-(1 6)-(2-0-acetyl--D-glucopyranosyloxy)]-2H-benzopyran-2-one. The structure of haploperoside E has been established as 7-[0--L-rhamnopyranosyl-(1 2)-0--L-rhamnopyranosyl-(1 6)--D-glucopyranosyloxy]-2H-benzopyran-2-one. The structures of haploperosides A and B have been refined. An assignment has been made of the carbon signals in the¹³C NMR spectra of haploperosides A, D, C, and E.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 27–35, January–February, 1985.     

Triterpene glycosides ofHedera canariensis. I. Structures of glycosides L-A,L-B1, L-B2, L-C,L-D,L-E1 1, L-G1, L-G2, L-G3, L-G4, L-H1, L-H2, AND L-I1 from the leaves ofHedera canariensis

From the leaves of Algerian ivyHedera canariensis Willd. (fam. Aralaceae) we have isolated 13 triterpene glycosides: the 3-O--L-arabinopyranosides of oleanolic acid (A), of echinocystic acid (B₁), and of hederagenin (B₂); the 3-O-[O--L-rhamnopyranosyl-(2)--L-arabinopyranoside]s of oleanolic acid (C), of echinocystic acid (D), and of hederagenin (E₁); the 3-O--L-rhamnopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--gentiobioside of hederagenin (G₁); the 3-O-[O--L-rhamnopyranosyl-(12)--L-arabinopyranoside] 28-O--gentiobioside of hederagenin (G3); the 3-O-[O--L-rhamnopyranosyl-(12)--L-arabinopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--gentiobioside]s of oleanolic acid (G₂), of echinocystic acid (H₁), and of hederagenin (H₂); the 3-O-[O--L-rhanmopyranosyl-(12)--D-glucopyranoside] 28-O-(O--L-rhamno-pyranosyl-(14)--gentiobioside] of hederagenin (H₂); and the 3-O-(O--L-rhamnopyranosyl-(12)-O-gentiobiosyl)-O-(14)--L-rhamnopyranosyl-(12)-a-L-arabinopyranoside] of hederagenin (G₄). The structures of the substances isolated have been established on the basis of chemical transformations and¹³C NMR spectroscopy.Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 377–383, May–June, 1996. Original article submitted December 3, 1995.     

Glycosides of marine invertebrates. Structure of holothurin A2 from the holothurianHolothuria edulis

The structure of a new glycoside fromHolothuria edulis, holothurin A₂, has been established with the aid of periodate oxidation, methylation, Smith degradation, and¹³C NMR spectroscopy. The structure of the glycoside has been determined as holost-9(11)-ene-3,12,17-triol 3-0-{2-0-[3-0-methyl--D-glucopyranosyl-(13)-0--D-glucopyranosyl-(14)-0--D-quinovopyranosyl]-4-0-sulfate--D-xylopyranoside}.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 215–219, March–April, 1982.     

New data on the structure of laminaran fromChorda filum (L.) Lam. and reserve glucans from other brown algae

M-chains of highly branched (13),(16)--D-glucan (laminaran) isolated previously from the brown algaChorda filum contain 1-glucosylated and 1,6-bis-glucosylatedD-mannitol residues, as shown by methylation analysis and enzymolysis. The latter structural element is found in laminarans for the first time. Structural investigation of laminarans from six other brown algae shows that the polysaccharides consist predominantly of (13)-linked -D-glucopyranose residues with a small number of (16)-glycosidic bonds in chains and branching points. Mannitol residues was not detected in laminarans from twoCystoseira species.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1660–1664, September, 1993.     

Structure électronique de la formamide et de l'urée

Résumé La structure électronique de la formamide et de l'urée est étudiée par la méthode L.C.A.O. améliorée. L'énergie de transition N V obtenue pour la formamide (7,3 eV) est en bon accord avec la valeur expérimentale (7,2 eV). La première transition N V de l'urée se situe vers 7,5 eV. Expérimentalement la valeur de celle-ci n'est pas connue, cependant ce résultat paraît correct par comparaison avec les énergies de transition dans la série des dérivés thio correspondants.

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The electronic structure of formamide and urea is studied by the improved LCAO method. The N V transition energy obtained for formamide (7,3 ev) agrees well with the experimental value (7,2 ev). The first urea N V transition should lie at 7,5 ev. An experimental value for it is not known, but this result seems to be correct in view of the transition energies in the corresponding thio derivatives.

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Zusammenfassung Die Elektronenstruktur des Formamids und des Harnstoffs wird mit Hilfe des verbesserten LCAO-Verfahrens untersucht. Die für den N V-Übergang des Formamids berechnete Energie (7,3 eV) stimmt gut mit dem experimentellen Wert (7,2 eV) überein. Der erste N V-Übergang des Harnstoffs sollte bei 7,5 eV liegen. Ein experimenteller Wert dafür fehlt: jedoch scheint der Wert im Vergleich mit den Anregungsenergien der entsprechenden Thioderivate vernünftig zu sein.

     

Excited Π states of divinyl chalcogenides and chalcophenes

Electron transitions in divinyl chalcogenides (CH₂=CHXCH=CH₂, where X is S, Se, or Te) have been analyzed using UV absorption spectra of dialkyl and alkyl vinyl chalcogenides. The following relations for the orbital energies are found: ^* < ^* < ^* < ^* for Te and ^* < ^* < ^* < ^* for S and Se. For chalcophenes, a correlation between the energy of the excited state (E ^*) of specific symmetry, the ionization potential (I) and the electron affinity (EA) is obtained:E ^*=const+(I+EA)/2. The electron affinity of divinyl chalcogenides is estimated. The correlation between the excited ^* states of divinyl chalcogenides and chalcophenes is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 831–835, May, 1994.     

Origin of the conical intersection between the singlet ionic excited surfaces of twisted ethylene

The potential surfaces of the two valence ionic singlet excited states of twisted ethylene are known to exhibit a conical intersection for a twist angle of the double bond near 82°, and no pyramidalization of the CH₂ groups. The factors responsible for the stabilization of the symmetric excited state near 90° are shown to be ( )² and ( ^*)² double excitations. The analysis is performed in the Quasi Degenerate Perturbation Theory formalism. The analogy with the ¹ A _g ³ B _u ordering problem of the diradical ground and lower triplet states through a double spin polarization of the system is established.     

Structures of some lilioglycosides from the bulbs ofLilium regale

Six steroid glycosides, which gave been called lilioglycosides B, C, E, F, H, and I have been isolated from fresh bulbs ofLilium regale Wills. The structure of each compound has been determined by methods of physicochemical analysis. This is the first time that lilioglycosides B, C, H, and I, have been described; they are, respectively: (25S)-spirost-5-ene-3,27-diol3-O--D-glucopyranoside; (25R)-spirost-5-ene-3,27-diol3-O--D-glucopyranoside27-(3-hydroxy-3-methylglutarate); (25S)-spirost-5-ene-3,27-diol3-O-{[O--L-rhamnopyranosyl-(12)],[O--D-glucopyranosyl-(13)]--D-glucopyranoside}; and (25S)-spirost-5-ene-3,27-diol 3-O-{[O--L-rhamnopyranosyl-(12)],[O--D-glucopyranosyl-(13)]-O--D-glucopyranoside} 27-[(S)-3-hydroxy-3-methylglutarate].Institute of Genetics, Academy of Sciences of the Republic of Moldava, 2002, Kishinev, ul. Padurilor, 20. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 841–847, November–December, 1997.     

Triterpene glycosides of alfalfa. III. Medicoside I

On the basis of chemical transformations and with the aid of physicochemical results, the structure of glycoside I isolated from the roots of the plantMedicago sativa has been established as hederagin 3-O-[O--L-arabinopyranosyl-(1 2)--D-glucopyranosyl-(1 2)--L-arabinopyranoside] 28-O--D-glucopyranoside. Compound (I), C₅₂H₈₄O₂₂, mp 210–212°C, [] _D ²¹ +38.4° (c 1.48; methanol). Acid hydrolysis of (I) led to hederogenin (II) — C₃₀H₄₈O₄, mp 326–330°C, [] _D ²³ +84.2° (c 0.19; pyridine. The Hakomorimethylation of glycoside (I) yielded the permethylate (IV) — C₆₅H₁₁O₂₂ [] _D ²³ +41.6° (c 1.79; methanol). The GLC analysis of the products of the methanolysis of compound (IV) showed the presence of 3,4,6-tri-O-methyl-D-glucopyranose, 2,3,4,6-tetra-O-methyl-D-glucopyranose, 3,4-di-O-methyl-L-O-arabinopyranose, and 2,3,4-tri-o-methyl-L-arabinopyranose. The alkaline hydrolysis of glycoside I gave compound (III) with mp 230–233°C, [] _D ²¹ +35.2° (c 0.21; methanol), which was identified as medicoside C. Details of the PMR spectrum are given for compound (IV) and of the IR spectrum for compound (I).Institute of the Chemistry of Plant Substances of the Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 607–610, September–October, 1986.     

Metal bioaccumulation by the freshwater algaScenedesmus quadricauda

Bioaccumulation of six metals (Cu²⁺, Cu⁺, Mo⁶⁺, Mn²⁺, V⁵⁺, Ni²⁺) and their combinations by algaScenedesmus quadricauda was determined by using radio nuclide X-ray fluorescence (RXFA). The metals were added into the cultivation medium in concentrations corresponding with EC₅₀ value for each metal. The obtained results indicate that Ni²⁺, Cu²⁺ and Cu⁺ were accumulated in high amounts (20%, 17.5% and 15.19%) the Mo⁶⁺ ion (<0.2%) was accumulated in the lowest amount. For metal-metal interactions in accumulation of metal ions by algaS. quadricauda three types of answers were determined: inhibition (MoCu²⁺, Ni, Mn, V; VNi, Mn; MnNi, Cu²⁺, Cu⁺; Cu⁺Ni; Cu²⁺Ni; NiMn, V), enhancement (VCu⁺; Cu²⁺Mn;Cu⁺V, Mn; MnV; NiCu²⁺, Cu⁺) and neutral effect (VMo; Cu²⁺Mo; Cu⁺Mo; MuMo; NiMo).     

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.     

The influence of solvation on the calculated activation energy for the reaction CH3F+F−

The influence of the solvent on the activation energy of the synchronous, concerted, narcissistic reaction: CH₃F + F^–¦CH₃F₂&#x00A6;^–FCH₃+F^–, has been investigated by means of CNDO/2 method. The reaction path has been fully followed in vacuo, and at a suitable point only, of reaction coordinate, in solution. The geometries of H₂O, F^–, CH₃F, and ¦CH₃F₂¦^–, in vacuo and in different hydrated cages, have been optimized.

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Zusammenfassung Der Einfluß des Lösungsmittels auf die Aktivierungsenergie der synchronverlaufenden Reaktionen CH₃F+F^–¦CH₃F₂¦FCH₃+ F^–, wurde mit der CNDO/2 Methode geprüft. Der Reaktions-Ablauf wurde in Vakuum vollkommen und in der Lösung an einem geeigneten Punkt der Reaktionskoordinate durchgeführt. Die Geometrien von H₂O, F^–, CH₃F, und ¦CH₃F₂¦^– im Vakuum und in verschiedenen hydrierten Käfigen wurden optimalisiert.

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Résumé L'influence du solvent sur l'énergie d'activation de la réaction synchronique, concertée, narcissistique: CH₃F+ F^–¦CH₃F₂¦^–FCH₃+F^– a été examinée par la méthode CNDO/2. On a suivie l'entier chemin de réaction in vacuo, alors qu'on a observé un seul point convenable de la coordonée de réaction en solution. On a optimize les geometries de H₂O, F^–, CH₃F, et ¦CH₃F₂¦^– in vacuo et en differentes cages hydratés.

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Financial aid from Italian Centro Nazionale delle Ricerche is gratefully acknowledged.     

Recherches théoriques sur la structure électronique de molécules contenant des atomes hybridés en sp:

Résumé La théorie L. C. A. O. améliorée est appliquée à l'étude de la molécule C₃. Afin de satisfaire l'égalité nécessaire entre les éléments de matrice non diagonaux L _pq et L _qp, nous avons introduit un déplacement électronique le long des liaisons . Les charges nettes portées par les atomes terminaux sont: + 0,09. La distance C-C calculée (1,286 Å) est en bon accord avec l'expérience. Les énergies des deux premières transitions NV: ¹ _g ^{+ 1} _u ^– et¹ _g ^{+ 1}_u sont: 4,7 et 4,8 eV. Ces valeurs ne sont pas en contradiction avec l'expérience qui situe ces transitions au delà de 4,1 eV, limite à partir de laquelle l'absorption de l'atmosphère terrestre rend impossible l'étude des spectres cométaires.

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The improved LCAO theory is applied to the C₃ molecule. In order to satisfy the necessary equality between the non-diagonal matrix elements L _pq and L _qp, we have introduced an electron shift along the bonds. The net charges borne by the terminal atoms are: + 0.09. The computed C-C distance (1.286 Å) is in good agreement with experiment. The two first NV transition energies: ¹ _g ^{+ 1} _u ^– and ¹ _g ^{+ 1}_u are: 4.7 and 4.8 eV. These values are not in contradiction with experiment which places these transitions beyond 4.1 eV, limit from which the terrestrial atmospheric absorption makes impossible to study the comets' spectra.

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Zusammenfassung Die verbesserte LCAO-Theorie wird auf die C₃-Molekel angewandt. Um die nötige Gleichheit der nicht-diagonalen Matrixelemente L _pq und L _qp zu erhalten, haben wir eine Elektronenverschiebung längs der -Bindungen eingeführt. Die Ladungen der Endatome sind: + 0,09. Die berechnete C-C-Bindungslänge (1,286 Å) stimmt mit der Erfahrung überein. Die berechneten Energien der zwei ersten NV-Übergänge: ¹ _g ^{+ 1} _u ^– und ¹ _g ^{+ 1}_u sind: 4,7 und 4,8 eV. Diese Werte sind nicht in Widerspruch mit der Erfahrung, die diese Übergänge über 4,1 eV ansetzt; denn das Stadium der Kometenspektren ist über dieser Grenze wegen der Luftabsorption unmöglich.

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Nous remercions le Professeur P. Swings (Institut d'Astrophysique, Cointe-Sclessin, Belgique) ainsi que le Professeur Ch. Fehrenbach (Observatoire de Marseille), pour les échanges de vue que nous avons eu avec eux sur ce sujet.     

New triterpene glycoside from the holothurianNeothyonidium magnum

The main component of the triterpene glycosides from the holothurianNeothyonidium magnum — neothyonidioside C — has been isolated and its structure has been determined by physical and chemical methods as 16-acetoxy-3-[O-(3-O-methyl-6-O-(sodium sulfato)--D-glucopyranosyl-(1 3)-O--D-xylopyranosyl-(1 4)-O--D-quinovopyranosyl-(1 2)-(4-O-(sodium sulfato)--D-xylopyranosyloxy)]holosta-7,25-diene.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 53–57, January–February, 1990.     

Hypothetical transformation of Ca(OH)<Subscript>2</Subscript> into CaCO<Subscript>3</Subscript> in solid-state reactions of portland cement

Summary Previous study of the hydration and ageing products of two cement pastes created the basis for the postulate of the course of solid-state reactions between the portlandite Ca(OH)₂ and the CO₂ from air in the hydrated and air dry cement. XRD basal spacing d(001) of portlandite exceeded the nominal value and increased with ageing, with the wetting and drying procedure and with carbonate content of the paste, indicating that a part of OH^- ions was gradually substituted by CO₃^2- ions, which are about twice bigger. IR spectroscopy showed a considerable content of portlandite, of CO₃^2- of water and silicates. Also HCO₃^- H₂O and CO₂ in cavities between hexagonal rings and hexagonal hydrates were indicated. By MS (mass spectrometry) in vacuum the evaporation of sorbed water was detected at 100-120°C, of gel water at 350°C of portlandite water at 400°C and of high temperature water between 500 and 700°C, simultaneously with CO₂ escape. Slightly higher peak temperatures were found by the TG test either in air or in argon. From these results and from geometric considerations it is postulated that the solid-state reactions take place on ageing of the cement paste and on its heating: hexagonal portlanditecalcium carbonate hydroxy hydratecalcium carbonate hydratehexagonal vaterite and/or orthorhombic aragoniterhombohedral calcite The analysis of the standard files of the calcium carbonate hydroxy hydrates supports this postulate and indicates a gradual transformation.     

Triterpene glycosides ofCauliphyllum robustum. The structures of caulosides B and C

Summary Two triterpene glycosides — caulosides b and c — have been isolated from a methanolic extract of the leaves ofCaulophyllum robustum maxim. Cauloside b has been identified as hederagenin 3--L-rhamnopyranosyl-(12)--L-arabinopyranoside, while cauloside c has the structure of hederagenin 3-0--L-arabinopyranosyl(13)--L-pyranosyl-(12)--L-arabinopyranoside.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center of the Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 174–176, March–April, 1979.