Triterpene glycosides ofHedera taurica XV. Structures of glycosides St-I3, St-I4a, St-I4b, and St-I5 from the stems of Crimean ivy

From the stems of Crimean ivyHedera taurica Carr. (fam. Araliaceae) we have isolated the new triterpene glycosides St-I₃, St-I₅, and St-I_4a, which are, respectively, the 3–0--D-glucopyranoside 28-O-[O--L-rhamnopyranosyl-(14)-O-(6-O-acetyl--D-glucopyranosyl)-(16)-O--D-glucopyranosides] of oleanolic acid and of hederagenin and the 3-O--D-glucopyranuronoside 28-O--gentiobioside of oleanolic acid, and also the previously known 3-O-[O--D-galactopyranosyl-(12)--D-glucopyranuronoside 28-O--D-glucopyranoside] of oleanolic acid (glycoside Rb-4).Simferopol' State University. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 404–410, May–June, 1997.     

PbO·6 Al2O3, eine neue Verbindung vom Typus des β-Al2O3

Zusammenfassung Eine kurze Übersicht über die Struktur der verschiedenen Verbindungen vom Typus des -Al₂O₃ wird gegeben und ein Vergleich mit dem Mineral Magnetoplumbit vorgenommen. Es wird die Ansicht vertreten, daß sämtliche Verbindungen des -Typus analog kristallisieren wie Magnetoplumbit. Die Alkali- und auch Erdalkali-Ionen können aber teilweise aus dem Gitter entfernt werden, wodurch die wechselnden analytischen Ergebnisse bedingt sind. Ein bisher fehlendes Glied in der Reihe der -Verbindungen mit der Zusamensetzung PbO·6 Al₂O₃ wurde dargestellt und beschrieben. Diese als Blei--Al₂O₃ bezeichnete Verbindung stellt ein direktes Analogon zu Magnetoplumbit dar.

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The structures of various compounds of the type of -Al₂O₃ are reviewed, and compared with the mineral magnetoplumbite. The opinion is advocated that all compounds of the type of -Al₂O₃ crystallize analogous to magnetoplumbite. The ions of the alkali metals and alkaline earths can, however, partially be removed from the lattice, thereby leading to the various analytical compositions. One as yet missing link in this line of -compounds of the composition PbO· 6 Al₂O₃ was synthesized, and is described. this Lead--Al₂O₃ is a directly analogous to magnetoplumbite.

     

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.     

Synthesis of esters of α-chloroacetoxy-β,β,β,-trichloroethylphosphonic acids

Summary The synthesis of 11 previously unreported dialkyl esters of -mono-, -di-, and -trichloroacetoxy-,,-trichloroethylphosphonic acids has been effected.     

Triterpene Glycosides of Astragalus and Their Genins. LXI. Occurrence of Cycloartane 6-O-Monodesmosides

Cyclosiversigenin 6-O--L-rhamnopyranoside and 6-O--D-glucopyranoside were isolated fromAstragalus coluteocarpusBoiss. (Leguminosae) andAstragalus dissectusB. Fedtsch. et N. Ivanova, respectively. Cyclosiversigenin 5-O--L-rhamnopyranoside was shown to be an artifact forAstragalus coluteocarpus.Thus, the cyclosiversigenin 6-O--D-glucopyranoside that was isolated from certainAstragalusspecies is hypothesized also to be an artifact. Glycosylation of the 6 -hydroxyl group of cycloartanes by D-glucose and D-xylose, in contrast with other substituents, does not change the low-field position of the PMR signal of the 4-CH ₃ group (1.65 2.01 ppm) that is caused by the influence of deuteropyridine directly on the 6 -hydroxyl. Obviously one of the hydroxyls of the -D-glucopyranoside or -D-xylopyranoside residues has the same effect in this instance.     

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.     

Reaction of dimethylaminomethylenemalonaldehyde bis-N,O-acetal with ketones. A novel route to N-methylpyrroles

Condensation of the bis-N,O-acetal of amethylarrtinomethylenerrzalonaldehyde with ketones, -dimethylaminovinylketones, and -dimethylaminodienones is accompanied by an unusual intramolecular cyclization to give cross conjugated cyclic or acylic ketones containing an N-methyl pyrrole ring in the - or - and'-positions. This is a novel route to substituted pyrroles. Treatment of the bis-N,O-acetal of dimethylaminomethylenemalonaldehyde with 2-(3'-dimethylaminopropen-2'-ylidene)cyclopentanone gave a polyenyl tris-dimethylaminodiketone.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 117913. Translated from Khimiya Geterotsiklicheskikh Soednenii, No.5, pp. 654–662, May, 1996. Original article submitted February 14, 1996.     

Steroid glycosides of the roots ofCapsicum annuum. II. The structure of the capsicosides

Two tigogenin glycosides and two diosgenin glycosides have been isolated from a methanolic extract of the roots of bush red pepper. An attempt to isolate the individual spirostanol glycosides directly was unsuccessful. These compounds have very similar structures. For their separation, acetylation and epoxidation of the double bond of the aglycon, diosgenin, in the corresponding glycosides was performed. The derivatives obtained were purified by chromatography. To establish the complete chemical structure of each capsicoside we used both chemical and physical methods; complete and partial acid hydrolysis, methylation followed by methanolysis, IR spectroscopy, mass spectroscopy, etc. It was shown that capsicoside A₂ is (25R)-5-spirostan-3-ol 3-O--D-galactopyranoside, capsicoside B₂ is (25R)-5-spirostan-3-ol 3-O-[O--D-glucopyranosyl(14)--D-galactopyranoside], capsicoside A₃ is (25R)-spirost-5-en-3-ol 3-O--D-galactopyranoside, and capsicoside B₃ is identical with funkioside C.Institute of Chemistry, Academy of Sciences of the Moldavian SSR, Kishinev. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 242–246, March–April, 1987.     

Octahedral and tetrahedral configuration changes of nickel(II) chloro complexes from spectrophotometric studies in aprotic solvents

Four NiII chloro complexes were identified spectrophotometrically in aprotic media such as DMSO, DMF and propylene carbonate for the first time. An original multiwavelength numerical treatment, based on a Marquardt method, results in the determination of the individual electronic spectra of the mononuclear chloro complexes and of their stability constants, the values of which indicate the presence of rather weak complexes in DMSO and DMF, much stronger in the less solvating propylene carbonate solvent. The overall stability constants calculated for the NiII chloro complexes are: 1=52, 2=140, 3=160, 4=210 in DMSO, 1=60, 2=110, 3=900, 4=15000 in DMF, 1=1.6×109, 2=6.4×1015, 3=2.7×1021, 4= 5.1×1026 in PC.The solvent effect is discussed in terms of the quantitative results obtained from this spectrophotometric study and reveals that the stability of the complexes is an inverse function of the donor properties of the solvent. This result illustrates the general behavior of complex formation in dipolar aprotic solvents, i.e. the substitution of one solvent molecule in the inner coordination sphere by the ligand is easier if the solvation strength of the solvent is lower. The solvent effect is also described in terms of the variation of shifts of the calculated absorption maxima for the individual electronic spectra of the chloro complexes. This result is used to identify clearly at which step of coordination the octahedral configuration of the nickel ion changes to the tetrahedral configuration, by comparison with the well-known structural properties of these complexes in the solid state.     

Cardenolide glycosides ofCheiranthus allioni. XV. Glucocheiranthoside

Another new cardenolide glycoside has been isolated from the plantCheiranthus allioni Hort., and has been named glucocheiranthoside. Its chemical structure has been established as 3-(4-O--D-glucopyranosyl--D-gulmoethylpyranosyloxy)-14-hydroxy-19-oxo-5,14-card-20(22)-enolide.State Scientific Center for Drugs, Ukraine, 310085, Kharkov, USSR. ul. Astronomicheskaya, 33. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 269–271, March–April, 1994.     

Coupling of Antibodies to β-Cyclodextrin-Coated Gold Surfaces via an Intermediate Adamantyl-Modified Carboxymethylated Dextran Layer

-cyclodextrin-coated sensors chips were obtained by grafting amino--cyclodextrin or amino-polymers of -cyclodextrin (poly--CD-NH₂) to functionalized gold surfaces. An additional carboxymethylated dextran bearing adamantyl groups (Ad-Dex-COOH) was then immobilized onto the surface by formation of inclusion complexes between -cyclodextrin cavities and adamantyl groups. Such multilayered structures were stable in aqueous media. However, the initial -cyclodextrin-coated surface could be recovered by using sodium dodecylsulfate solutions (SDS). After activation withN-hydoxysuccinimide, dextran-coated sensor chips were used to bind antibodies. The immunoreactivity of the resulting biosensors was examined. Moreover, conditions leading to the complete regeneration of the initial surface were investigated. Throughout this study, interfacial adsorption and desorption phenomena were followed in real time by an optical technique, Surface Plasmon Resonance (SPR).     

Triterpene Glycosides from Plants of the Astragalus Genus. Structure of Cyclounifolioside A from Astragalus unifoliolatus

The known compound oleanolic acid (1) and a new cycloartane glycoside cyclounifolioside A (2), which has the structure 6,16-di-O-acetyl-24R-cycloartan-6,16,24,25-pentaol 3-O--D-glucopyranoside, were isolated from Astragalus unifoliolatus Bunge. The structures of the isolated compounds were established using chemical transformations and two-dimensional spectra (TOCSY, ROESY, HMBC, HSQC, COSY).     

Synthesis of fluoroalkyl-containing β-hydroxyketones by reduction of the corresponding β-diketone derivatives

The rcgioselective synthesis of fluoroalkyl-containing P-hydroxyketones by the reduction of the salts of the corresponding -diketones with LiAlH₄ was proposed. This is the sole method for the synthesis of -hydroxyketones with two fluoroalkyl substituents.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1493–1495, June, 1996.     

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.     

Steroid compounds of marine sponges. IV. New sterols with unusual side chains from the fungusHalichondria sp 1

Five new steroid alcohols have been isolated in the form of their acetates from extracts of the spongeHalichondria sp ₁ by column chromatography on silica gel and they have been identified as 24-isopropyl-5-cholest-22z-en-3-ol, 24-isopropylcholesta-5, 22Z-dien-3-ol, 24,24,26,26-tetramethylcholesta-5,25(27)-dien-3-ol, 24,24,26,26-tetramethylcholesta-5,22E,25(27)trien-3-ol, and 24-isopropenyl-25-methylcholesta-5,22E-dien-3-ol. The structures were established by an analysis of spectral characteristics.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. 232–239, March–April, 1985.     

Nitroderivate vonβ,β,β-Trihalo-α,α-bis-(4-alkoxybzw. 4-oxy-phenyl)-äthanen

Zusammenfassung Auf Grund von Modellbetrachtungen wurde die Existenz der in der Literatur beschriebenenOctanitro-Derivate von ,,-Trihalo-,-bis-(4-alkoxy-phenyl)-äthanen in Zweifel gezogen. Entsprechende Untersuchungen ergaben, daß es sich bei ihnen umTetranitro-Verbindungen handelt und daß es nicht möglich ist, diese DDT-Analogen mehr als vierfach zu nitrieren. Die Konstitution der Tetranitro-Verbindungen wurde durch Abbau bewiesen: Beim ,,-Trichlor-,-bis-(3,5-dinitro-4-methoxy-phenyl)-äthan (II) durch Überführung in das entsprechende Keton (VII), beim ,,-Trichlor-,-bis-(3,5-dinitro-4-äthoxy-phenyl)-äthan (IV) durch Entalkylierung und Methylierung zu II. Der Beweis der 3,3, 5,5-Stellung der Nitrogruppen in II und IV ist auch für andere Tetranitro-Derivate von ,,-Trihalo-,-bis-(4-X-phenyl)-äthanen (X=Substituenten I. Ordnung) von Bedeutung.Mitt. II der Reihe: Stereochemische Untersuchungen in der Diphenylmethanreihe.     

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.     

Triterpene glycosides ofClimacoptera transoxana. III. The structures of copterosides E and F

New triterpene glycosides have been isolated from the epigeal part ofClimacoptera transoxana (Iljin) Botsch. — copterosides E and F. According to chemical transformations and physicochemical characteristics, copteroside E has the structure of oleanolic acid 28-O--D-glucopyranoside 3-O-{[O--D-xylopyranosyl-(12)]-[O--D-xylopyranosyl-(14)]--D-glucuronopyranoside} and copteroside F that that of hederagenin 28-O--D-glucopyranoside 3-O-{[O--D-xylopyranosyl-(12)]-[O--D-xylopyranosyl-(14)]--D-glucopyranoside}.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 596–601, September–October, 1983.     

Withasteroids ofPhysalis. V. A study of the1H and13C NMR spectra of the withasteroids visconolide and 28-hydroxywithaperuvin C

The PMR and¹³C NMR spectra of new withasteroids — visconolide and 28-hydroxywithaperuvin C, isolated fromPhysalis viscosa L. — have been investigated. A detailed analysis of the spectral characteristics obtained is given. For visconolide is proposed the structure of 4,12,17,28-pentahydroxy-1-oxo-5, 6-epoxy-22R-witha-2,24-dienolide, and for 28-hydroxywithaperuvin C that of 6,14,17,20R, 28-pentahydroxy-l-oxo-22R-witha-2, 4, 24-trienolide.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 657–663, September–October, 1985.     

Comparative study on inclusion complexations of antiinflammatory drug flurbiprofen with β-cyclodextrin and methylated β-cyclodextrins

Abstruct Some physicochemical properties of methylated -cyclodextrins, i.e., heptakis(2,6-di-O-methyl)--cyclodextrin (DM--CyD) and heptakis(2,3,6-tri-O-methyl)--cyclodextrin (TM--CyD) were compared with those of natural -cyclodextrin (-CyD). Inclusion behaviors of -CyD and methylated -CyDs in water and in solid state were studied by solubility analysis, spectroscopies (UV, CD,¹³C-NMR and IR), X-ray diffractometry and thermal analysis, using an antiinflammatory drug flurbiprofen (FP) as a guest molecule. The spectral data suggest that the inclusion mode of FP-TM--CyD is somewhat different from those of FP--CyD and FP-DM--CyD. The solid complexes of FP with - and methylated -CyDs were obtained in molar ratio of 11, and their dissolution behavior and release from suppository base were examined. The data are presented suggesting that DM--CyD is particularly useful for improving the pharmaceutical properties of FP in various dosage forms.