New cardenolides from the leaves ofGomphocarpus fruticosus

Two new glycosides, gomphotin (1) and gomphotoxin (13), and also the known gomphoside (9) have been isolated from the leaves ofGomophocarpus fruticosus. Compounds (1) and (9) contain a 4,6-dideoxyhexosulose residue as the sugar component, and (13) a 6-deoxyhexosulose, which are attached to glycolic OH groups of the aglycons by 3-O-1,2-O-2 (9, 13) and 3-O-1,4-O-2 (1) acetal-ketal bonds. The structures of the new compounds are represented by the names (3-O-1,4-O-2)-(2,3-dihydroxy-4, 6dideoxyhexulosido)-14-hydroxy-5-card-20(22)-enolide* (1) and (3-O-1,2-O-2)-(2,3,4-trihydroxy-6-deoxyhexulosido)-14-hydroxy-5-card-20(22)-enolide* (13).State Scientific Center for Drugs of the Ministry of Health and the National Academy of Sciences of the Ukraine, Kharkov, fax 441118. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 824–832, November–December, 1995. Original article submitted May 22, 1995.     

<Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR spectra of some drimanic sesquiterpenoids

One- and two-dimensional homo- and heteronuclear correlation proton, carbon, proton—proton, and proton—carbon NMR spectra of fifteen drimanic sesquiterpenoids: 11,12-dibromodrima-5,8-dien-7-one, drim-8-en-7-one, 11-hydroxydrim-8-en-7-one, 11,12-dihydroxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 8,9-epoxydriman-7-one, 8,9-epoxydriman-7-ol, 11,12-diacetoxydrim-8-en-7-ol, drimane-7,8,11-triol, 7,8-isopropylidenedioxydriman-11-al, 9, 11-dihydroxydrim-7-en-6-one, drimane-7,8,9-triol, drimane-7,8,11-triol, and drim-8-ene-7,11,12-triol were studied. The proton and carbon chemical shifts were assigned.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2589–2594, December, 2004.     

Supramolecular Polymers Formed by Modified Cyclodextrins

6-Hydrocinnamoyl -cyclodextrin(6-HyCiO--CD), 6-hydrocinnamoyl -cyclodextrin(6-HyCiO--CD), 6-cinnamoyl -cyclodextrin(6-CiO--CD), and 6-cinnamoyl -cyclodextrin (6-HyCiO--CD) have been prepared.6-HyCiO--CD formed an intramolecular complex in an aqueous solution. 6-HyCiO--CD formed weak intermolecular complexes.6-CiO--CD formed intermolecular complexes to give supramolecular oligomers. 6-CiO--CD formed insoluble supramolecular complexes in the solid state. The structures of these complexes are discussed.     

Transformed steroids. 189. Synthesis and transformations of 21-hydroxy-5α-H-pregnane 2′,2′-dimethyl-[16α,17α-d]-thioxalanes

In a continuation of the research on use of 20-keto-16,17-epoxysteroid 20-hydrazones for synthesis of 17-thio analogs of 20-ketosteroid 16,17-acetonides [2, 3], we synthesized 5-H-pregnane-3,16,21-trihydroxy-17-thiol-20-one 16,17-acetonide and found methods for its microbiological dehydrogenation and hydroxylation into ⁴-3-keto-and 9-hydroxy-⁴-3-keto derivatives.See [1] for Communication 188.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1182–1186, May, 1992.     

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.     

The problem of identifying an adequate kinetic equation for a chemical transformation in thermal analysis

Additional criteria are suggested for the selection of an adequate functiong() describing the mechanism of a chemical transformation using the Satava method.

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Zusammenfassung Zusätzliche Kriterien werden zur Auswahl der geeigneten Funktion g() zur Beschreibung des Mechanismus der chemischen Umwandlung mit der Satava-Methode vorgeschlagen.

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g() .

     

Reduction of some D-homosteroids with an aromatic a ring with alkali metals under the conditions of Birch's reaction. II.

Summary 1. The reduction of 3-methoxy-D-homoestra-1, 3, 5(10), 8-tetraen-17a-ol (IV) with alkali metals in the presence of ammonium chloride or alcohol gives, in addition to 8, 9-dihydro derivatives, the 8, 9 and 8, 9-epimers, the structure of which has been shown partly by independent synthesis and partly on the basis of chemical reactions and NMR spectra.2. Hydrolysis of the reduction products has given 19-nor-D-homotestosterone (III) and its 8- and 9, 10-epimers (V) and (VI). The ketols (III) and (V) readily form hydroperoxides in air.3. The reduction of the ethylene ketal of 3-methoxy-D-homoestra-1, 3, 5(10), 8-tetraen-17a-one (XIX) takes place stereodirectively and gives only 8, 9-dihydro derivatives.Khimiya Prirodnykh Soedinenii, Vol. 1, No. 2, pp. 90–100, 1965     

Structure and configuration of korseverinine

Conclusions 1. By separating the mixture of bases obtained from the fresh epigeal part ofKorolkowia sewerzowii Rgl. with respect to solubility in different solvents, the alkaloids korseverine, korsinine, korsine, korseveriline, korseveridine, korseveramine, and korseverinine have been been isolated.2. On the basis of a study of chemical transformations and IR, NMR, and mass spectra, the configuration, 5,12,14,13,17,20,22,25-cev-8-ene-3,6-diol has been proposed for korseverinine.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 767–773, November–December, 1971.     

Esters of (1,2, 5-trimethyl-4-hydroxy-4-piperedyl)- and phenyl-(1,2, 5-trimethyl-4-hydroxy-4-piperidyl) acetic acids

The methyl ester of a new hydroxy acid of the piperidine series (-phenyl--(1,2, 5-trimethyl-4-hydroxy 4-piperidyl)acetic acid) has been prepared. Ethyl -(1,2, 5-trimethyl-4-hydroxy-4-piperidyl)acetate has been converted into the substituted pyridine, 1,1-diphenyl-2-(2-5-dimethyl-4-pyridyl)ethylene.     

Synthesis of α-alkyl- and α,α-dialkyl-β-phenyltryptamines

A new method was developed for the synthesis of -alkyl- and ,-dialkyl--phenyltryptamines based on alkylation of nitroalkanes with -phenyl-nor-gramine.     

Mono- and sesquiterpenoids of the oleoresin ofAbies nephrolepis. Crystal structure of (+)-β-cedrol

The composition of the mono- and sesquiterpenoids from the oleoresin of the Khingan fir has been studied. Thirteen monoterpenoids have been identified — bornyl acetate, -terpenyl acetate, geranyl acetate, citronellyl acetate, -fenchyl acetate, linalool, geraniol, terpineol-4, -terpineol, -fenchol, borneol, sabinene hydrate and thymol methyl ether; and 19 sesquiterpenoids — -longipinene, longicyclene, longifolene, -copaene, -ylangene, sibirene, -and -selinenes, - and -cadinenes, -muurolene, caryophyllene, -humulene, - and -bisabolenes, ar-curcumene, nerolidol, bisabolol, and -cedrol. The crystal structure of -cedrol has been investigated by x-ray structural analysis.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 41–45, January–February, 1985.     

Synthesis and biological activity of methyl derivatives of dl-19-nor-D-homotestosterone

Summary The synthesis of racemates of the 2-methyl, 4-methyl, 17-methyl, and 2, 17-dimethyl derivatives of 19-nor-D-homotestosterone has been described. Biological tests have shown that the introduction of a CH₃ group into positions 2 and 17 totally suppresses both androgenic and anabolic activity. The introduction of a CH₃ group into position 4 leads to a divergence of the anabolic and androgenic effects.Khimiya Prirodnykh Soedinenii, Vol. 4, No. 1, pp. 3–9, 1968     

Triterpene glycosides of Hedera taurica

From the leaves of Crimean ivy we have isolated the previously known glycosides 3-O--L-Ara_p-28-O-[O--L-Rha_p-(14)-O--D-Glc_p-(16)--D-Glc_p]hederagenin, 3-O-[O--L-Rha_p-(12)--L-Ara_p]-28-O-[O--L-Rha_p-(14)-O--D-Glc_p-(16)--D-Glc_p]oleanic acid and -hederagenin, and 3-O-[O--L-Rha_p-(12)--L-Ara_p]-28-O-[O--D-Glc_p-(16)--D-Glc_p]hederagenin and a new one: tauroside H₁ — 3-O-[O--L-Rha_p-(12)-O--L-Ara_p]-28-O-[O--L-Rha_p-(14)-O--D-Glc_p-(16)--D-Glc_p]echinocystic acid.M. V. Frunze Simferopol' State University. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 522–528, September–October, 1992.     

Synthesis and1H NMR and13C spectroscopy of L-arabinopyranosyl biosides

Conclusions The 3-0- and 4-0-trityl ethers of the acetates of methyl -L- arid methyl -L-arabinopyranosides were synthesized. The glycosylation of the ethers with the aid of 3,4-di-0-acetyl-1,2-0-(1-exo-cyano)ethylidene--L-arabinopyranose and the subsequent deacetylation of the synthesized products yielded the disaccharides: methyl 4-0-(-L-arabinopyranosyl)-,methyl 4-0-(-L-arabinopyranosyl)-, and methyl 3-0-(-L-arabinopyranosyl)--L-arabinopyranoside; and methyl 4-0-(-L-arabinopyranosyl)-, methyl 4-0-(-L-arabinopyranosyl)-, methyl 3-0-(-L-arabinopyranosyl)-, and methyl 3-0-(-L-arabinopyranosyl)--L-arabinopyranoside.The assignment of the signals in the PMR and¹³C NMR spectra of the synthesized arabinopyranosyl biosides was carried out, allowing the determination of the type and configuration of the glycosidic bond by means of which the arabinopyranose residues are linked in the oligo- and polysaccharide chains.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 200–209, January, 1986.     

Studies on the Colloidization and Stability of Layered M(IV) Phosphates in Aqueous Amine Solutions

For the purpose of preparing pillared materials and multifunctional films,the colloidization and hydrolysis of -Zr(HPO4)2·H2O(-ZrP), -Sn(HPO4)2·H2O (-SnP)and -Ti(HPO4)2·H2O (-TiP) in alkylamineand alcohol amine solutions were investigated. The phosphates colloidizeat a low level of amine intercalation but recrystallize at high levels ofamine uptake. Alcohol amines are more efficient in colloidization ofphosphates than alkylamines, and in the same amine solution -ZrPand -SnP colloidize more readily than -TiP. Thehydrolytic reaction of the phosphates following the course of intercalationin different amine solutions were studied. The dissolution of the metal ionsaccompanying the hydrolysis of HPO42- leads to the destruction ofthe sheet structure. The strong hydrolytic reaction of -TiP causesit to colloidize with difficulty. The phase transformations of the wet amineintercalates during air drying were detected by XRD. The interlayer aminemolecules may arrange in monolayer, bilayer or intermediate orientation,depending on the nature and content of the amines.     

New α,ω-diamido and α,ω-diamino mono-and bi-bridged acridine dimers

A novel set of dimers derived from 9-amino acridine was prepared and characterized by¹H and¹³CNMR. These derivatives are bridged at several different positions of the heterocyclic moieties, by the way of ,-diamido or ,-diamino side-chains. Additionally the preparation of some bi-bridged compounds was achieved.

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Neue ,-Dimaido- und ,-Diamino-Mono- und Bi-überbrückte Acridin-Dimere

Zusammenfassung Es wurde eine neue Reihe von Dimeren des 9-Aminoacridins hergestellt und mittels¹H und¹³C-NMR charakterisiert. Diese Derivate sind an verschiedenen Positionen des Heterocyclus mit ,-Diamido- oder ,-Diamino-Seitenketten überbrückt. Zusätzlich wurden auch einige zweifachüberbrückte Verbindungen hergestellt.

     

Triterpene glycosides of Pulsatilla dahurica structures of glycosides A,B, C,and D

The isolation of four triterpene glycosides from the roots of the dahurian anemonePulsatilla dahurica (Fisch. ex DC) Spreng, is described together with their identification, on the basis of chemical transformations, spectral characteristics, and literature analogies, as hederagenin 3-O--L-arabinoside, hederagenin 3-O-[O--D-glucopyranosyl-(12)--L-arabinopyranoside], hederagenin 3-O--L-arabinopyranoside 28-O-[O--L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranoside], and hederagenin 3-O-[O--D-glucopyranosyl-(14)--L-arabinopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranoside].Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 349–356, May–August, 1992.     

Synthesis and study of L-arabinopyranosides of 5- and 6-nitroindoles

Condensation of 5- or 6-nitroindoline with L-arabinose gave 1--L-arabinopyranosyl-5 (or 6)-nitroindolines, which, after acetylation, dehydrogenation, and removal of the protective groups, are converted to 1--L-arabinopyranosyl-5(or 6)-nitroindoles and then to the corresponding amino derivatives. 1--L-Arabinopyranosyl-6-nitro-3-bromo-(iodo)indoles were obtained. The selective 2-O- and 3-O-deacetylation of 1-(2, 3, 4-tri-O-acetyl)--L-arabinopyranosyl-6-nitroindole was accomplished.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 224–229, February, 1979.     

Substituted hydrazides of hydroxycarboxylic acids

The action of N-methylpiperazine and , -dimethylpyrrolidine on chloroacetyl derivatives of phenylhydrazides of diaryl- and dialkylglycolic acids has given the previously unknown N-methylpiperazinoacetyl and , -dimethylpyrrolidnoacetyl derivatives of these phenylhydrazides.For part XL, see [1].     

Steroid compounds from the starfish Lysastrosoma anthosticta collected in the Sea of Japan

Six polyhydroxylated steroids and their derivatives were isolated from the starfish Lysastrosoma anthosticta collected in the Posyet Bay, Sea of Japan. These include a new glycoside of the steroid polyol, lysastroside A (1), which was identified as (25S)-26-O--d-xylopyranosyl-5-cholestane-3,6,8,15,16,26-hexaol, and the previously known pycnopodioside C monoglycoside (2), marthasterone sulfate (3), (25S)-5-cholestane-3,6,8,15,16,26-hexaol (4), (25S)-5-cholestane-3,6,7,8,15,16,26-heptaol (5), and (25S)-5-cholestane-3,6,7,8,15,16,26-heptaol (6). The compounds were tested for the haemolytic activity and the action on the embryogenesis of the sea urchin Strongylocentrotus intermedius.