Iriterpene glycosides of Astragalus and their genins XLIII. Cycloaraloside B from Astragalus amarus

The structure of a new cycloartane glycoside, cycloaraloside B, isolated from the roots ofAstragalus amarus Pall. (Leguminosae) has been established on the basis of chemical transformations and spectral characteristics: it is 20R,24S-epoxycycloartane-3,6,16,25-tetraol 3-O-[O--L-rhamnopyranosyl-(12)-(6-O-acetyl--D-glucopyranoside)].Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 528–531, September–October, 1992.     

Steroids of the spirostan and furostan series from Nolina microcarpa I. Structures of nolinospiroside C and nolinofurosides A and C

In addition to the know steroid sapogenin (25S)-ruscogenin (I), three new glycosides have been isolated from the leaves ofNolina microcarpa S. Wats. (family Dracaenacea), and the following structures are suggested for them: (25S)-spirost-5-ene-1,3-diol 1-O--D-fucopyranoside (nolinospiroside C, II), (25S)-furost-5-ene-1,3,22,26-tetraol 1-O--D-fucopyranoside (nolinofuroside A, III), and (25S)-furost-5-ene-1, 3, 22, 26-tetraol 1-O--D-fucopyranoside 26-O--D-glucopyranoside (nolinofuroside C, V).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. 672–678, September–October, 1991.     

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.     

Triterpene glycosides of Astragalus and their genins XLIV. Structure of cyclocarposides A and C

The structures of two new cycloartane glycosides — cyclocarposides A and C, isolated from the herbAstragalus coluteocarpus Boiss. — have been established on the basis of spectral characteristics and chemical transformations. Cyclocarposides A and C are: 204R,24S-epoxycycloartane-3,6,17,25-tetraol 3-O-(2-O-acetyl--D-xylopyranoside)6-O-(2-O-acetyl--L-rhamnopyranoside) and 20R,24S-epoxycyloartane-3,6,16,25-tetraol 3-O-(2-O-acetyl--D-xylopyranoside) 6-O--L-rhamnopyranoside, respectively.Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Pamir Biological Institute, Tadzhikistan Academy of Sciences, Khorog. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 694–698, November–December, 1992.     

Triterpene Glycosides and Their Genins from Tragacantha stipulosa. Structure of Cyclostipuloside C

A new cycloartane glycoside of the cyclostipuloside C series, 3-O--D-xylopyranoside-6,16-di-O--D-glucopyranoside-20S-24R-epoxycycloartan-3,6,16,25-tetraol is isolated from aerial organs of Tragacantha stipulosa Boriss.     

1-Aryl-6-azauracile, 5. Mitt.: Die Synthese von 1-(β-Pyridyl)-6-azauracil-5-carbonsäure und einiger ihrer Derivate

Zusammenfassung Analog wie in vorherigen Mitteilungen^1–4 wurden -Pyridyl-hydrazono-cyanacetylcarbamidsäureäthylester (1), 1-(-Pyridyl)-5-cyan-6-azauracil (2), 1-(-Pyridyl)-6-azauracil-5-carbonsäure (3), deren Thioamid (4), und Amidoxim (5), welches in 1-(-Pyridyl)-5-[5-methyl-1,2,4-oxdiazolyl(3)]-6-azauracil (6) überge-führt wurde, hergestellt.

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-Pyridylhydrazono-cyanacetylcarbamic acid ethyl ester (1), l-(-pyridyl)-5-cyano-6-azauracil (2), 1-(-pyridyl)-6-azauracil-5-carboxylic acid (3), its thioamide (4) and amidoxime (5) were prepared as described in preceding communications. (5) was converted into l-(-pyridyl)-5-[5-methyl-1,2,4-oxdiazolyl(3)]-6-azauracil (6).

     

Transformations of solasodine

Solasodine (I) has been subjected to a number of transformations. The following compounds have been obtained from it by described procedures: 3-acetoxypregna-5,16-dien-20-one (II), 3-acetoxypregn-5-en-20-ol (III), and 3-acetoxypregn-5-en-20-ol (IV). The oxidation of (III) and (IV), the formation of an oxime, and the reduction of the oxime with sodium in ethanol, followed by Hess methylation, has led to 20-dimethylaminopregn-5-en-3-ol (IX) and to 20-dimethylaminopregn-5-en-3-ol (X). From compounds (IX) and (X), by analogy with (III) and (IV) by their oxidation and the preparation of oximes, which were then reduced and methylated, the following were obtained: 3,20-bisdimethylaminopregnane (XVII) and 3,20-bisdimethylaminopregnane (XVIII), and also quaternary salts of the latter.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 370–374, May–June, 1980.     

Triterpene Glycosides of Astragalus and Their Genins. LXVII. Structure of Cycloexoside B

Another seven components from the roots of Astragalus exilis A.Kor. (Leguminosae) were identified using spectral data and chemical transformations. A triterpenoid of genin nature was identical to cyclosiversigenin. One compound of glycosidic nature turned out to be a new cycloartane glycoside called by us cycloexoside B of structure 20R,24S-epoxycycloartan-3,6,16,25-tetraol 3-O--D-(2-Oacetyl) xylopyranoside. Five glycosides were identified as cyclosiversigenin 3-O--D-xylopyranoside and cyclosiversiosides B, C, D, and G.     

Cardenolides of the seeds ofCoronilla glauca and ofC. scorpioides. New glycosides alloglaucoside and scorpiosidol

Two new glycosides have been isolated from the seeds ofCoronilla glauca L. and C. scorpioides Koch: 3-(0-D-glucopyranosyloxy)-14. 15-dihydroxy-19-oxo-5-card-20(22)-enolide (alloglaucoside) and 3-(-D-gluco-ucofuranosyloxy)-5,14,19-trihydroxy-5-card-20(22)-enolide (scorpiosidol), together with a glycoside previously unknown for theCoronilla genus — 3-(-D-glucopyranosylo)g)-14-hydroxy-5-card-20(22)-enolide (desglucouzarin) and known aglycons (corotoxigenin, alloglaucotoxigenin, coroglaucigenin) and glycosides (glucocorotoxigenin, coronillobioside, glucocoroglaucigenin, coronillobiosidol and scorpioside).Ukraine Pharmaceutical Academy, Kharkov–2. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 372–376, May–June, 1996. Original article submitted August 14, 1995.     

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 polyols from the Far-Eastern starfish Henricia sanguinolenta

A new polyhydroxylated steroid (20R,24S)-5-cholestane-3,6,15,24-tetraol and a known glycoside, laeviuscoloside G, was isolated from the Far-Eastern starfish Henricia sanguinolenta, collected in the sea of Okhotsk, and characterized.     

Mass spectrometric study of monoalkyl-substituted thiacyclanes

Monosubstituted - and -alkylthiophans and -, -, and -alkylthiacyclohexanes were subjected to a comparative mass spectrometric study. The stability of the M⁺ ion increases on passing from - to -alkylthiophans and from - to - and -alkylthiacyclohexanes. In the case of -alkylthiophans and - and -alkylthia-cyclohexanes the principal process is associated with ejection of the substituent as a whole, whereas a portion of the alkyl substituent, with retention of one CH₂ group in the composition of the charged fragment, is eliminated from the molecular ions of -alkylthiophans and -alkylthiacyclohexanes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 176–181, February, 1978.     

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 reaction of hypophosphorous acid with chloral

Conclusions The condensation of chloral with hypophosphorous acid has given,,-triebloro--hydroxyethyl phosphonous and bis-(, ,-trichloro--hydroxyethyl)-phosphinic acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, p. 1095, June, 1966.     

Direction of nucleophilic substitution in α, β-unsaturated imino compounds with a donor substituent in the beta position

A mechanism of conversion of -aminovinyl ketones into -aminovinylimines is disclosed. It has been found that in this and a series of other reactions (various conversions of -aminovinyl ketones, -aminovinylimines, and -alkoxyvinylimino salts and their vinyl analogs, cyano compounds, etc.), the intermediate determining the course of the reaction is an ,-unsaturated imino cation. The result of the reaction depends on the site and efficiency of the nucleophilic attack by tautomeric imino salt compounds possessing an unshared electron pair distributed over the various electrophilic sites of the molecule.     

<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.     

Triterpene glycosides ofSalsola micranthera. I. Structures of salsolosides C and D

New triterpene glycosides — salsolosides C and D — have been isolated from the epigeal part ofSalsola micranthera Botsch. On the basis of chemical transformations and physicochemical measurements, salsoloside C has been assigned the structure of oleanolic acid 28-0--D-glucopyranoside 3-0-[0--D-xylopyranosyl-(1 4)--D-glucuropyranoside], and salsoloside D has the structure of hederagenin 28-0--D-glucopyranoside 3-0-[0--D-xylopyranosyl-(1 4)--D-glucuropyranoside].Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 727–732, November–December, 1983.     

Phytoecdysteroids of Rhaponticum carthamoides. II. Rhapisterone B

A new ecdysteroid (rhapisterone B) has been isolated from the seeds ofRhaponticum cathamoides (Willd.) Iljin. (familyCompositae). It has been shown that it is 2, 3, 11, 14, 20R, 24-hexahydroxy-5-cholest-7-en-6-one.Institute of the Chemistry of Plant Substances, Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 806–808, November–December, 1991.     

Triterpene glycosides of Astragalus and their genins XL. Cyclocarposide B from Astragalus coluteocarpus

In addition to cyclosieversigenin, -sitosterol -D-glucopyranoside, and cyclocarposide, we have isolated another three glycosides of triterpene nature from the epigeal part of the plantAstragalus coluteocarpus Boiss. (Leguminosae). On the basis of chemical transformations and spectral characteristics, the structure of one of the new glycosides, which we have called cyclocarposide B, has been established as 20R,24S-epoxycycloartane-3,6,16,25-tetraol 6-O--L-(2-O-acetylrhamnopyranoside) 3-O--D-xylopyranoside.Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 227–231, March–April, 1992.     

Triterpene glycosides of Astragalus and their genins XXXVII. Cycloaraloside F from Astragalus amarus and Astragalus villosissimus

The glycosides of the plantAstragalus villosissimus Bunge have been studied. Four glycosides have been isolated from the roots of this plant, and two of them have been identified as -sitosterol -D-glucopyranoside and cycloaraloside C. The most polar glycoside, which has also been isolated from the roots ofAstragalus amarus Pall., proved to be a new triterpene glycoside of the cycloartane series and has been called cycloaraloside F. It is a trioside of cyclosieversigenin containing two molecules of D-glucose and one molecule of D-apiose. On the basis of chemical transformations and spectral characteristics, the structure of cycloaraloside F has been established as 20R, 24S-epoxycycloartane-3,6,16,25-tetraol 3-0-[O-D-apio--D-furanosyl-(12)--D-glucopyranoside] 25-O--D-glucopyranoside.Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 374–377, May–June, 1991.