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 ofScabiosa soongorica

Partial syntheses of glycosides of oleanolic acid — the 3-0--D-xylopyranoside (songoroside A), the 3,28-bis-0--D-xylopyranoside, and the 28-0--gentiobioside-3-0--D-xylopyranoside — and also the formation of 3-0--D-xylopyranosyloleanolic acid 13,28-lactone are described.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Institute of the Physiology and Experimental Pathology of High Mountain Regions of the Academy of Sciences of the KirgSSR, Frunze. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 668–673, September–October, 1979.     

Triterpene saponins fromThalictrum minus. IV. The structure of thalicoside A

The predominating saponin, which has been called thalicoside A, has been isolated from low meadow rue (Thalictrum minus). It has been established by chemical and spectral methods that thalicoside A is 3,16,22(S),29-tetrahydroxy-9,19-cyclo-20(S)-lanost-24-ene 3-O--D-galactopyranoside 29-O--D-glucopyranoside.Irkutsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. 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. 213–219, March–April, 1984.     

Alkaloids of Aconitum kirinense. Structure of akirine

The known alkaloid lepenine and the new diterpene alkaloid akirine have been isolated from the epigeal part ofAconitum kirinense Nakai. To establish the structure of akirine, its spectral characteristics have been studied and an x-ray structural analysis has been made. It is 1,8-dihydroxy-16-methoxy-9,14-methylenedioxy-3,4-epoxy-N-ethylaconitane — the first diterpene alkaloid with a lycoctonine skeleton containing a 9,14-methylenedioxy group and a -oriented substituent at C14.Institute of Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 534–538, September–October, 1992.     

Steroid glycosides XXI. The structure of polygonatoside E′ and protopolygonatoside E′ from the leaves ofPolygonatum latifolium

Summary The chemical structures of two new steroid glycosides from the leaves ofPolygonatum latifolium have been shown. Polygonatoside E is 3-[0--D-glucopyranosyl-(1 3)-0--D-glucopyranosyl-(1 4)-0--d-galactopyranosyl-(1 3)--D-glucopyranosyloxy]-(25R)-spirost-5-ene, and protopolygonatoside E is 26--D-galactopyranosyl-(1 3)--D-glucopyranosyloxy]-(25R)-furost-5-en-22-ol.Institute of Chemistry, Academy of Sciences of the Moldavian SSR, Kishenev. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 350–354, May–June, 1978.     

Triterpene glycosides ofAstragalus and their genins. XXII. Cycloorbicoside A fromAstragalus orbiculatus

The quantitatively main glycoside — cycloorbicoside A — has been isolated from the epigeal parts of the plantAstragalus orbiculatus, 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 3-0--D-xylopyranoside.Institute of the Chemistry of Plant Substances Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 719–726, November–December, 1986.     

Triterpene glycosides ofAstragalus and their genins XLIX. Structures of cycloalpigenin C and cycloalpioside C

The structures of the new cycloartane triterpenoid cycloalpigenin C and its glycoside cycloalpioside C, isolated from the epigeal pan of Astragalus alopecurus Pall. (Leguminosae), have been determined. Cycloalpigenin C is 20R, 24S-epoxycycloartane-3,12,16, 25-tetraol, and cycloalpioside C is the 3-O- D-xylopyranoside of cycloalpigenin C.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 89 14 75. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 88–95, January–February, 1995. Original article submitted October 25, 1994.     

Steroid saponins and sapogenins ofAllium. XV. Eruboside B fromAllium erubescens

A new steroid glycoside of the spirostan series — eruboside B (I) — has been isolated from an ethanolic extract of the bulbs ofAllium erubescens C. Koh. In an acid hydrolysate, the aglycone -chlorogenin (II) and the sugars D-glucose and D-galactose in a ratio of 3:1 have been found. By methylation, partial hydrolysis, and oxidation the structure of the spirostanol (I) has been established as (25R)-5-spirostan-3,6-diol 3-O-{[O--D-glucopyranosyl-(13)]-[O--D-glucopyranosyl-(12)]-O--D-glucopyranosyl-(14)--D-galactopyranoside}.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Tbilisi State Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 509–514, July–August, 1979.     

Triterpene glycosides of Astragalus and their genins XXXII. Cyclocarposide from Astragalus coluteocarpus

A new triterpene glycoside of the cycloartane series, which has been called cyclocarposide, has been isolated from the epigeal part of the plantAstragalus coluteocarpus Boiss. (Leguminosae). The structure of cyclocarposide has been established on the basis of chemical transformations and spectral characteristics as 20R,24S-epoxycycloartane-3,6,16,25-tetraol 6-0--L-rhamnopyranoside 3-0--D-xylopyranoside.Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Pamir Biological Institute, Academy of Sciences of the Tadzhik SSR, Khorog. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 653–656, September–October, 1990.     

Triterpene glycosides ofSilphium perfoliatum. III. Structure of silphioside E

A new triterpene glycoside — silphioside E — has been isolated from the epigeal part ofSilphium perfoliatum L. and its structure has been established on the basis of chemical transformations and spectral characteristics as oleanolic acid 28-0--D-glycopyranoside 3-0-[0--D-glycopyranosyl-(1 2)--D-glucopyranoside].Pyatigorsk Pharmaceutical Institute. Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnikh Soedinenii, No. 6, pp. 750–753, November–December, 1984.     

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.     

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.     

New polyhydroxysteroids from the far-eastern starfish Henricia sp.

From the far-eastern starfishHenricia sp. we have isolated and characterized the new polyhydroxysteroid (24S)-5-cholestane-3,4,6,8,15,24-hexaol and three new glycosides: (24S)-5-cholestane-3,4,6,8,15,24-hexaol 3-O-(2,4-di-O-methyl--D-xylopyranoside) (henricioside H₁), 24-methyl-5-cholesta-4,22E-diene-3,6,8,15,16,26-hexaol 3-O-(2,3-di-O-methyl--D-xylopyranoside) (henricioside H₂), and the 22,23-dihydro derivative of henricioside H₂ (henricioside H₃).Pacific Ocean Institute of Bioorganic Chemistry, Far-Eastern Scientific Center, Russian Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 249–253, March–April, 1993.     

Synthesis of p-nitrophenyl glycosides of N-aminoacyl derivatives of D-glucosamine. II

Summary 1. A method has been developed for the synthesis of p-nitrophenyl -D-glucosaminides acylated with glucine and alanine.2. p-Nitrophenyl N glycyl--D-glucosaminide has been found to be a substrate of a neutral D-hexosaminodase.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. 3, pp. 379–381, May–June, 1976.     

Reaction of benzylidene-2-naphthylamine with the ethyl ester of 3-pyridyl-β-oxopropionic acid

The reaction of benzylidene-2-naphthylamine with ethyl -(3-ethyl)--oxopropionate under various conditions gave the ethyl ester of -(2-naphthylamino)benzyl--(3-pyridyl)--oxopropionic acid, 1-(3-pyridyl)-3 phenylbenzo[f]quinoline, ethyl ester of 1-(3-pyridyl)-3-phenylbenzo[f]quinoline-2-carboxylic acid, and N-(2-naphthyl)amide of -(3-pyridyl)--oxopropionic acid. The IR, UV, and mass spectra of the products were studied and the pathways for their formation were discussed.Institute of Physical Organic Chemistry, Belorussian Academy of Sciences, Minsk 220603. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 807–810, June, 1996. Original article submitted December 30, 1995.     

Synthesis of derivatives of pentopyranic acid

N⁴-Benzoylcytosine 1-(methyl 2,3,4-tri-O-acetyl--D-glucopyranosiduronate) has been obtained with a yield of 70% by the glycosylation of the trimethylsilyl derivative of N⁴-benzoylcytosine with methyl 1,2,3,4-tetra-O-acetyl--D-glucopyranuronate in the presence of three equivalents of SnCl₄ as condensing agent. Cytosine 1-(-D-glucopyranosiduronamide) (IV) — the amide of pentopyranic acid — has been synthesized in practically quantitative yield by the ammonolysis of the nucleoside (I).Peat Institute, Academy of Sciences of the Belorussian SSR, Minsk. Institute of Bioorganic Chemistry, Academy of Sciences of the Belorussian SSR, Minsk. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 617–619, September–October, 1983.     

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.     

Bromination of regioisomeric fluorine-containing β-aminovinyl ketones

Bromination of -aminovinyl ketones (AVK) with geminal arrangement of the fluoroalkyl and amino groups gives N-bromo derivatives. Regioisomeric AVK with the amino groups in the -position relative to the fluoroalkyl group undergo bromination under analogous conditions to give a mixture of the -bromo and ,N-dibromo derivatives. -Bromo derivatives of AVK disproportionate upon storage.Division of Fine Chemical Synthesis, Institute of Organic Chemistry, Urals Branch, Russian Academy of Sciences, 620219 Ekaterinburg. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 746–749, March, 1992.