Triterpene glycosides ofAstragalus and their genins. XLVIII. The structures of cycloalpigenin B and cycloalpioside B

The structures of the new cycloartane methylsteroid cycloalpigenin B and its glycoside cycloalpioside B, isolated fromAstragalus alopecurus Pall. (Leguminosae) have been determined on the basis of chemical transformations with the assistance of¹H and¹³C NMR spectroscopy and 2D NMR¹H-¹H and¹H-¹³C correlations of chemical signals and IR, CD, and electron-impact mass spectrometry. Cycloalpigenin B is 20R,24S-epoxycycloartane-3,12,16,25-tetraol. A transition from cycloalpigenin B to cycloalpigenin A has been achieved. Cycloalpioside B is 20R,24S-epoxycycloartane-3,12,16,25-tetraol 3-O--D-xylopyranoside.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. 4, pp. 515–521, July–August, 1994.     

Astragalus triterpene glycosides and their genins. I. Structures of cycloalpigenin and cycloalpioside

Another two methylsteroids of the cycloartane series have been isolated from the epigeal part ofAstragalus alopecurus. The structures of the compounds isolated, cycloalpigenin and cycloalpioside, have been established as (20R,24R)-16,24:20, 24-diepoxycycloartane-3,7,25-triol and (20R,24R)-16, 24:20,24-diepoxycycloartane-3,7, 25-triol 3-O--D-xylopyranoside, respectively, on the basis of chemical transformations and spectral characteristics. The structure of cycloalpigenin has been confirmed by chemical correlation with that of cycloalpigenin D.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. 5, pp. 700–708, September–October, 1995. Original article submitted February 1, 1995.     

Triterpene glycosides of Astragalus and their genins. XXXVIII. Cycloalpigenin D and cycloalpioside D from Astragalus alopecurus

Eight compounds of triterpenoid nature have been isolated from the epigeal parts of the plantAstragalus alopecurus Pall. (Leguminosae) and have been designated in order of increasing polarity as substance 1–8. On the basis of chemical transformations and spectral characteristics, we have established the structures of 4 and 8, which have been called cycloalpigenin D and cycloalpioside D, respectively. Cycloalpigenin D is 20R,24S-epoxycycloartane-3,7,16,25-tetraol. Cycloalpioside D is cycloalpigenin D 3-O--D-xylopyranoside.Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 377–384, May–June, 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.     

New asterosaponins from the starfishDismolasterias nipon

Three new glycosides, D₁, D₂, and D₃, have been isolated from the Far Eastern starfishDistolasterias nipon. They have been identified by chemical and physicochemical methods as 5-cholestane÷3,6,8,15,24-pentaol 3,24-di-O--D-xylopyranoside, t-cholest-22-ene-3,6,8,15,24-pentaol 3,24-di-O--D-xylopyranoside (II), and 5-cholestane-3,6,8,15,24-pentaol 24-O--D-glucopyranoside 3-O--D-xylopyranoside (III).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. 250–255, March–April, 1987.     

Triterpene glycosides ofAstragalus and their genins. XLVII. Structures of cycloalpigenin A and cycloalpioside A

The structures of two new cycloartane triterpenoids, cycloalpigenin A and cycloalpioside A, isolated from Astragalus alopecurus Pall. (Leguminosae) have been established on the basis of chemical transformations together with¹H,¹³C, and 2D¹H-¹H and¹H-¹³C chemical shift correlation NMR spectroscopy and IR, mass, and CD spectra. Cycloalpigenin A is 3,16,25-trihydroxy-20R,24S-epoxycycloartan-12-one, and cycloalpioside A is cycloalpigenin A 3-O--D-xylopyranoside.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, FAX (3712) 62 73 48. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 379–385, May–June, 1994.     

Polyhydroxysteroids from the Far-Eastern starfishCtenodiscus crispatus

Four new polyhydroxysteroids, 5-cholesta-3,5,6,15,16,25,26-heptaol, 24-ethyl-5-cholesta-3,5,6,15,28,29-heptaol-29-sulfate, (22E)-24-methyl-5-cholest-22-ene-3,5,6,15,25,26-hexaol-26-sulfate, 24-propyl-5-cholesta-3,5,6,8,15,28,29-heptaol, and the known 5-cholesta-3,5,6,15,16,26-hexaol, have been isolated from the starfishCtenodiscus crispatus.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1821–1825, October, 1994.     

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.     

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.     

Triterpene glycosides of Astragalus and their genins XXXV. Cycloaraloside C from Astragalus amarus

A new triterpene glycoside of the cycloartane series (cycloaraloside C) has been isolated from the roots of the plantAstragalus amarus Pall. (Leguminosae). Cycloaraloside C is a bioside of cyclosieversigenin including one D-glucose residue and one D-apiose residue. The structure of the glycoside has been shown on the basis of the chemical transformations and spectral characteristics as 20R,24S-epoxycycloartane-3,6,16,25-tetraol 3-O-[O-(D-apio--D-furanosyl)-(1 2)--D-glucopyranoside]. This is the first time that D-apiose has been found among cycloartane glycosides.Institute of Chemistry of Plant Substances, Academy of Sciences of the Uzbek, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 783–787, November–December, 1990.     

Some Pharmaceutical Properties of a New Branched Cyclodextrin, 6-O-α-(4-O- α-D-Glucuronyl)-D-glucosylβ-cyclodextrin

Some physicochemical and biological properties of a new branched cyclodextrin, 6-O--(4-O--d-glucuronyl)-d-glucosyl--cyclodextrin GUG--CyD) were investigated. Further, theinteraction of GUG--CyD with several drugs was studied by the solubility and spectroscopic methods, and compared with those of parent -CyD and 6-O--maltosyl--CyD(₂--CyD).The hemolytic activity of GUG--CyD on rabbit erythrocytes was lower than those of -CyD and ₂--CyD. GUG--CyD and ₂--CyD showed negligible cytotoxicity on Caco-2 cells up to at least 0.1 M. The inclusion ability of GUG--CyD to neutral and acidic drugs was comparable to or slightly smaller than those of -CyD and ₂--CyD, probably because of a steric hindrance of the branched sugar. On the other hand, GUG--CyD showed greater affinity for the basic drugs, compared with -CyD and ₂--CyD, owing to the electrostatic interaction of its carboxylate anion with positive charge of basic drugs. Thus GUG--CyD may be useful as a safe solubilizing agent particularly for basic drugs.     

Pulchellin C and inuchinenolide C from Inula caspica

The pseudoguaianolide inuchinenolide C and the eudesmanolide pulchellin C have been isolated for the first time from the flower heads and leaves ofInula caspica Blume, and their spatial structures have been established by an x-ray structural experiment as 2,6-diacetoxy-6-hydroxy-1,7(H),8,10(H)-pseudoguai-11(13)-en-8,12-olide and 2,3-dihydroxy-5,7,8(H)-eudesma-4(15),11(13)-dien-8,12-olide, respectively.Institute of Organic Synthesis and Coal Chemistry, Academy of Sciences of the Kazakh SSR, Karaganda. A. N. Nesmeyanov Institute of Organometallic Compounds, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 748–757, November–December, 1990.     

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.     

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.     

Über die Darstellung von 3β, 16α-und 3β, 16β-Diacetoxy-5α-pregnan-20-on

Zusammenfassung Die Synthese von 3, 16-Diacetoxy-5 -pregnan-20-on (VI) aus 3-Acetoxy-5 -pregn-16-en-20-on und eine verbesserte Darstellung von 3, 16-Diacetoxy-5 -pregnan-20-on (III) aus 3-Acetoxy-pregna-5, 16-dien-20-on werden beschrieben.     

Triterpene glycosides ofAstragalus and their genins. VIII. Askendoside C fromAstragalus taschkendicus

A new glycoside of the cycloartane series — askendoside C — has been isolated from the roots of the plantAstragalus taschkendicus Bge., and its structure has been established on the basis of chemical transformations and spectral characteristics as 24R-cycloartane-3,6,16,24,25-pentaol 3-[0--L-arabinopyranosyl-(12)--D-xylopyranoside].Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 173–180, March–April, 1983.     

13C NMR spectra and stereoisomerism in series of androstano-and estrano-D′-pentaranes

Conclusions The stereoisomerism in series of androstano- and estrano-D-pentaranes in solution has been investigated by¹³C NMR. The orientation of the D ring in the 15,16-, 15,16-, and 15,16-isomers relative to the steroid skeleton, as well as the boat conformation of the D ring, were determined from the¹³C chemical shifts.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1038–1045, May, 1984.     

Researches on 2, l, 3-thia- and selenadiazole

4-(,-Dicarboethoxy--acetylamino) ethyl-7-aminobenzo-2,1, 3-thiadiazole (IV) and ethylene oxide form mainly the 7-(-hydroxyethyl) amino derivative (V); the 7- di (-hydroxyethyl) amino derivative VII was isolated in low yield. Action of POCl₃ on compound VII gave the 7-di (-chloroethyl) amino derivative VIII, which was converted into 4-(-amino--carboxy)-ethyl-7 -di (-chloroethyl) aminobenzo-2, 1, 3-thiadiazole (IX). 5-(, -dicarboethoxy--acetylamino) ethyl-4-nitrobenzo-2, 1, 3-thiadiazole (XI) was converted to 5-(-carboxy--amino) ethyl-4-nitrobenzo-2, 1, 3-thiadiazole hydrochloride (XII), from which was prepared, by known routes, and in satisfactory yield, 5-(-carboxy--amino) ethyl-4-di (-chloroethyl)-aminobenzo-2, l, 3-thiadiazole hydrochloride (XVII).For Part XXXIX see [8].     

Order and disorder in mixed metal linear chains: The homo and heterobimetallic EDTA (M(H2O)4OIOII)[M′(EDTA)] · 6H2O complexes (M = Mg,Mn, Co,Zn and Ni; M′ = Co,Ni, Cu and Zn)

Summary Polymetallic solid solutions of the ethylenediaminetetracetic acid (EDTA) and six divalent metal ions exist in the range: MgMnCoZnNiCu(EDTA) · 6H₂O where + + + + + =2, 01, 0,,2, 0, 1.This type of structure is characterized by the presence of two different octahedral carboxylate-bridged coordination sites forming infinite zig-zag chains. Visible and i.r. spectra and t.g.a. analysis show that there is occupational preference for the two coordination sites in the crystalline structure.Due to this preference, and also to the structural features, the heterobimetallic MM(EDTA) · 6H₂O compounds constitute a structurally new class of materials which can be described as ordered alternating-heterobimetallic polymeric coordination complexes.     

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.