Steroid glycosides from the starfish Crossaster papposus

Two new steroid glycosides have been isolated from an ethanolic extract of the starfishCrossaster papposus — crossasterosides P₁ and P₂. On the basis of chemical transformations and spectral characteristics, the structure of crossasteroside P₁ has been established as (24R)-24-ethyl-5-cholestane-3,6,8,15,16,29-hexaol 29-O-[2-O-methyl--D-xylopyranosyl-(1 2)--D-galactofuranoside]. Crossasteroside P₂ is its 4-hydroxy analogue.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 669–673, September–October, 1989.     

Fluorine containing β-lactones

Summary Ring opening of -trifluoromethyl- -methyl- -propiolactone is unidirectional and leads to derivatives of -trifluoromethyl- -hydroxybutyric acid.     

The preparation and properties of 6-phenylacetamido- and 6-phenoxyacetamidopenicillan-3-acetic acids (“homopenicillins”)

6-Phenylacetamido- and 6-phenoxyacetamidopenicillan-3 -acetic acids (homopenicillins) have been obtained from benzyl- and phenoxymethylpenicillins respectively, via their diazoketones. In these compounds, the carboxyl group is separated from the basic thiazolidine--lactam ring of the penicillins by a methylene group, The homopenicillins, which were characterized as their anilides, possess low antibacterial activity and are powerful penicillinase inducers.     

Proanthocyanidins of Polygonum coriarium. I

Six proanthocyanidins have been isolated from the roots ofPolygonium coriarium. The structures of three oligomeric proanthocyanidins have been established: taranin, consisting of [epigallocatechin gallate]-(48)-[epigallocatechin gallate]-(48)-[epigallocatechin-(48)-epigallocatechin₂-(48)-epigallocatechin; taranoside A - [epigallocatechin gallate]-7-0-[-(16)--D-Glcp]₃-(48)-[epigallocatechin-(48)-epigallocatechin]₂-(48)-gallocatechin; and taranoside B - [epigallocatechin gallate]-7-O-[-(16)--D-Glcp]₄-(48)-[epigallocatechin-(48)-epigallocatechin]₂-(48)-epigallocatechin-(48)-[epigallocatechin gallate).Institute of the Chemistry of Plant Substances, Uzbekistan Republic Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 59–67, January–February, 1992     

Enhanced dissolution and oral bioavailability of α-tocopheryl esters by dimethyl-β-cyclodextrin complexation

Inclusion complexation of heptakis (2,6-di-O-methyl)--cyclodextrin (DM--CyD) with -tocopheryl acetate and -tocopheryl nicotinate in aqueous solution was studied by the solubility method. The aqueous solubilities of the esters were about 10⁵ times increased by DM--CyD complexation. The phase-solubility diagram of the tocopheryl ester-DM--CyD systems showed a typicalA _p type, and the stability constants (K) of high-order complexes were estimated by analyzing the upward curvature of the diagrams. The solid complex of -tocopheryl nicotinate with DM--CyD in a molar ratio of 12 was prepared by the kneading method. The dissolution rate of the solid complex was much greater than that of the drug itself, and the rapidly dissolving form of -tocopheryl nicotinate, as an example, showed a markedly increased bioavailability (about 70-fold) after oral administration to fasted dogs.     

Preparation and properties of cyclodextrin inclusion compounds of organometallic complexes. Ferrocene inclusion compounds

Inclusion compounds of ferrocene(FcH) and its derivatives with cyclodextrins(CDs; -CD, -CD, and -CD) were prepared. CD-ferrocene inclusion compounds were obtained in a crystalline state in high yield. -CD and -CD formed 11 stoichiometric inclusion compounds with ferrocene and its derivatives. -CD formed 21 (CD:guest) complexes with ferrocene and the monosubstituted derivatives, but did not form complexes with 1,1-disubstituted derivatives, -CD-FcH and -CD-FcH complexes are thermally stable and do not liberate ferrocene on heating at 100°C in vacuo. The cyclodextrin inclusion compounds were characterized by¹H-NMR, IR, UV, and CD spectra. A large positive induced Cotton effect was observed in the case of -CD-FcH complex, while the -CD-FcH complex showed a negative spectrum. The binding mode is discussed. -Cyclodextrin was found to form inclusion complexes in ethylene glycol, diethylene glycol, triethylene glycol, methyl cellosolve, ethyl cellosolve, methyl alcohol, and glycerine solutions. -CD also formed complexes in ethylene glycol solution. The binding of ferrocene by -CD is stronger in ethylene glycol than in dimethyl sulfoxide and dimethyl formamide.     

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.     

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.     

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.     

Molecular Recognition Based on Roof-shaped Diol Hosts. X-Ray Crystal Structures of Inclusion Compounds with Methanol, Pyridine and Toluene

Three crystalline inclusion compounds of roof-shapedtrans-11,12-bis(diaryl-hydroxymethyl)-9,10-dihydro-9,10-ethanoanthracene host molecules [where aryl is 4-methyl-phenyl (3) or4-t-butylphenyl (4)] have been studied by X-ray diffraction.The crystals of both the 3methanol (2 : 1) [a = 10.755(1),b = 11.571(1), c = 14.697(2) Å, = 75.12(1), = 89.67(1), = 87.13(1) °] and the 4-pyridine (2 : 3) compounds[a = 14.045(3), b = 14.366(3), c = 15.607(3) Å, = 91.62(1), = 103.65(1) and =116.05(1)°] are triclinic (P–1),while the 3toluene (1 : 1) complex has orthorhombic (Fddd) symmetry [a = 16.041(1), b = 25.008(1), c = 40.440(4) Å]. The host–guest interactions in both triclinic crystals are characterised by hydrogen bonds, with different patterns however. The determined crystal structures indicate a compromise between the requirement of hydrogen bonding on the one hand and close packing on the other. The highly symmetrical host framework in the toluene (1 : 1) complex of 3 seems to be the result of shape recognition, although atendency towards weak (C_methyl)H _arylinteractions [C_methyl = 3.533(7) and 3.674(6) Å] between the hosts was observed. The present roof-shaped diol hosts give excellent examples of molecular recognition by exhibiting two significantly different conformations, mostly depending on the proton donor/acceptor ability of the guest component. (O)H O intramolecular bonding between the two alcoholic groups characterises the so-called active form, whereas weaker (O)H and interactions stabilise the `inactive'conformation.     

Enantiomer separations with chromatographic supports based on β-cyclodextrin polymers immobilized on porous silica. Role of the polymer structure in separating ability

Summary Two -cyclodextrin (-CD)-containing polymers have been prepared either by condensation of -CD molecules with a bifunctional reagent or by grafting a -CD derivative on to a linear polymer (polyvinylimidazole). HPLC stationary phases were obtained by adsorption of the -CD polymers on to silica. The ability of these chromatographic supports to resolve racemic mixtures of organic compounds such as amino acid derivatives, phenylhydantoins, barbiturates, and hydroxycoumarin derivatives has been investigated. Results were found to depend on the chemical structure of the -CD polymers     

Synthesis of 2β, 3β, 14α-trihydroxy-Δ4,7-6-ketosteroids and their derivatives

A scheme using -sitosterol as an example for synthesizing 2, 3, 14-trihydroxy-^4,7-6-ketosteroids and their derivatives from 3-hydroxy-⁵-steroids was developed.Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, 220141, Belarus, Minsk, ul, akad. Kuprevicha, 5/2. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 244–248, May–June, 2000.     

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.     

Steroid saponins and sapogenins ofAllium IX. The structure of aginoside

Summary From a methanolic extract of the skins of the bulbs ofAllium giganteum Rgl, a new steroid glycoside has been isolated — aginoside, which is (25R)-5-spirostan-2, 3, 6-triol 3-0-{[0--D-xylopyranosyl-(13)-]-[0--D-glucopyranosyl-(12)]-0--D-glucopyranosyl-(14)-0--D-galactopyranoside}.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 480–486, July–August, 1976.     

Synthesis of pyridine and quinoline derivatives of ferrocene from β-chloro-β-ferrocenylacrolein

2-Ferrocenylquinolines that contain a hydroxy or methoxy group in the 7 position were obtained by the reaction of -chloro--ferrocenylacrolein with m-anisidine and with m-aminophenol. The introduction of aniline in this reaction leads to the formation of -ferrocenyl--phenylaminoacrolein anil hydrochloride, which cannot be converted to 2-ferrocenylquinoline. 2,3,6-Trisubstituted pyridines that contain a ferrocenyl substituent in the 6 position were obtained by condensation of -chloro--ferrocenylacrolein with -dicarbonyl compounds.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1376–1378, October, 1981.     

Unsaturated esters of N-(β-hydroxyethyl) lactams

A general method is developed for synthesizing methacrylic esters with a 5-, 6-, or 7-membered lactam ring to the carboxyl group, by reacting the sodio-derivatives of the lactams with -chloroethyl methacrylate. The esters synthesized are prone to thermal polymerization, and able to copolymerize with other monomers in the presence of azodiisobutyronitrile. The following copolymers are prepared; -(N-pyrrolidonyl) ethyl acrylate with methyl acrylate, -(N-pyrrolidonyl) ethyl, -(N-2-oxotetramethyleneimino) ethyl, and -(N-2-oxopentamethyleneimino) ethyl methacrylates withmethyl methacrylate.     

Secondary metabolites of Astragalus danicus Retz. and A. inopinatus Boriss.

The chemical composition of the above-ground parts of Astragalus danicus and A. inopinatus collected in the Baikal region (Eastern Siberia) was studied for the first time. From A. danicus, pentacyclic triterpene saponins were isolated and identified, viz., 3-O-(-glucuronopyranosyl)-3,22,24-trihydroxyolean-12-ene, 3-O-[O-(-d-xylopyranosyl)-(12)-(-glucuronopyranosyl)]-3,22,24-trihydroxyolean-12-ene, 3-O-[O-(-d-glucopyranosyl)-(12)-(-glucuronopyranosyl)]-3,22,24-trihydroxyolean-12-ene, 3-O-[O-(-l-rhamnopyranosyl)-(12)-O-(-d-xylopyranosyl)-(12)-(-glucuronopyranosyl)]-3,22,24-trihydroxyolean-12-ene, 3-O-[O-(-l-rhamnopyranosyl)-(12)-O-(-d-glucopyranosyl)-(12)-(-glucuronopyranosyl)]-3,22,24-trihydroxyolean-12-ene, 3-O-methyl-d-chiro-inositol, and linolenic acid. In A. inopinatus, the same saponins were identified as well as tricosan-1-ol and tetracosan-1-ol, 5,7,4"-trihydroxyflavon (apigenin), and a tetracyclic triterpenoid, 20(R),24(S)-epoxycyclolanost-9(11)-ene-3,6,16,25-tetrol (cycloastragenol). All reported compounds from the both genus of Astragalus were isolated for the first time. Methanolic extracts of A. danicusand A. inopinatus exhibited low inhibitory activity with respect to the growth of HeLa cells. The chloroform fraction of A. danicus showed a strong antimicrobial activity against Staphylococcus aureus and a strong cytotoxic activity against HeLa cells.     

The Interactions of Titanocene Dihalides with α-, β- and γ-cyclodextrin Host Molecules

The inclusion of titanocene dihalides (X = F, Cl) into -, - and -cyclodextrin hosts was studied by NMR spectroscopy, thermal analysis and mass spectrometry. It was found that -cyclodextrin does not form inclusion complexes with titanocene halides whereas - and -cyclodextrin do form such complexes. According to the changes in NMR spectra we propose that there is a shallow penetration of a guest molecule of titanocene dihalide into the cavity in the case of -cyclodextrin, but deeper penetration in the case of -cyclodextrin. The stability of the latter inclusion complexes was studied by NMR shift titration.     

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 the holothurian Eupentacta pseudoquinquisemita

The holothurianEupentacta pseudoquinquisemita Deichmann collected in Kraternaya Bay, Ushishir Islands has yielded two triterpene pentaosides — the previously known cucumarioside C₂, and cucumarioside H, which is a new glycoside. With the aid of¹³C NMR spectroscopy and solvolytic desulfation its structure has been determined as 6-acetoxy-3-([3-O-methyl--D-xylopyranosyl-(1 3)--D-glucopyranosyl-(1 4)] [-D-xylopyranosyl-(1 4)] [-D-xylopyranosyl-(1 2)]--D-quinovopy-ranosyl-(1 2)-(4-O-sulfato--D-xylopyranosyloxy)holosta-7,22,24(trans)-triene. Cucumarioside H was also identified inEupentacta (=Cucumaria)fraudatrix from Posyet Bay, Sea of Japan.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 221–225, March–April, 1988.