Glycosides of marine invertebrates. XII. Structure of a new triterpene oligoglycoside from holothurians of familyStichopodidae

From an ethanolic extract of the holothuriansStichopus chloronotus by column chromatography on silica gel a new triterpene oligoside has been isolated the structure of which has been established as 23(S)-acetoxy-3-{4-O-[O-(3-O-methyl--D-glucopyranosyl)-(13)--D-glucopyranosyl]-2-O-[O-(3-O-methyl--D-glucopyranosyl(-(13)-O--D-xylopyranosyl-(14)--D-glucopyranosyl]--D-xylopyranosyloxy}holost-7-ene. A hypothesis has been put forward concerning the biosynthesis of the carbohydrate chains in the glycosides of holothurians of the orderAspidochirota from bioside blocks.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. 200–204, March–April, 1982.     

Rearrangement ofα -trifluoromethyl-β-dialkylamino-β-fluoroacrylic acid N.N-dialkylamides

Conclusions When heated in the presence of a catalytic amount of BF₃ etherate,-trifluoromethyl--diethylamino--fluoroacrylic acid N, N-dimethylamide is reversibly isomerized to-trifluoromethyl--dimethylamino--fluoroacrylic acid N, N-diethylamide. The methyl esters of-trifluoromethyl--diethylammo--fluoroacrylic acid and-trifluoromethyl--phenoxy--fluoroacrylic acid N,N-dimethylamide are not isomerized under the same conditions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No.1, pp.137–141, January, 1976.     

Ultrasonic study of the molecular encapsulation and the micellization processes of dodecylethyldimethylammonium bromide-water solutions in the presence of β-cyclodextrin or 2,6-di-o-methyl-β-cyclodextrin

Aqueous solutions of -cyclodextrin (-CD) or 2,6-di-o-methyl--cyclodextrin (DM--CD) and dodecylethyldimethylammonium bromide (D₁₂EDMAB) have been studied from speed of sound (u) data at 298.15 K, using a pulse-echo-overlap technique. The molecular encapsulation process of the surfactant monomer into the cyclodextrin cavity and its effect in the micellization process of the surfactant have been analyzed from theu measurements: I) as a function of [D₁₂EDMAB] in the presence of several initial cyclodextrin concentrations (-CD or.DM--CD); II) as a function of [cyclodextrin] (-CD or DM--CD), for an initial micellar solution of D₁₂EDMAB and; III) as a function of the [cyclodextrin]/[surfactant] stoichiometric concentrations. Both inclusion complexes formed (-CDD₁₂EDMAB) and (DM--CDD₁₂EDMAB) have stoichiometries of 11, and their association constantK have been determined using a model proposed in this work, based on the additivity of the different contributions of the involved species to the speed of sound. The apparent critical micellar concentration, cmc^*, of D₁₂EDMAB is found to increase linearly upon the addition of cyclodextrin (-CD or DM--CD). The free surfactant concentration in the micellar region, [D₁₂EDMAB]_f, decreases in the presence of -CD and slightly increases in the presence of DM--CD. The influence of the parcial methylation of the -cyclodextrin (-CDDM--CD) and of the polar head of the surfactant (D₁₂TAB D₁₂EDMAB) on the complextion and micellar parameters are also discussed.Supplementary material available: Tables of speed of sound (14 pages) are available from the authors.     

Eine Ringschlußreaktion zu Derivaten der β-{Benzo[b]thienyl(3)}-propionsäure

Zusammenfassung Acylierung von p-Methylthioanisol mit Bernsteinsäureanhydrid ergab -(2-Methylthio-5-methyl-phenyl)--oxo-buttersäure, welche mit Chloressigsäure zu -{2-Carboxy-5-methylbenzo[b]thienyl-(3)}-propionsäure ringgeschlossen wurde.Partielle Decarboxylierung lieferte -{5-Methyl-benzo[b]-thienyl-(3)}-propionsäure.Acylation of p-methylthioanisole by succinic acid anhydride gave -(2-methylthio-5-methyl-phenyl)--oxo-butyric acid, which reacted with chloroacetic acid to give -{2-carboxy-5-methyl-benzo[b]thienyl-(3)}-propionic acid.Partial decarboxylation yielded -{5-methyl-benzo[b]thienyl-(3)}-propionic acid.Herrn Prof.L. Schmid mit besten Wünschen zum 70. Geburtstag gewidmet.     

Radiation-induced reactions of cholesterol in an aqueous medium

⁶⁰Co -ray radiolysis of cholesterol /3-hydroxy-5-cholestene/ /I/ in the two-phase system /water-ethyl acetate/ and in the presence of air has been studied using TLC and GC methods. The following products were observed in the irradiated mixture: 3, 7-dihydroxy-5-cholestene /II/, G O. 36, 3-hydroxy-7-keto-5-cholestene /III/, G 1.48, 3-hydroxy-7-keto-5-cholestane /IV/, G 0.22, 3,5,6-trihydroxy-5-cholestane /V/, G 0.83, 5,6-epoxy-3-hydroxy-5-cholestane /VIa/, G 0.26, 5,6-epoxy-3-hydroxy-5-cholestane /VIb/, G 0.24, and 2, 3-dihydroxy-5-cholestene /VII/, G 0.22. The dose dependence of the formation of these products shows that the cholesterol derivatives substituted in the position 7 /II–IV/ are formed from a common precursor — the radical Ia. On the other hand, the products of the 5–C=C double bond reactions /V and VI/ are formed independently. Also the product VII is formed independently. A reaction scheme that is in agreement with these results is proposed.     

Triterpene Glycosides of Fatsia japonica. VI. Structures of Glycosides D3a and D3b

Seeds of Fatsia japonica (Araliaceae) yielded the new glycosides of gypsogenin: 3-O--D-glucopyranosyl-(12)-O--D-glucopyranoside and 3-O--D-galactopyranosyl-(12)-O--D-glucopyranoside. The structures of these compounds were established by chemical methods and NMR spectroscopy.     

Complexation of the Non-steroidal Anti-inflammatory Drug Loxoprofen with Modified and Unmodified β-Cyclodextrins

The inclusion complex of the anti-inflammatory drug, loxoprofen, with -cyclodextrin-(CD), sulfated -CD, and glycerol ether -CD was studied by UV-VIS absorption and ¹H-NMR spectroscopy in solution. The inclusion complex of loxoprofen with -CDs was prepared by freeze-drying, and then characterized in the solid state by thermal analysis, X-ray diffraction, FT-IR and FT-Raman spectroscopy, and scanning electron microscopy (SEM). Furthermore, a physical mixture of loxoprofen/-CD (1/1, mol-%) in the solid state was also characterized. The solubility of the loxoprofen increased on addition of -CDs. The solubility enhancement of the loxoprofen with -CDs is in the following order: glycerol ether -CD > sulfated -CD > -CD.     

Oligomeric proanthocyanidin glycosides ofRhodiola pamiroalaica. II

In a continuation of investigations of proanthocyanidins of the roots ofRhodiola pamiroalaica, we have isolated proanthocyanidins RP-3 and RP-4. Their compositions, structures, and relative configurations have been investigated: RP-3 is 7-O-(6-O-galloyl--D-Glcp)-3-O-galloyl-(-)-epigallocatechin-(4-8)-[(-)-epicatechin-(4-8)-(3-O-galloyl-(-)-epigallocatechin)]₂-(4-8)-[5-O-(-D-GlcpO--D-Glcp)-(+)-catechin], and RP-4 is 7-O-(6-O-galloyl--D-Glcp-3-O-galloyl-(-)-epigallocatechin-(4-8)-[3-O-galloyl-(-)-galloyl-5-(-D-GlcpO--D-Glcp)-(-)-epigallocatechinTranslated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 42–49, January–February, 1999.     

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

The known compound trojanoside A (1) and a new cycloartane glycoside cyclostipuloside E (2) were isolated from the aerial parts of Tragacantha stipulosa Boriss. The structure of cyclostipuloside E was proposed as 24R-cycloartan-3,6,16,24,25-pentaol 6,16,25-tri-O--D-glucopyranoside 3-O--D-xylopyranoside based.     

Indole derivatives

A series of -, -substituted -(3-indolyl) ketones was obtained by the reaction of indole with , -unsaturated ketones in the presence of perchloric acid.     

Effect of 2-Hydroxypropyl-β-cyclodextrin on Release Rate of Metoprolol from Ternary Metoprolol/2-hydroxypropyl-β-cyclodextrin/Ethylcellulose Tablets

The effect of 2-hydroxypropyl--cyclodextrin (HP--CyD) on the release of a water-soluble ₁-selective adrenoreceptor antagonist, metoprolol (Met), from ternary Met/HP--CyD/ethylcellulose (EC) tablets was investigated. The release rate of Met from the ternary tablets was dependent on amounts of HP--CyD in the tablets, i.e., the rate decreased when small amounts of HP--CyD were added, while large amounts of HP--CyD accelerated the rate. The slowest rate was observed for the tablet consisted of a 30/10/60 weight ratio of Met/HP--CyD/EC. The analyses of the release rates by the Korsmeyer equation and their temperature dependence suggested that Met is released from the EC matrix containing HP--CyD according to the diffusion-controlled mechanism. The water penetration studies and the micro- and macroscopic observations suggested that the retarding effect of HP--CyD is attributable to a viscous gel formation in small pores on the surface of the tablets, where HP--CyD gels may work as a barrier for the water penetration into the tablets and the release of the drug from the tablets. The in-vitro release property of the ternary tablets was reflected in the in-vivo absorption profile in dogs. The results indicated that a combination of HP--CyD and EC is useful for the release control of water-soluble drugs such as Met.     

Nitrosation of mefenorex in the presence of cyclodextrins

- and -Cyclodextrin (CD) and heptakis-2,6-di-O-methyl--cyclodextrin (DIMEB) form soluble inclusion compounds with mefenorex (MEF); with -CD a partial inclusion occurs. No solid inclusion compound could be obtained with the four CDs. -, -CD and DIMEB, but not -CD, enhance the nitrosation rate of MEF if the nitrosation assay procedure (NAP test) is applied. During this reaction with - and -CD, solid inclusion compounds of the CDs and nitrosomefenorex (NMEF) precipitate.Part of the Ph.D. thesis of V. Wedelich, Freie Universität Berlin, 1985.     

Steroids

Summary 1. A new type of steroido[17, 16-d]-3-(methyl, phenyl)isoxazoles has been synthesized by the cyclization of the syn-oximes of acylated 3-hydroxy-16, 17-oxidopregn-5-en-20-ones or their 5-saturated derivatives and acylated 17-benzoyl-3-hydroxy-16, 17-oxidoandrost-5-ones.2. It has been established that the Beckmann rearrangement of the anti-oximes of acylated 17-benzoyl-3-hydroxy-16, 17-androst-5-enes leads to a mixture of anilides and steroidoisoxazoles, which shows the inversion of the configuration of the oximes (from the anti to the syn form) during the rearrangement.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 5, pp. 325–333, 1966     

Recent progress in tartaric acid‐modified Raney nickel system for enantio‐differentiating hydrogenation

Tartaric acidmodified Raney nickel (TAMRNi) is an enantiodifferentiating catalyst for hydrogenation of ketones. The stereochemical models explaining the enantiodifferentiation of ketoester and 2alkanone were unified as an extended stereochemical model by the experimental supports. Based on this new model, a working hypothesis to improve the enantiomeric excess (ee) of the ketoester/TAMRNi system was developed, and the ee was improved to 96%. By further fine tuning of this system, almost perfect enantiodifferentiation resulting in over 98% ee was achieved.     

Two new triterpene glycosides from the holothurian Duasmodactyla kurilensis

Two new glycosides have been isolated from the total triterpene glycosides of the holothurianDuasmodactyla kurilensis: kurilosides A (III) and C (IV). It has been established that (III) is 16-acetoxy-3-{[O--D-glucopyranosyl-(1 4)-O--D-quinovopyranosyl-(1 2)]-[O-(3-O-methyl--D-glucopyranosyl)-(1 3)-O-(6-O-(sodium sulfato)--D-glucopyranosyl)-(1 4)]--D-xylopyranosyloxy}-4,4,14-trimethylpregen-9(11)-en-20-one, while the minor glycoside (IV) is 16-acetoxy-3-{O--D-quinovopyranosyl-(1 2)-[O-(3-O-methyl--D-glucopyranosyl-(1 3)-O-(6-O-(sodium sulfato)--D-glucopyranosyl)-(1 4)]--D-xylopyranosyloxy}-4,4,14-trimethylpregn-9(11)-en-20-one.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 221–226, March–April, 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.     

Indole derivatives

A method is described for the preparation of -(3-indolyl)acrolein. Oximation of this followed by dehydration gives -(3-indolyl)acrylonitrile. Reduction gives -(3-indolyl)allyl alcohol.For part XXXII, see [1].     

Structures of some lilioglycosides from the bulbs ofLilium regale

Six steroid glycosides, which gave been called lilioglycosides B, C, E, F, H, and I have been isolated from fresh bulbs ofLilium regale Wills. The structure of each compound has been determined by methods of physicochemical analysis. This is the first time that lilioglycosides B, C, H, and I, have been described; they are, respectively: (25S)-spirost-5-ene-3,27-diol3-O--D-glucopyranoside; (25R)-spirost-5-ene-3,27-diol3-O--D-glucopyranoside27-(3-hydroxy-3-methylglutarate); (25S)-spirost-5-ene-3,27-diol3-O-{[O--L-rhamnopyranosyl-(12)],[O--D-glucopyranosyl-(13)]--D-glucopyranoside}; and (25S)-spirost-5-ene-3,27-diol 3-O-{[O--L-rhamnopyranosyl-(12)],[O--D-glucopyranosyl-(13)]-O--D-glucopyranoside} 27-[(S)-3-hydroxy-3-methylglutarate].Institute of Genetics, Academy of Sciences of the Republic of Moldava, 2002, Kishinev, ul. Padurilor, 20. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 841–847, November–December, 1997.     

Komplexbildung im System Ni2+—o-Methylbenzamidoxim

Zusammenfassung Die Komplexe des Ni²⁺ mit o-Methylbenzamidoxim wurden in neutraler und in alkalischer Lösung spektrophotometrisch untersucht. Die Bildungskonstanten sindK ₁=40 für 11 undK ₂=1,7·10² für 12 in neutraler Lösung und ₁ = =(3,92 ±0,2) · 10⁴für 11 und lgK = lg ₁ + lg ₂ = 3,45 ± ±0,15 für 12 bei 25° und =1 in alkalischer Lösung.

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Complex formation in the systemeNi ²⁺—o-methylbenzamide oxime

The complexes of Ni²⁺ with o-methylbenzamide oxime were investigated spectrophotometrically in neutral as well as in alkaline solution. The formation constants areK ₁=40 for 11 andK ₂=1.7·10² for 12 in the neutral solution and ₁ = =(3.92 ±0.2) · 10⁴ for 11 and lgK = lg ₁ + lg ₂ = 3.45 ± ±0.15 for 12 at 25° and =1 for the alkaline solution. *** DIRECT SUPPORT *** A3615139 00007