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.     

Polyhydroxylated steroids from the starfishPatiria pectinifera

By chromatography on Polikhrom-1, silica gel, and Florisil, an ethanolic extract of the digestive organs of the starfishPatiria pectinifera has yielded the steroid polyols 5-cholestan-3,6,8,15,16,26-hexaol and 5-cholestan-3,4,6,7,8,15,16,26-octaol 6-(sodium sulfate). The structures of the compounds have been shown by spectral characteristics and chemical transformations.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 738–741, November–December, 1984.     

ESR studies of the generation of adsorbed oxygen radicals under irradiation of CaO in the range of surface absorption

Anion-radicals of oxygen O ₂ ^– and complexes of molecular oxygen with hole centers [X·O₂] (g₁=2.002, g₂=2.009, g ₃ ¹ =2–015, g ₃ ² =2.016) and [Y·O₂] (g=2.004, g=2.012) have been found to form under CaO irradiation in the range of surface absorption (h4 eV). ESR spectra of X and Y centers have not been observed. They are suggested to be anion-radicals O _st ^– in various coordinations: (O _3C ^– )_st and (O _4C ^– )_st, respectively.

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- O ₂ ^– [XO₂] (g₁=2.002, g₂=2.009, g ₃ ¹ =2.015, g ₃ ² =2.016) (g=2.004, g=2.012) CaO (h4 ). X Y . , - O _st ^– , : (O _3C ^– )_st (O _4C ^– )_st, .

     

Chemistry and Structure of Diterpene Compounds of the Kaurane Series: IV.1 Acylation of Reduction Products of the Isosteviol Keto Group

Acetylation with acetic anhydride of (4,8,13)-16-hydroxy-13-methyl-17-norkaurane-18-carboxylic acid and its methyl ester, obtained by reduction of isosteviol and (4,8,13)-18-methoxycarbonyl-13-methyl-16-oxo-17-norkaurane, respectively, gives rise to (4,8,13)-16-acetoxy-13-methyl-17-norkaurane-18-carboxylic acid and (4,8,13)-16-acetoxy-18-methoxycarbonyl-13-methyl-17-norkaurane. The molecular and crystal structures of the compounds were established by X-ray diffraction.     

Triterpene glycosides of Hedera taurica

From the leaves of Crimean ivy we have isolated the previously known glycosides 3-O--L-Ara_p-28-O-[O--L-Rha_p-(14)-O--D-Glc_p-(16)--D-Glc_p]hederagenin, 3-O-[O--L-Rha_p-(12)--L-Ara_p]-28-O-[O--L-Rha_p-(14)-O--D-Glc_p-(16)--D-Glc_p]oleanic acid and -hederagenin, and 3-O-[O--L-Rha_p-(12)--L-Ara_p]-28-O-[O--D-Glc_p-(16)--D-Glc_p]hederagenin and a new one: tauroside H₁ — 3-O-[O--L-Rha_p-(12)-O--L-Ara_p]-28-O-[O--L-Rha_p-(14)-O--D-Glc_p-(16)--D-Glc_p]echinocystic acid.M. V. Frunze Simferopol' State University. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 522–528, September–October, 1992.     

Alkyl-substituted dipyrrylmethenes and their oxa- and thia-analogs: “structure—solvation properties” correlations

New data on the spectral properties and solution enthalpies of unsymmetrically substituted 2-(alkyl-2-pyrrolylmethylidene)methylpyrrolium bromides (or ,-dipyrrylmethene hydrobromides), their ,-, ,-isomers, as well as their oxa and thia analogs, that is, 2-(2-furylmethylidene)- and 2-(2-thienylmethylidene)-3,4,5-trimethyl-1H-pyrrolium bromides, in solutions of organic solvents of different nature are presented. A decrease in the number of substituents, as well as replacement of the heteroatom (N) in one five-membered ring of the dipyrrylmetnehe by oxygen or sulfur atoms cause a monotonic hypsochromic shift of absorption bands in the electronic absorption spectrum and weakening of the chromophore properties of the compounds. The chromophore properties of isomers are weakened from the ,- to ,- and ,-dipyrrylmethenes. Main trends in the influence of structural factors on the specific features of thermooxidative destruction of the above-mentioned compounds were analyzed.     

Nitroderivate vonβ,β,β-Trihalo-α,α-bis-(4-alkoxybzw. 4-oxy-phenyl)-äthanen

Zusammenfassung Auf Grund von Modellbetrachtungen wurde die Existenz der in der Literatur beschriebenenOctanitro-Derivate von ,,-Trihalo-,-bis-(4-alkoxy-phenyl)-äthanen in Zweifel gezogen. Entsprechende Untersuchungen ergaben, daß es sich bei ihnen umTetranitro-Verbindungen handelt und daß es nicht möglich ist, diese DDT-Analogen mehr als vierfach zu nitrieren. Die Konstitution der Tetranitro-Verbindungen wurde durch Abbau bewiesen: Beim ,,-Trichlor-,-bis-(3,5-dinitro-4-methoxy-phenyl)-äthan (II) durch Überführung in das entsprechende Keton (VII), beim ,,-Trichlor-,-bis-(3,5-dinitro-4-äthoxy-phenyl)-äthan (IV) durch Entalkylierung und Methylierung zu II. Der Beweis der 3,3, 5,5-Stellung der Nitrogruppen in II und IV ist auch für andere Tetranitro-Derivate von ,,-Trihalo-,-bis-(4-X-phenyl)-äthanen (X=Substituenten I. Ordnung) von Bedeutung.Mitt. II der Reihe: Stereochemische Untersuchungen in der Diphenylmethanreihe.     

Triterpene Glycosides of Astragalus and Their Genins. LXI. Occurrence of Cycloartane 6-O-Monodesmosides

Cyclosiversigenin 6-O--L-rhamnopyranoside and 6-O--D-glucopyranoside were isolated fromAstragalus coluteocarpusBoiss. (Leguminosae) andAstragalus dissectusB. Fedtsch. et N. Ivanova, respectively. Cyclosiversigenin 5-O--L-rhamnopyranoside was shown to be an artifact forAstragalus coluteocarpus.Thus, the cyclosiversigenin 6-O--D-glucopyranoside that was isolated from certainAstragalusspecies is hypothesized also to be an artifact. Glycosylation of the 6 -hydroxyl group of cycloartanes by D-glucose and D-xylose, in contrast with other substituents, does not change the low-field position of the PMR signal of the 4-CH ₃ group (1.65 2.01 ppm) that is caused by the influence of deuteropyridine directly on the 6 -hydroxyl. Obviously one of the hydroxyls of the -D-glucopyranoside or -D-xylopyranoside residues has the same effect in this instance.     

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.     

Synthesis of esters of α-chloroacetoxy-β,β,β,-trichloroethylphosphonic acids

Summary The synthesis of 11 previously unreported dialkyl esters of -mono-, -di-, and -trichloroacetoxy-,,-trichloroethylphosphonic acids has been effected.     

Synthesen von Heterocyclen, 117. Mitt.: Eine Synthese von β-Lactamen

Zusammenfassung Aus Mono-und Dihalogen-essigsäuren bilden sich mitSchiff-schen Basen in Dimethylformamid (DMF) und POCl₃ (bzw. POBr₃) über labile Addukte -Lactame. Analog reagieren -Chlor-und -Brom-propionsäure.

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The reaction of -chloro and -bromo acetic or propionic acids withSchiff bases inDMF in the presence of POCl₃ or POBr₃ yields -lactames via unstable adducts.

     

Synthesis of the 3,22,23-triacetates of 28-homotyphasterol and its (22S,23S)-isomer

Acetates of the brassinosteroids 28-homotyphasterol and (22S,23S)-28-homotyphasterol have been obtained from stigmasterol. The scheme of synthesis includes the epoxidation of the corresponding 2,22-diene-6-ketone, reduction of the 2, 3:22,23-diepoxy-6-ketone formed with lithium tetrahydroaluminate to a 22,23-epoxy-3,6-diol, oxidation of the 6-hydroxy group to a 6-ketone, and conversion of the 22,23-epoxides into cis-22,23-diols.Institute of Bioorganic Chemistry, Belarus Academy of Sciences, 220141, Minsk, ul. Zhodinskaya, 5/2. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 694–699, September–October, 1995. Original article submitted January 30, 1995.     

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.     

Investigations in the field of complex lipids

Summary 1. The synthesis of L-(+)--oleoyl--linoleoyl--glycerylphosphorylethanolamine has been effected.2. During the investigations the following substances were isolated and characterized: L--oleoyl--glycerylphosphoryl-N-phthaloylethanolamine and L---linoleoyl--glycerylphosphoryl-N-phthanoylethanolamine.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 2, pp. 80–83, 1966     

Optimization of mobile phases for HPLC of cis-trans carotene isomers

Summary Various methanol-based, binary and ternary solvent systems were compared with respect to resolution of cis isomers of and -carotene by reversed-phase HPLC. A ternary system: acetonitrile-methanol-methylene chloride (751510), or a binary system: acetonitrilemethanol (9010 or 595) provided the best separation of -carotene and its four cis isomers, 9-cis, 13-cis, 15-cis and 13,15-di-cis--carotene. The elution order of 9-cis and 13-cis--carotene was dependent on the methanol concentration. Methanol-methylene chloride (991) resolved -carotene and its three cis isomers, 9-cis, 13-cis, and 15-cis--carotene. It also proved the best for simultaneous separation of cis isomers of and -carotene. Sample solvent can affect the separation efficiency of each isomer. The presence of cis isomers of and -carotene in fresh and cooked carrots was also determined.     

Normal and reversed-phase HPLC for more complete evaluation of tocopherols,retinols, carotenes and sterols in dairy products

Summary We have previously described a normal-phase HPLC method for the simultaneous determination of , , and tocopherol, thecis andtrans isomers of retinol, and total carotenes in different Italian cheeses and milk. In this paper we describe a reversed-phase HPLC method using solely methanol as the mobile phase for the determination of -tocopherol, -+-tocopherols, total retinols, cholesterol, -sitosterol, campesterol and stigmasterol, and - and -carotene. The method developed has been applied to some new dairy products such as natural Quark, with olive, basil or banana and to processed cheese with tomato and the results have been compared with the corresponding results obtained by the normal-phase method. The conclusion is that more complete evaluation of the tocopherol, retinol, carotene and sterol content of dairy products, especially when vegetables and fruits are present, is necessary and can be obtained using both the normal- and reversed-phase HPLC methodologies.     

Solvent/water partitioning of dimethylmethylphosphonate (DMMP) as a probe of solvent acidity

Experimentally determined partition coefficients for DMMP between NaCl-saturated water and 20 solvents were correlated using the solvatochromic parameters , , and ^*. An inverted LSER was then used to predict for 7 additional solvents. The new cohesion parameters and ^*2 were found to be more representative of cavity formation than _H ² . Most importantly, it was essential to include either or _H ² in the LSER. The partition method appears to be a useful adjunct to solvatochromic techniques in refining and extending the scale of solvent acidity and could be used to rationalize solvent selection in extraction processes.     

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.     

Triterpene glycosides ofHedera taurica XV. Structures of glycosides St-I3, St-I4a, St-I4b, and St-I5 from the stems of Crimean ivy

From the stems of Crimean ivyHedera taurica Carr. (fam. Araliaceae) we have isolated the new triterpene glycosides St-I₃, St-I₅, and St-I_4a, which are, respectively, the 3–0--D-glucopyranoside 28-O-[O--L-rhamnopyranosyl-(14)-O-(6-O-acetyl--D-glucopyranosyl)-(16)-O--D-glucopyranosides] of oleanolic acid and of hederagenin and the 3-O--D-glucopyranuronoside 28-O--gentiobioside of oleanolic acid, and also the previously known 3-O-[O--D-galactopyranosyl-(12)--D-glucopyranuronoside 28-O--D-glucopyranoside] of oleanolic acid (glycoside Rb-4).Simferopol' State University. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 404–410, May–June, 1997.     

Prostanoids: LXXVII. Synthetic Approaches to Sterically Overcrowded Cyclopentenones

Condensation of (±)-5-allyl-2,3,5-trichloro-4,4-dimethoxy-2-cyclopentenone with phenylethynylmagnesium bromide in THF gave (±)-5-allyl-2,3,5-trichloro-4,4-dimethoxy-1-phenylethynyl-2-cyclopenten-1-ol which chemoselectively reacted with ozone at the terminal double bond, affording (±)-2,3,5-trichloro-5-formylmethyl-4,4-dimethoxy-1-phenylethynyl-2-cyclopenten-1-ol. Oxidation of the latter with H₂CrO₄ yielded a mixture of the expected product, (±)-5-carboxymethyl-2,3,5-trichloro-4,4-dimethoxy-1-phenylethynyl-2-cyclopenten-1-ol, and anomalous profound oxidation product, (±)-2,3,5-trichloro-5-carboxymethyl-4,4-dimethoxy-1-(2-oxo-2-phenylacetyl)-2-cyclopenten-1-ol. Attempts to remove protective methoxy groups in these compounds under standard conditions were unsuccessful.