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.     

α,β-Butenolides

,-Dibromo--('-carbethoxyacetony)-^,-butenolide (I) reacts with amines in diethyl ether solution to give -bromo-amino--('-carbethoxyacetony)-^,-butenolides. Compounds n are converted to -bromo-amino--('-carbethoxyacetony)-^,-butenolides on reaction with amines. The corresponding arylhydrazones (VI and VII) are obtained by the reaction of I and II with p-nitro- and 2,4-dinitrophenylhydrazines. Compound I reacts with phenylhydrazine to give furopyridazine VIII.See [1] for communication IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 867–871, July, 1972.     

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.     

<Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR spectra of some drimanic sesquiterpenoids

One- and two-dimensional homo- and heteronuclear correlation proton, carbon, proton—proton, and proton—carbon NMR spectra of fifteen drimanic sesquiterpenoids: 11,12-dibromodrima-5,8-dien-7-one, drim-8-en-7-one, 11-hydroxydrim-8-en-7-one, 11,12-dihydroxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 8,9-epoxydriman-7-one, 8,9-epoxydriman-7-ol, 11,12-diacetoxydrim-8-en-7-ol, drimane-7,8,11-triol, 7,8-isopropylidenedioxydriman-11-al, 9, 11-dihydroxydrim-7-en-6-one, drimane-7,8,9-triol, drimane-7,8,11-triol, and drim-8-ene-7,11,12-triol were studied. The proton and carbon chemical shifts were assigned.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2589–2594, December, 2004.     

Unusual oxidation reactions of 7α-methyl- and 7α-phenylcholest-5-ene-3β,7β-diol

Summary Ozonation of 7-methyl (or 7-phenyl) cholest-5-ene-3,7-diol 3-TBDMS ether afforded the corresponding 5,6-epoxy derivatives. The same product was formed byMCPBA oxidation. The reaction of 7-phenylcholest-5-ene-3,7-diol with CrO₃ yielded 3,7-dioxo-6,7-seco-7-phenylcholest-4-ene-5-carboxaldehyde. An analogous B-seco aldehyde was obtained from 7-methylcholest-5-ene-3,7-diol in addition to 7-methylcholesta-4,6-dien-3-one.Jones oxidation of 7-phenylcholest-5-ene-3,7-diol or B-seco-aldehyde gave 3,7-dioxo-6,7-seco-7-phenylcholest-4-en-6-oic acid isolated as its methyl ester upon treatment with diazomethane.

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Ungewöhnliche Oxidation von 7-Methyl- und 7-Phenylcholest-3-en-3,7-diol

Zusammenfassung Ozonolyse von 7-Methyl- bzw. 7-Phenyl-cholest-3-en-3,7-diol-3-TBDMS-ether ergab die entsprechenden 5,6-Epoxy-Derivate.MCPBA-Oxidation führte zum gleichen Ergebnis. Bei der Reaktion von 7-Phenyl-cholest-5-en-3,7-diol mit CrO₃ wurde 3,7-Dioxo-6,7-seco-7-phenyl-cholest-4-en-5-carbaldehyd gebildet. Einen analogen B-seco-Aldehyd erhält man neben 7-Methyl-cholesta-4,6-dien-3-on auch aus 7-Methyl-cholest-5-en-3,7-diol. DurchJones-Oxidation von 7-Phenyl-cholest-5-en-3,7-diol oder B-seco-Aldehyd erhält man 3,7-Dioxo-6,7-seco-7-phenylcholest-4-en-6-carbonsäure, die nach Behandlung mit Diazomethan als ihr Methylester isoliert wurde.

     

13C NMR spectra of acetylated methyl glycosides of monosaccharides

Summary A comparative discussion of the signals in the¹³C NMR spectra of acetylated methyl - and -D-xylopyranosides, - and -D-glucopyranosides, - and -D-galactopyranosides, - and -L-arabinopyranosides, - and -L-fucopyranosides, and - and -L-rhamnopyranosides and of the corresponding free glycosides has shown a similarity of the effects of substitution at C₅ with a longer-range nature of these effects in the case of the acetylated glycosides.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. 1, pp. 6–8, January–February, 1979.     

Synthesis of triterpene glycosides

Summary The acyl -D-glucopyranoside, the acyl -D-xylopyranoside, the acyl D- and L--arabinopyranosides, and the acyl -D-lactoside of 18-glycyrrhetic acid, and also the acyl -D-lactoside of 18-glycyrrhetic acid have been synthesized. The acid and alkaline hydrolysis of the compounds obtained has been studied.Khimiya Prirodnykh Soedinenii, Vol. 4, No. 1, pp. 13–19, 1968     

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.     

Steroid glycosides ofNicotiana tabacum seeds I. The structures of nicotianosides A, B, and E

Two steroid glycosides of the spirostan series — nicotianosides A and B — and one glycoside of the furostan series — nicotianoside E — have been isolated from the seeds ofNicotiana tabacum L. Nicotianoside A is (25S)-5-spirostan-3-ol 3-O--D-glucopyranoside, nicotianoside B is (25S)-5-spirostan-3-ol 3-O-[O--L-rhamnopyranosyl-(12)-gb-D-glucopyranoside], and nicotianoside E is (25S)-5-furostan-3,22,26-triol 26-O--glucopyranoside 3-O-[O--L-rhamnopyranosyl-(12)--D-glucopyranoside].Institute of Genetics, Academy of Sciences of the Republic of Moldava, Kishinev, ul. Lesnaya, 20. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 737–742, November–December, 1994.     

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.     

Investigations in the field of lipids

Summary 1. The synthesis of the following neutral plasmalogens has been effected: -O-(octadec-1-enyl)-, distearoylglycerol, -O-(octadec-1-enyl)-, -dipalmitoylglycerol, -O-(hexadec-1-enyl)-, -distearoylglycerol, and -O-(pentadec-1-enyl)-, -dipalmitoylglycerol.2. During the synthesis, the following compounds were isolated and characterized by their physicochemical constants: the -octadec-1-enyl ether of glycerol, -(2-hydroxyoctadecyl) , -isopropylideneglyceryl ether, the tosylate of -(2-hydroxyoctadecyl) , -isopropylideneglyceryl ether, and -O-(2-tosyloxyoctadecyl) glycerol.3. The IR spectra of the -octadec-1-enyl ether of glycerol and the neutral plasmalogens have been studied.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 6, pp. 367–371, 1966     

Triterpene glycosides ofAstragalus and their genins XLV. The chemical transformation of cycloartanes 1. Synthesis of 25-norglycosides

Literature information is given on the current state of the study of the chemical transformation of cycloartane triterpenoids. A method has been developed for the transformation of the genin part of glycosides of 20,24-epoxycycloartan-25-ols with retention of the carbohydrate constituents. Three 25-norglycosides have been synthesized from natural cyclosieversigenin glycosides, namely 16-acetoxy-3,6-dihydroxy-20R,25-norcycloartan-20,24-olide 3-O-[O--L-arabinopyranosyl-(12)--D-xylopyranoside] 6-O--D-xylopyranoside (VIII), sodium 3,6,16,20-tetrahydroxy-20R,25-norcycloartan-24-oate 6-O--D-glucopyranoside 3-O--D-xylopyranoside (XII), and 20R,25-norcycloartane-3,6,16,20,24-pentaol 6-O--D-glucopyranoside 3-O--D-xylopyranoside (XIII).Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 710–718, September–October, 1993.     

Synthesis and Dehydrohalogenation of 3 β-Chloro-5 α,7 α-dibromo-6-ketosteroids of the Stigmastane and Cholestane Series

3-Chloro-5,7-dibromo-6-ketosteroids 5a and 5b are synthesized from -sitosterol (1a) and cholesterol (1b). Dehydrohalogenation of these forms 7-bromo-2,4-dien-6-ones (6a-b), 2,4-dien-6-ones (7a-b), and 14-hydroperoxy-2,4,7-trien-6-ones (8a-b). Woodward hydroxylation of dienone 6a produces 2-iodo-7-bromo-3-acetoxy-⁴-6-ketone 9 and 7-bromo-2,3-diacetoxy-⁴-6-ketone 10. 2-Iodo-3-acetoxy-^4,7,14-trien-6-one 11 is prepared analogously from trienone 8a.     

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.     

Interactions of Nabumetone with Cyclodextrins in Solution and in the Solid State

The interactions of nabumetone (NAB) with -cyclodextrin (-CD) and-cyclodextrin (-CD) were studied in aqueous solution by meansof phase-solubility analysis. Solid dispersions of NAB with -cyclodextrin(-CD), -cyclodextrin (-CD), methyl- (M-CD),hydroxypropyl-cyclodextrin (HP-CD) were prepared by coevaporationand kneading and also by coprecipitation in the case of -CD. X-ray diffractometry, thermal analysis and infrared spectroscopy (FTIR) were used to study the possibility of complexation of the drug with the different cyclodextrins. Solid dispersions of nabumetone with -CD showed a remarkable improvement in the dissolution rate of nabumetone.     

GC-MS characterization and quantification of sterols and cholesterol oxidation products

Summary A GC-MS method has been studied for characterization and quantification of phytosterols, cholesterol and cholesterol oxidation products. Baseline separations have been achieved between cholesterol, cholesterol 5-6-epoxide, 5-cholestene-3-ol-7one (7-keto-cholesterol), cholestene-3-5-6-triol, 5-cholestene-3-25-diol (25-hydroxycholesterol), 5-cholestene-3-20-diol (20-hydroxycholesterol), 5-cholestene-3-7-diol (7-hydroxycholesterol) and 5-cholestene-3-19-diol (19-hydroxycholesterol) as well as between -cholestane, cholesterol, stigmasterol, campesterol and -sitosterol. Excellent linearity of response has been obtained permitting reliable quantification. The characterization of each derivatized sterol has been performed by mass-spectrometry. The results confirm the utility of combined gas chromatography-mass spectrometry in the analysis and characterization of sterols and cholesterol oxidation products.     

Researches on imidazoles

A study is made of the reaction of the sodium and ammonium salts of 1 -alkyl- and 1, 2-dialkyl-4-nitro-5 mercaptoimidazoles with -halogenoketones, -halogenoalcohols, and — and -halogeno acids, to give a number of 1 -alkyl- and 1, 2-dialkyl-4-nitro-5- [-ketoalkyl (aralkyl)-, -hydroxyethyl-, and -and -carboxyalkyl] mercaptoimidazoles.For Part XXIV see [6].     

Structure and configuration of korseverinine

Conclusions 1. By separating the mixture of bases obtained from the fresh epigeal part ofKorolkowia sewerzowii Rgl. with respect to solubility in different solvents, the alkaloids korseverine, korsinine, korsine, korseveriline, korseveridine, korseveramine, and korseverinine have been been isolated.2. On the basis of a study of chemical transformations and IR, NMR, and mass spectra, the configuration, 5,12,14,13,17,20,22,25-cev-8-ene-3,6-diol has been proposed for korseverinine.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 767–773, November–December, 1971.     

Steroid compounds from the starfish Lysastrosoma anthosticta collected in the Sea of Japan

Six polyhydroxylated steroids and their derivatives were isolated from the starfish Lysastrosoma anthosticta collected in the Posyet Bay, Sea of Japan. These include a new glycoside of the steroid polyol, lysastroside A (1), which was identified as (25S)-26-O--d-xylopyranosyl-5-cholestane-3,6,8,15,16,26-hexaol, and the previously known pycnopodioside C monoglycoside (2), marthasterone sulfate (3), (25S)-5-cholestane-3,6,8,15,16,26-hexaol (4), (25S)-5-cholestane-3,6,7,8,15,16,26-heptaol (5), and (25S)-5-cholestane-3,6,7,8,15,16,26-heptaol (6). The compounds were tested for the haemolytic activity and the action on the embryogenesis of the sea urchin Strongylocentrotus intermedius.     

New cardenolides from the leaves ofGomphocarpus fruticosus

Two new glycosides, gomphotin (1) and gomphotoxin (13), and also the known gomphoside (9) have been isolated from the leaves ofGomophocarpus fruticosus. Compounds (1) and (9) contain a 4,6-dideoxyhexosulose residue as the sugar component, and (13) a 6-deoxyhexosulose, which are attached to glycolic OH groups of the aglycons by 3-O-1,2-O-2 (9, 13) and 3-O-1,4-O-2 (1) acetal-ketal bonds. The structures of the new compounds are represented by the names (3-O-1,4-O-2)-(2,3-dihydroxy-4, 6dideoxyhexulosido)-14-hydroxy-5-card-20(22)-enolide* (1) and (3-O-1,2-O-2)-(2,3,4-trihydroxy-6-deoxyhexulosido)-14-hydroxy-5-card-20(22)-enolide* (13).State Scientific Center for Drugs of the Ministry of Health and the National Academy of Sciences of the Ukraine, Kharkov, fax 441118. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 824–832, November–December, 1995. Original article submitted May 22, 1995.