Transformed steroids. 121. Synthesis of the δ-lactone of 3β-acetoxy-16α-hydroxy-6-oxo-24-nor-5α-chol-17(20)-en-23-oic acid

The synthesis of the ¹⁷⁽²⁰⁾-16 analog of natural chiogralactone is described. Attempts to introduce a 6-oxo group directly into the -lactone proved unsuccessful, since the first stage — saponification — took place with the formation of three products: the 3-hydroxy--lactone, the 3-hydroxy-²⁰⁽²²⁾-lactone, and the 15,17(20)-dienoic acid. The synthesis of the desired compound was effected from the ethyl ester of the 5,16-dienoic acid by the scheme 3-acetate3-tosylate6-hydroxy-3,5-cyclosteroid6-oxo-3,5-cyclosteroid6-oxo-5H--lactone. It has been shown that the cyclopropane ring in the 3,5-cyclosteroid -lactone is extremely stable under the conditions of acid treatments.N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 184–187, March–April, 1981.     

Versuche zur Darstellung von 4- Vinyltriarylmethylradikalen

Zusammenfassung Beim Versuch zur Darstellung von 4-Vinyltriarylmethylradikalen durch Umsetzung von 4-Vinyltriarylmethylchloriden mit Metallen entstehen intermediär Radikale, die jedoch sofort in einer mesomeren Form weiterreagieren, wobei Polymere mit Chinodimethan-Strukturen entstehen. Als Modell hierfür dient das gelbe 1,4-,-Diphenylchinodimethan, das aus 4-Methyltriphenylmethylchlorid und Pyridin in Lösung erhalten werden kann; es ist nicht in fester Form isolierbar und polymerisiert sich leicht zu Poly-1,4-,-diphenylxylylen, das durch IR- und NMR-Spektren identifiziert wird.

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The attempted preparation of 4- vinyltriarylmethyl radicals

The attempted preparation of 4-vinyltriarylmethyl radicals by interaction of 4-vinyltriarylmethylchlorides with metals yielded unstable radical intermediates immediately undergoing further reaction to give polymers of a quinodimethane structuretype. 1,4-,-Diphenylquinodimethane, obtained from 4-methyltriphenylmethyl chloride and pyridine in solution, was used as a model compound. It cannot be isolated and readily polymerizes to give poly-1,4-,-diphenylxylylene identified by IR and NMR spectra.

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Mit 2 Abbildungen     

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.     

Charge-transfer Interaction: A Driving Force for Cyclodextrin Inclusion Complexation

PM3 calculations were performed on the complexation of -cyclodextrin (-CD) with nitrobenzene, benzoic acid, benzoate anion, 4-nitrophenol, and 4-nitrophenolate anion. The results, in agreement with the experimental observations, indicated that the complex -CD-benzoic acid was more stable than -CD-nitrobenzene, and -CD-4-nitrophenolate was more stable than -CD-4-nitrophenol. Frontier orbital analysis suggested that charge-transfer interaction led to such behaviors, and hence constituted a nontrivial driving force in the molecular recognition of -CD.     

Approaches to the synthesis of 9α,21-dihydroxy-16α,17α-epoxypregn-4-ene-3,20-diones

Various approaches to the synthesis of 16,17-epoxypregn-4-ene-9,21-diol-3,20-dione were studied. A preparative method was found for the synthesis of this compound by the microbiological transformations of 20,20-dimethoxy-16,17-epoxypregn-5-ene-3,21-diol using Rhodococcus sp. with subsequent removal of the dimethyl acetal protection in 20,20-dimethoxy-16,17-epoxypregn-4-ene-9,21-dio-1-3-one.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 690–693, March, 1990.     

Saponins of dioscorea XV. Caucasosaponin and caucasoprosapogenin fromD. caucasica

Summary Two new saponins have been isolated from the rhizomes ofD. caucasica: the water-soluble caucasosaponin—a rhamnosotriglucoside of 25 D-22-spirost-22-en-3-ol—and the water insoluble caucasoprosapogenin—a glucosotrioside of 25 D-22-spirost-5-en-3-ol-, and also the previously known rhamnosidodiglucoside of 25 D-22-spirost-5-en-3-ol—gracillin.Khimiya Prirodnykh Soedinenii, Vol. 3, No. 4, pp. 237–241, 1967     

Transformed steroids. 160. Reaction of 20,20-dimethoxy-16α,17α-epoxypregn-5-ene-3β, 21-diol-20-one with pyridine thiocyanate and carbethoxyhydrazine

Conclusion The reaction of 20,20-dimethoxy-16,17-epoxypregn-5-ene-3,21-diol-20-one with pyridine thiocyanate in the presence of carbethoxyhydrazine proceeds by two competing paths: cisopening of the oxide ring by a -SCN ion at the C¹⁷ atom, and substitution of one of the methoxyl groups by -NCS ion. As a result 2,20-dicarbethoxyhydrazones of pregn-5-ene-3,21-diol-20-one-[17,16-d]-1,3-oxathiolan-2-one and 20-methoxy-16,17-epoxypregn-5-ene-3-ol-[20,21-d]-1,3-oxazolidine-2-thione are formed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 911–914, April, 1987.     

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     

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.     

Über halogen- und stickstoffhaltige Derivate aliphatischer Carbonsäuren, 6. Mitt.: Über die Gewinnung von α-Oximino- und α-Nitrodicarbonsäureestern

Zusammenfassung Aus den entsprechenden -Bromestern werden durch Umsetzung mit Natriumnitrit die -Oximinodicarbonsäuredimethylester C₇ und C₉ und der , -Dioximinoazelainsäuredimethylester erhalten. -Methyladipinsäure wird zum Gemisch aus -Bromund -Bromester umgesetzt. Mit Natriumnitrit wird -Nitro-und -Oximino--methyladipinsäuredimethylester erhalten.

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The -oximino dicarboxylic dimethyl esters of C₇ and C₉ and the , -dioximino azelaic acid dimethyl ester are received from the corresponding -bromo esters by reaction with sodium nitrite. -Methyladipic acid is reacted with bromine to a mixture of the -bromo and -bromo ester. Reaction with sodium nitrite gives the -nitro ester and the -oximino ester of -methyl adipic acid.

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5. Mitt.:H. Reinheckel, Mh. Chem.98, 1217 (1967).     

Steroid compounds from the Pacific starfish Lysastrosoma anthosticta

Two new steroid compounds, 3,6-dihydroxy-5-cholesta-9(11),24-dien-23-one 3-sulfate and 3,6-dihydroxy-5-cholest-9(11)-en-23-one 3-sulfate, were isolated from the Pacific starfish Lysastrosoma anthosticta as the corresponding sodium salts and identified. Two previously known glycosides of 24(S)-5-cholestane-3,6,8,15,24-pentol were also isolated and identified as sodium 24-O--d-glucopyranoside 6"-sulfate (pycnopodioside C) and sodium 24-O--d-xylopyranoside 4"-sulfate (luridoside A).     

Reduction of some D-homosteroids with an aromatic a ring with alkali metals under the conditions of Birch's reaction. II.

Summary 1. The reduction of 3-methoxy-D-homoestra-1, 3, 5(10), 8-tetraen-17a-ol (IV) with alkali metals in the presence of ammonium chloride or alcohol gives, in addition to 8, 9-dihydro derivatives, the 8, 9 and 8, 9-epimers, the structure of which has been shown partly by independent synthesis and partly on the basis of chemical reactions and NMR spectra.2. Hydrolysis of the reduction products has given 19-nor-D-homotestosterone (III) and its 8- and 9, 10-epimers (V) and (VI). The ketols (III) and (V) readily form hydroperoxides in air.3. The reduction of the ethylene ketal of 3-methoxy-D-homoestra-1, 3, 5(10), 8-tetraen-17a-one (XIX) takes place stereodirectively and gives only 8, 9-dihydro derivatives.Khimiya Prirodnykh Soedinenii, Vol. 1, No. 2, pp. 90–100, 1965     

Transformed steroids. 189. Synthesis and transformations of 21-hydroxy-5α-H-pregnane 2′,2′-dimethyl-[16α,17α-d]-thioxalanes

In a continuation of the research on use of 20-keto-16,17-epoxysteroid 20-hydrazones for synthesis of 17-thio analogs of 20-ketosteroid 16,17-acetonides [2, 3], we synthesized 5-H-pregnane-3,16,21-trihydroxy-17-thiol-20-one 16,17-acetonide and found methods for its microbiological dehydrogenation and hydroxylation into ⁴-3-keto-and 9-hydroxy-⁴-3-keto derivatives.See [1] for Communication 188.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1182–1186, May, 1992.     

Steroid compounds of marine sponges. VIII. 24-Isopropyl-5α-cholest-22-ene-2β,3α,6α-triol trisulfate — A new steroid identified in the spongeTrachyopsis halichondrioides

A new sulfated steroid triol has been identified in extracts of the spongeTrachyopsis halichondrioides and its structure has been established as 24-isopropyl-5-cholest-22-ene-2,3,6-triol trisulfate. The possibility has been shown for the first time of the existence of identical side chains for free sterols and trisulfated steroids.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 111–115, January February, 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.     

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.     

Oxidative methods for synthesis ofα,α′-dioxygen-containing derivatives of dehydrodesthiobiotin

Conclusions The action of selenium dioxide in dioxane on the ethyl ester of-ketodebydrodesthiobiotin and of lead tetraacetate in glacial acetic acid on its N,N-diacetyl derivative give the corresponding ethyl esters of,-dioxodehydrodesthiobiotin and-oxo--acetoxy-N,N-diacetyldehydrodesthiobiotin.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2025–2028, September, 1972.     

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.     

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     

Triterpene glycosides ofHedera taurica. XI. Structures of taurosides St-G1, St-H1, and St-H2 from the stems of Crimean ivy

The previously known glycosides 3-O--L-arabinopyranosyl-28-O-[-L-rhamnopyranosyl-(14)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl]hederagenin and 3-O-[-L-rhamnopyranosyl-(12)-O--L-arabinopyranosyl]-28-O-[-L-rhamnopyranosyl-(14)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl]hederagenin and the new triterpene glycoside tauroside St-H₁ — 3-O--D-glucopyransyl-28-O-[-L-rhamnopyranosyl-(14)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl]hederagenin — have been isolated from the stems ofHedera taurica Carr.M. V. Frunze Simferopol' State University. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 571–579, July–August, 1993.