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.     

Crystal and molecular structures of the sesquiterpene lactone ajafinin

An x-ray structural analysis has been made with the aim of reliably determining the spatial structure of the sesquiterpene lactone ajafinin. It has been established that it has the structure and configuration of 1,2--epoxy-3,4,10-trihydroxy-5,6(H),7(H)-guai-11(13)-en-6,12-olide.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 291–295, May–June, 1986.     

Synthesis of α-alkyl- and α,α-dialkyl-β-phenyltryptamines

A new method was developed for the synthesis of -alkyl- and ,-dialkyl--phenyltryptamines based on alkylation of nitroalkanes with -phenyl-nor-gramine.     

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.     

LLX separation of carrier-free,94,95,97,103Ru,93,94,95,96,99mTc and95,96Nb produced in alpha-particle activated molybdenum by TOA

A radiochemical charged particle activation procedure for the simultaneous production of carrier-free radioisotopes of more than one element in a single target and their subsequent separation through LLX has been demonstrated. The carrier free isotopes,^95,96Nb,^{93,94,95,96,99m}Tc and^94,95,97,103Ru formed through Mo(,pxn), Mo(,pxn) and Mo(,xn) nuclear reactions with 40 MeV -particle as detected by nondestructive -ray spectroscopy, have been effectively separated through LLX using TOA as an anionic extractant. Separation of the bulk matrix of molybdenum from the carrier free products has been monitored radiometrically using isotopic^93,99mMo formed through the Mo(,xn) reaction, as radioindicators for the target element. Purity of the separated carrier free radionuclide has been verified by -ray spectrometry.     

Complex polarizability as used to analyze dielectric relaxation measurements

The effect of representing dielectric properties in terms of the complex polarizability ^c = – i is examined. Loss curves ( and tan ) are shifted towards higher frequencies, revealing the existence of new relaxations and allowing the clarifications of ones already known. We have calculated the shift ratios (at maximum or tan )/ (at maximum or tan ) from the more conventional empirical equations representing the dielectric behavior. Some examples are given.     

Extraction of Polonium from Aqueous α-Hydroxyisobutyric Acid Solutions Using Dioctyl Sulphide, Cyanex 272, Cyanex 301 or Cyanex 302 in Toluene

A study of the extraction of polonium from aqueous solutions containing -hydroxyisobutyric acid (-HIBA) was performed with four different extractants, di-n-octyl sulphide (DOS), Cyanex 272, Cyanex 301 and Cyanex 302, dissolved in toluene. The extracted complex for DOS at low -HIBA concentrations is most likely PoO(-HIB)₂·2DOS, while at higher -HIBA concentrations there seems to be a solvating effect implicating an extracted complex of the type PoO(-HIB)₂(-HIBA)₂·2DOS. For the extraction of polonium with Cyanex 272 the results are inconclusive. The extracted complex is either PoOA₂ or PoO(-HIB)₂·2HA. For extraction with Cyanex 301 or Cyanex 302 the major extracted species does not contain any -HIBA molecules. The neutral species in both cases is PoOA₂, extracted at low extractant concentrations, while at higher extractant concentrations a complex of the type PoOA₂·xHA is extracted. The extraction of polonium increases in the order Cyanex 272 < DOS < Cyanex 302 < Cyanex 301.     

Arjunolic acid derivative glycoside from the stems of <Emphasis Type="Italic">Hedera colchica</Emphasis>

Five triterpenoid saponins were isolated from the stems of Hedera colchica K. Koch, Araliaceae. Two of them are new natural substances. HCSt-A (1): 3-O--D-arabinopyranoside; 28-O--L-rhamnopyranosyl-(1 4)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl-arjunolic acid. HCSt-B (2): 3-O--D-xylopyranoside; 28-O--L-rhamnopyranosyl-(14)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl-hederagenin. The derivative of arjunolic acid is described for the first time in Araliaceae family. The chemical structures of isolated compounds were established on the base of chemical and 1D and 2D NMR experiments.Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 461–463, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Telomerization of ethylene and carbon tetrachloride or chloroform in the presence of the hexacarbonyls of chromium,molybdenum, and tungsten

summary The reaction of telomerization of ethylene with carbon tetrachloride or chloroform is initiated by hexacarbonyls of chromium, molybdenum, and tungsten at 115–120, forming ,,,-tetrachloroalkanes and ,,-trichloroalkanes. respectively.     

Triterpene glycosides ofCauliphyllum robustum. The structures of caulosides B and C

Summary Two triterpene glycosides — caulosides b and c — have been isolated from a methanolic extract of the leaves ofCaulophyllum robustum maxim. Cauloside b has been identified as hederagenin 3--L-rhamnopyranosyl-(12)--L-arabinopyranoside, while cauloside c has the structure of hederagenin 3-0--L-arabinopyranosyl(13)--L-pyranosyl-(12)--L-arabinopyranoside.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. 2, pp. 174–176, March–April, 1979.     

Isomerization of (Het)arylbenzoins in Basic Media

The isomerization of the hetaryl analogs of unsymmetrical benzoins on heating in basic media is a convenient preparative method for the production of -hydroxyacyl derivatives of -excessive heterocycles. The motivating force here for the isomerization is the formation of a thermodynamically more stable product. It was established that isomerization is promoted by increase in the difference between the electron-donating characteristics of the (het)aryl residues     

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).     

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     

On the relationship between the structures of Cu(II) complexes and their chemical transformations

The paper deals with the relationship between the crystal and molecular structures of CuSO₄.5 H₂O, CuSO₄.3 H₂O and CuSO₄.H₂O on the one hand, and the stoichiometries of their thermal decompositions on the other. With the use of methods of X ray powder diffractograms, i.r. and electronic spectra, evidence is provided that the intermediates of the thermal decomposition of CuSO₄.5 H₂O have the same crystal and molecular structures as CuSO₄.3 H₂O and CuSO₄.H₂O prepared by other procedures. It is also shown that at temperatures near that of the thermal decomposition, certain, not further identified structural changes take place in CuSO₄.5 H₂O.

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Zusammenfassung Es wird einerseits der Zusammenhang der Kristall- und Molekularstruktur von CuSO₄ · 5H₂O, CuSO₄ · 3H₂O und CuSO₄ · H₂O behandelt und andererseits die Stöchiometrie ihrer thermischen Zersetzung. Mit der Auswertung der Röntgen-Pulverdiffraktogramme, der IR- und Elektronenspektren wurde der Beweis erbacht, da\ die Zwischen-produkte der thermischen Zersetzung von CuSO₄ · 5H₂O dieselben Kristall- und Molekül-strukturen besitzen, wie auf anderen Wegen hergestelltes CuSO₄ · 3H₂O bzw. CuSO₄ · H₂O. Ferner wurde gezeigt, da\ bei Temperaturen in der NÄhe der thermischen Zersetzungstemperatur gewisse, jedoch noch nicht identifizierte StrukturÄnderungen in dem CuSO₄ · 5H₂O stattfinden.

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Résumé L'article examine la corrélation entre les structures cristallines et moléculaires de CuSO₄.5 H₂O, CuSO₄.3 H₂O et CuSO₄.H₂O d'une part et la stoechiométrie de leur décomposition thermique de l'autre. En se servant des méthodes des diffraction des rayons X sur poudre et des spectres infra-rouges et électroniques on montre que les produits intermédiaires de la décomposition thermique de CuSO₄.5 H₂O ont les mÊmes structures cristallines et moléculaires que celles de CuSO₄.3 H₂O et de CuSO₄.H₂O préparées par d'autres procédés. On montre également qu'à des températures proches de celle de la décomposition thermique de CuSO₄. 5H₂O des changements structuraux non encore identifiés ont lieu.

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uSO₄ · 5₂, uSO₄ · ₂ uSO₄ · ₂, — . , , , uSO₄ · 5₂ uSO₄ · ₂ uSO₄ · ₂, . , , uSO₄, · 5₂ , .

     

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].     

Über die roten Anile. 2. Mitt.

Zusammenfassung Bei der Spaltung des -(p-Dimethylaminophenylimino)--keto--(3,4,5-trimethoxyphenyl)-valeriansäurenitrils (V) mit Chlorwasserstoffsäure entsteht die -Keto--(3,4,5-trimethoxyphenyl)-buttersäure (VII) und nicht, wie infolge des Versagens einiger typischen -Ketocarbonsäurereaktionen vermutet wurde, die 3-Hydroxy-4,5,6-trimethoxy-indan-3-carbonsäure.1. Mitt.:J. Michalský undL. Sadílek, Mh. Chem.90, 171 (1959).     

Effect of the medium on the oxidation of aliphatic monocarboxylic acids

Oxidation rates and k₂/k₆ ratios are given for some acids from propionic to lauric. The k₂/k₆ ratio is shown to be influenced by the electrostatic effect of the solvent. A linear dependence between the isodielectric values of k₂/k₆ and the number of methylene groups in the acid molecules is described.

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k₂/k₆ . k₂/k₆ k₂/k₆ .

     

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     

Thermal properties of thio-and selenocyanatocopper(II) complexes with bipyridine and phenanthroline

The paper deals with the thermal properties of complex compounds of the general formula CuL₂(NCX)₂ (whereL=bipy or phen,X=S or Se). The phenanthroline complexes exhibit a higher thermal stability than those with bipyridine. For the latter complexes thermal decomposition begins with the release of bipyridine molecules, while for the phenanthroline complexes redox reactions of pseudohalogenide ligands with Cu(II) take place. The redox reactions start at a lower temperature for the selenocyanate complexes than for the thiocyanate complexes.

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Zusammenfassung Vorliegende Arbeit behandelt die thermischen Eigenschaften von Komplexverbindungen der allgemeinen Formel CuL₂(NCX)₂ (mitL=Bipyridin oder Phenanthrolin undX=S oder Se). Die Phenanthrolinkomplexe zeigen eine grössere thermische Stabilität als die Bipyridinkomplexe. Die thermiscne Zersetzung letzterer beginnt mit der Abgabe von Bipyridinmolekülen, während bei den Phenanthrolinkomplexen Redoxreaktionen von Pseudohalogenidliganden·mit Cu(II) stattfinden. Diese Redoxreaktionen beginnen bei den Selenozyanatkomplexen bei niedrigeren Temperaturen als bei den Thiozyanatkomplexen.

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CuL₂(NCX)₂, L= , X= . . , — . - , .