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.     

Zusammenhang zwischen den K α-Satelliten-Linien und den Röntgenübergängen vom Typ K 1 L 1→L 2 bei den Elementen Neon,Natrium, Magnesium,Aluminium und Silizium

Zusammenfassung Für die Elemente Neon, Natrium, Magnesium, Aluminium und Silizium werden mit einem quantenmechanischen Variationsverfahren unter Verwendung einer minimalen STF-Funktionenbasis Röntgenübergänge vom Typ K ¹L¹L² berechnet und den K -Satellit-Linien , , ₃, ₃ and ₄ zugeordnet.

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Relation between K -Satellits and X-ray-transitions of the type K ¹ L ¹L ² for Ne, Na, Mg, Al and Si

STF-Calculations are reported for X-ray-transitions of the type K ¹L¹L² for Ne, Na, Mg, Al and Si. It is shown that these transitions are correlated with the K -satellits , , ₃, ₃ and ₄.

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Die Wellenfunktionen können auf Anfrage zur Verfügung gestellt werden.     

1H-NMR Investigation of the Binding of 2-Methylnaphthalene to α-Cyclodextrin in D2O Solutions

As -cyclodextrin (-CD) was added to D₂Osolutions of 2-methylnaphthalene, its proton signals shifted to lower fieldsat low concentrations of -CD. At 2.0 × 10^-2 moldm^-3 of -CD, however, a reverse, higher-field shift wasobserved for the H-8 signal, indicating the formation of 1 : 1 and 2 : 1-CD–2-methylnaphthalene inclusion complexes. Intrinsic chemicalshift differences of all the protons in 2-methylnaphthalene have beenevaluated for both the 1 : 1 and the 2 : 1-CD–2-methylnaphthalene inclusion complexes. These intrinsicchemical shift differences suggest that the first -CD molecule has noselectivity in accommodating one end of uncomplexed 2-methylnaphthalene;-CD binds to a methyl group, as well as a naphthalene ring-end havingno methyl group, to form the 1 : 1 inclusion complex, resulting in theformation of two kinds of 1 : 1 complexes.     

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     

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     

Complete synthesis of serratamolide

Summary 1. A method for the separation and quantitative determination of - and -DNP derivatives of , -DABA, ornithine, and lysine has been proposed.2. A quantitative evaluation of the N N migration in four peptides of , -DABA has been carried out.3. The degree of migration in inactive polymyxin M and the DNP-peptides from a partial hydrolyzate of the inactivated antibiotic has been determined.4. The amino acid composition of the DNP peptide B1 from a partial hydrolyzate of active DNP-polymyxin M has been established.5. The quantitative aspect of the conversion of and diketopiperazines has been studied.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 4, pp. 277–284, 1966     

Enthalpy of solution of carbohydrates using a modified differential scanning calorimeter

A differential scanning calorimeter (DSC) was modified for the determination of enthalpies of solution. The measurements were performed on aqueous solutions of the deoxy- and fluoro-deoxy derivatives of D-glucopyranose (Glu) where the OH group on the C1, C2, C3, and C6 is replaced by H (1HGlu, 2HGlu, 3HGlu, and 6HGlu) and by F (1FGlu, 2FGlu, 3FGlu, and 6FGlu), 4-deoxy 4-fluoro--D-glucopyranoside (4FGlu), 1-methoxy--D-glucopyranoside (MeOGlu), 1-phenoxy--D-glucopyranoside (PheOGlu), D-mannopyranose (Man), and 3-methoxy--D-glucopyranoside (3MeOGlu), at 15.1, 25.0, 35.0, and 45.1°C. The enthalpies of solution _sH⁰(T) ranged from 1.00±0.25 kJ-mol^–1 for 6HGlu at 15.1°C to 20.4±1.4 for PhOGlu at 45.1°C and were in good agreement with literature values for Man, Glu, MeOGlu, and 3MeOGlu at 25.0 and 35.0°C and for MeOMan and 2HGlu at 35.0°C. _sH⁰(T) for the derivatives were then extrapolated up to the melting temperature T_m and compared with their enthalpies of fusion, _fH also determined from DSC measurements. If the agreement between _sH⁰(T_m) and _fH was within the 95% confidence level, then it was concluded that intermolecular interactions between the carbohydrate molecules in the liquid phase were the same as between the carbohydrate and water molecules in the solution phase. This agreement was observed for aqueous solutions of Man, Glu, MeOGlu, 3HGlu, 3FGlu, and 6FGlu.     

Diels-Alder reaction of 16-dehydropregnenolone acetate with 1,2-dimethylenecyclobutane

Conclusions 16-Dehydropregnenolone acetate undergoes condensation with 1,2-dimethylenecyclobutane in the presence of a Lewis acid to form a 16,17-monoadduct, namely, 3,4-ethano-16,17-cyclohex-3-enopregn-5-en-3-ol-20-one acetate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2397–2399, October, 1985.     

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.     

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.     

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.     

Synthesis of homologs of p-phenoxystyrene

Conclusions Homologs of p-phenoxystyrene that had not been described in the literature have been synthesized: -methyl-p-phenoxystyrene, -ethyl-p-phenoxystyrene, ,-dimethyl-p-phenoxystyrene, -methyl-p-phenoxystyrene, and ,-dimethyl-p-phenoxy styrene.     

A general differential technique for the determination of parameters for d(α)/dt=f(α)A exp (−E/RT)

A general differential method is developed and described which determines the Arrhenius parameters, energy of activation and the preexponential factor, as functions of degree of conversion from sets of two or more experiments with differing thermal programs. (These experiments may be performed at any combination of isothermal, constant heating rate or other temperature programs.) The method tests to see whether or not the kinetics follow the equation,f()=(1–)ⁿ, and calculates the correct reaction order, n, when such an equation is applicable. The correct energy of activation,E, is determined as a function of both temperature and conversion. The correct preexponential term,A, is calculated for all cases described by equation, d()/dt=f () A exp(–E/RT), except for the autocatalytic case in whichf()=0)=0. Calculation of parameters for equations involving other functions forf() will be described in a subsequent paper.

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Zusammenfassung Es wurde ein allgemeines Differentialverfahren entwickelt und beschrieben, das die Arrheniusschen Parameter, namentlich die Aktivierungsenergie und den präexponentiellen Faktor, als Funktion des Umsetzungsgrades aus Angaben über zwei oder mehrere Experimente mit verschiedenen Temperaturprogrammen beschreibt. (Diese Experimente können mit beliebigen Kombinationen aus isothermen Temperaturprogrammen, solchen mit konstanter Aufheizgeschwindigkeit oder anderen Temperaturprogrammen durchgeführt werden.) Das Verfahren überprüft, ob die Kinetik durch die Gleichungf()=(1–)ⁿ beschrieben werden kann und berechnet die richtige Reaktionsordnungn, wenn eine solche Gleichung anwendbar ist. Die richtige Aktivierungsenergie E wird als Funktion von Temperatur und Umsatz bestimmt. Der richtige präexponentielle Ausdruck wird für alle beschriebenen Fälle mittels der Gleichung d()/dt=f()A exp (-E/RT) berechnet. Eine Ausnahme bildet der Fall Autokatalyse, wobeif(=0)=0 gilt. Die Berechnung der Parameter für Gleichungen mit anderen Funktionen fürf() wird in einem späteren Manuskript beschrieben.

     

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.     

Über halogenierte Äther

Zusammenfassung Die Alkoholate einiger Halbäther des Äthylenglykols reagieren mit Trichloräthylen unter Bildung von ,-Dichlorvinyläthern. Diese Äther addieren Chlorwasserstoff unter Bildung von ,,-Trichloräthyläthern, deren Struktur durch Verseifung zu den Chloracetaten der Halbäther des Äthylenglykols bewiesen wird.     

Substituted hydrazides of hydroxycarboxylic acids

The action of N-methylpiperazine and , -dimethylpyrrolidine on chloroacetyl derivatives of phenylhydrazides of diaryl- and dialkylglycolic acids has given the previously unknown N-methylpiperazinoacetyl and , -dimethylpyrrolidnoacetyl derivatives of these phenylhydrazides.For part XL, see [1].     

Depsipeptides Communication 31. Synthesis of depsipeptides containing α-hydroxy α-amino acid residues

Summary Depsipeptides containing -hydroxy -amino acid residues as hydroxy-acid component were synthesized.Communication 11 of the series -Substituted -Amino Acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 1987–1992, November 1965     

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.     

Steroids

Conclusions 1. It has been established that the hydrogenation of 11-hydroxy-16-methylpregn-4-ene-3,20-dione and of 16-methylpregn-4-ene-3, 11 20-trione over 10% palladium on calcium carbonate in pyridine takes place stereospecifically and is determined by the substituent at C₁₁.2. It has been shown that a 16-methyl group has practically no influence on the stereochemical directivity of the hydrogenation of the ethylenic bond of the ⁴-3-oxo system.Khimiya Prirodnykh Soedinenii, Vol. 6, No. 1, pp. 53–56, 1970For part XXXVI se KhPS [Chemistry of Natural Compounds], 6, 33, 1970 [in this issue].