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.     

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.     

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.     

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 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).     

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.     

Circular Dichroism Spectra of 5- and 7-Bromo-6-ketosteroids

Circulardichroismspectra of 5- and 7-bromo-6-ketosteroidsof the cholestane and stigmastane serieswere studied. A negative Cotton effect corresponding to the n-* -transition of the ketone was observed in the CD spectra of 5-bromo-6-ketosteroids at 300 nm. The analogous Cotton effect was positive in CD spectra of 7-bromo-6-ketosteroids.     

Thermal decomposition of phosphorylated hemimercaptals

Conclusions The reaction of diphenylchlorophosphine with ,,-trichloro--hydroxyethyl ethyl sulfide in the presence of triethylamine leads to the formation of -ethylthio-,,-trichloroethyl diphenylphosphonite. The reaction of diphenylchlorophosphine with dimethyl -hydroxy--propylthiophosphonate in the presence of triethylamine gives -propylthio--dimethylphosphonoethyl diphenylphosphonite. The phosphorylated hemimercaptals obtained are thermally unstable and decompose to S-alkyl diphenylthiophosphonites and the corresponding carbonyl compounds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2619–2621, November, 1985.     

Triterpene glycosides from Pulsatilla chinensis

Four triterpene glycosides were isolated from the roots of Pulsatilla chinensis (Bunge) Regel (Ranunculaceae). Two new glycosides, chinensiosides A (1a) and B (2), were identified as 3-O-[-L-rhamnopyranosyl-(12)--L-arabinopyranosyl]-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid and 3-O-{-L-rhamnopyranosyl-(12)-[-D-glucopyranosyl-(14)]--L-arabinopyranosyl}-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid. The other two glycosides were identified as previously known hederasaponin C (3) from Hedera helix and glycoside III (4) from Pulsatilla cernua.     

Cell-Specific Gene Transfer by α-Cyclodextrin Conjugates with Mannosylated Polyamidoamine Dendrimers

To improve the activity and the cell specificity of gene transferof polyamidoamine starburst dendrimer, we prepared -CyD conjugates with mannosylateddendrimers (generation 2 (G2), man--CDE conjugates) having various degrees of substitution(DS) of mannose residue. The man--CDE conjugates (DS 1, 3 and 5) formed complexeswith plasmid DNA (pDNA), but man--CDE conjugate (DS 8) did not. The gene transferactivity of man--CDE conjugates (DS 1, 3 and 5) and -CDE conjugate was augmented with an increasein the charge ratio of vector/pDNA, without showing cytotoxicity. Man--CDE conjugates(DS 3 and 5) showed higher gene transfer activity than -CDE conjugate in A549 cells, whichrecognize mannose, but man--CDE conjugates (DS 1 and 8) showed almost comparable gene transfer activityto -CDE conjugate (G2). On the other hand, no appreciable enhancing effect of man--CDEconjugates (DS 3 and 5) on the transfer activity was observed in NIH3T3 cells, which do not recognizemannose. These findings suggest that man--CDE conjugates (DS 3 and 5) can be new preferablecell-specific non-viral vectors of pDNA to cells which recognize the mannose moiety.     

Porphyrins. 9. New data on the polyformylation of metal complexes of etioporphyrin I

The structures of the products of the polyformylation of Cu, Ni, and Co complexes of etioporphyrin (EP) as monoformyl-, ,-diformyl-, ,-diformyl-, and ,,-triformyl-EP were established by electronic, IR, and PMR spectroscopy and mass spectrometry. -Formyl--(N-methylformaldimine)-EP and porphyrins that contain a cyclopentane ring can be formed by alkaline treatment of the Vilsmeier formylation products.See [1] for communication 8.See [2] for our preliminary communication.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 767–775, June, 1979.     

Quantitative Bestimmung von Amingemischen durch multiplikative Verteilung

Zusammenfassung Es wird die quantitative Bestimmung der 5 Amine rac-N,N-Dibutyl-,-diphenyläthylendiamin (A), meso-N,N-Dibutyl-,-diphenyläthylendiamin (B), 1-Phenyl-1-butylamino-2-methyl-propan (C), N-Butyl-benzylamin (D) und Butylamin (E) in Reaktionsgemischen durch 54- und 95 stufige Craig-Nach-fraktionierungsprozesse in einer Verteilungsbatterie mit 35 Elementen nach Hecker [1] beschrieben. Durch graphische Auswertung der überlappenden Verteilungskurven wird eine quantitative Bestimmung auch bei 54 stufigen Prozessen, d.h. bei unvollständiger Trennung möglich.

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Quantitative determination of amine mixtures by multiplicative distributionOn the separation of organic bases by Craig distribution. IX

The quantitative evaluation of the 5 amines, rac-N,N-dibutyl-,-diphenylethylenediamine (A), meso-N,N-dibutyl-,-diphenylethylenediamine (B), 1-phenyl-1-butylamino-2-methyl-propane (C), N-butyl-benzylamine (D) and butylamine (E) in reaction mixtures by Craig after-fractionation processes of 54 and 95 steps in a distribution machine with 35 elements by Hecker [1] is described. By graphic evaluation of the overlapping distribution curves a quantitative determination is achieved, even with processes of 54 steps, i. e. incomplete separation.

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8.Mitteilung: Sohönenberger, H., Eder, M.: diese Z. 249, 117–120 (1970).

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Wir danken der Deutschen Forschungsgemeinschaft und dem Fonds der Chemischen Industrie für die Förderung unserer Untersuchungen.     

Synthesis of derivatives of the androstane series

Summary Hydrazones and symmetrical dihydrazones of 2-methyltestosterone and its 17-methyl and 17-ethyl derivatives have been synthesized.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 5, pp. 354–359, 1966     

Approaches to the synthesis of pregn-5-en-3β,21-diol-20-one-[16,17α-d]-2'-methyloxazoline

Conclusions Two independent methods were found for the preparation of pregn-5-en-3,21-diol-[16,-17-d]-2'-methyloxazoline: 1) by cis-opening of the aziridine ring of the 3;16,17;21-triacetate of 16,17-epiminopregn-5-en-3,21-diol-20-one and 2) by the 21-hydroxylation of pregn-5-en-3-o1-20-one-[16,17-d]-2'-methyloxazoline using iodosobenzoyl diacetate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2138–2141, September, 1984.     

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].     

Steroids

Summary 1. A new type of steroido[17, 16-d]-3-(methyl, phenyl)isoxazoles has been synthesized by the cyclization of the syn-oximes of acylated 3-hydroxy-16, 17-oxidopregn-5-en-20-ones or their 5-saturated derivatives and acylated 17-benzoyl-3-hydroxy-16, 17-oxidoandrost-5-ones.2. It has been established that the Beckmann rearrangement of the anti-oximes of acylated 17-benzoyl-3-hydroxy-16, 17-androst-5-enes leads to a mixture of anilides and steroidoisoxazoles, which shows the inversion of the configuration of the oximes (from the anti to the syn form) during the rearrangement.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 5, pp. 325–333, 1966     

Radiation-induced reactions of cholesterol in an aqueous medium

⁶⁰Co -ray radiolysis of cholesterol /3-hydroxy-5-cholestene/ /I/ in the two-phase system /water-ethyl acetate/ and in the presence of air has been studied using TLC and GC methods. The following products were observed in the irradiated mixture: 3, 7-dihydroxy-5-cholestene /II/, G O. 36, 3-hydroxy-7-keto-5-cholestene /III/, G 1.48, 3-hydroxy-7-keto-5-cholestane /IV/, G 0.22, 3,5,6-trihydroxy-5-cholestane /V/, G 0.83, 5,6-epoxy-3-hydroxy-5-cholestane /VIa/, G 0.26, 5,6-epoxy-3-hydroxy-5-cholestane /VIb/, G 0.24, and 2, 3-dihydroxy-5-cholestene /VII/, G 0.22. The dose dependence of the formation of these products shows that the cholesterol derivatives substituted in the position 7 /II–IV/ are formed from a common precursor — the radical Ia. On the other hand, the products of the 5–C=C double bond reactions /V and VI/ are formed independently. Also the product VII is formed independently. A reaction scheme that is in agreement with these results is proposed.     

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.     

On the dynamic mechanical behavior of nylon 66

Summary The dynamic mechanical properties of nylon 66 films and fibers have been examined, as a function of annealing and drawing, with a Vibron viscoelastometer. It is found that the transition is little affected by annealing treatments, but increase in orientation causes the transition to move to a higher temperature. Experiments, with X-ray diffraction of samples at elevated temperatures, lead to the conclusion that the triclinic to hexagonal phase change does not contribute significantly to the transition. Samples cut parallel and perpendicular to the drawing direction of nylon 66 film, have been used to show that the curves of dynamic tensile modulus versus temperature, for the parallel and perpendicular directions, cross in the neighborhood of the transition. This observation is discussed in relation to the suggestion that the transition is the glass transition in nylon 66.

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Zusammenfassung Die dynamisch-mechanischen Eigenschaften von Filmen und Fasern aus Nylon 66 wurden als Funktion der Temperung und Verstreckung mit einem Virbon-Viskoelastometer untersucht. Die -Umwandlung wird wenig durch die Temperung beeinflußt, aber erhöhte Orientierung läßt siezu höheren Temperaturen verlagern. Messungen der Röntgenstreuung bei erhöhten Temperaturen führen zu dem Schluß, daß der Übergang triklin/hexagonal nicht wesentlich zu der -Umwandlung beiträgt. Proben aus verstrecktem Nylon-66-Film, parallel und senkrecht zur Streckrichtung geschnitten, zeigen, daß die Kurven des dynamischenE-Moduls gegen die Temperatur für beide Orientierungen sich in der Nachbarschaft der -Umwandlung überkreuzen. Diese Beobachtung wird hinsichtlich der Vermutung diskutiert, daß die -Umwandlung den Glasübergang in Nylon 66 darstellt.

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With 5 figures and 2 tables