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 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).     

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 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.     

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).     

Triterpene glycosides and their genins fromThalictrum foetidum. V. Structure of cyclofoetoside B

A new glycoside (cyclofoetoside B) (I) has been isolated from the epigeal part of the plantThalictrum foetidum L. (Ranunculaceae). On the basis of chemical transformations and with the aid of physicochemical characteristics it has been established that cyclofoetoside B is 24S-cycloartane-3, 16, 24, 25, 29-pentaol 3-O--L-arabinopyranoside 16-O-[O--L-rhamnopyranoside-(1 6)--D-glucopyranoside], C₄₇-H₈₀O₁₇, mp 194–197°C (methanol); [] _D ²⁴ +15.7 ± 2° (c 0.88; pyridine). The enzymatic hydrolysis of (I) has yielded cyclofoetigenin B (III), 24S-cycloartane-3,16,24,25,29-pentaol 16-O--D-glucopyranoside, (IV), C₃₆H₆₂O₁₀, mp 223–225°C (acetone), [] _D ²⁴ +37 ± 2° (c 0.97; methanol) and 24S-cycloartane-3,16,24,25,29-pentaol 16-O-[O--L-rhamnopyranosyl-(1 6)--D-glucopyranoside, C₄₂H₇₂O₁₄, mp 229–231°C (methanol), [] _D ³⁰ +41 ± 2° (c 0.7; methanol). Details of the IR and¹H and¹³C NMR spectra of the compounds are given.Irkutsk Institute of Organic Chemistry, Academy of Sciences of the USSR. Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Trashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 341–345, May–June, 1986.     

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.     

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.     

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 cis- und trans-α-Phenylzimtsäure

Zusammenfassung Eswirdüber die Stabilität derisomeren -Phenylzimtsäurechloride bei der Umsetzung mit Glykolen und Äthylendiamin berichtet. cis--Phenylzimtsäure (cis-I) läßt sich aus dem Reaktionsprodukt derPerkin-Kondensation von Benzaldehyd mit Phenylessigsäure gewinnen.4. Mitt. der Reihe Zur Frage der cis-trans-Asymmetrie organischer Verbindungen. 3. Mitt. vgl. Fußnote 3.