The benzilic acid rearrangement of 3α,17β-Diacetoxy-11-hydroxy-12-oxo-5β-androst-9(11)-ene

Zusammenfassung Die Bildung von 11-Carboxy-3, 11, 17-trihydroxy-13-C-nor-5-androstan 11a,17-Lakton aus 3, 17-Diacetoxy-11-hydroxy-12-oxo-5-⁹(11)-androsten wird beschrieben. Der Mechanismus und die Stereochemie dieser Umwandlung (Retro-Aldolkondensation und Benzilsäureumlagerung) wird diskutiert.     

Synthese von 5α- und 5β-Androstan-17β-ol-3-on-17-acetat aus Hyodesoxycholsäure

Summary 5- and 5-androstane-17-ol-3-one-17-acetate have been prepared from 5-androstane-6, 17-diol-3-one-17-acetate by a synthesis involving directedHuang-Minlon-reduction.Separation of 5-androstane-17-ol-3-one from its 5-isomer could readily be achieved by crystallisation of their 3-ethylenketals from acetone.     

Starfish saponins VII. Structure of luzonicoside,a further steroidal cyclic glycoside from the pacific starfishEchinaster luzonicus

Summary On the basis of comparative chemical and spectral data, the structure of the major saponin, luzonicoside, from the starfishEchinaster luzonicus has been elucidated as2. This is a further example of a novel class of steroidal cyclic glycoside from starfish of the genusEchinaster. Its structure includes a ⁷, 3,6-dioxygenated-23-oxosteroidal moiety, already found in the saponins ofEchinaster sepositus, and a trisaccharide moiety, -D-galactopyranosyl-(12) -L-arabinopyranosyl-(12)--D-glucuronopyranosyl, bridging C-3 and C-6 of the steroid.This contribution is part of the Progetto Finalizzato Oceanografia e Fondi Marini del C.N.R., Roma.Acknowledgments. We wish to thank Mrs M. Pusset, Laboratoire des Plantes Médicinales du C.N.R.S., Nouméa, for the extraction of starfish and the divers of the Centre Q.R.S.T.O.M. de Nouméa for collection.     

Cytogénétique desLeggada: (1) La formule chromosomique deMus (Leggada)bufo Th., (2) Nouvelles données sur la délétion portant sur le bras court d'unX chezMus (Leggada)triton Th

Summary The author treats 2 topics connected with his studies on the cytogenetics of the African pigmy-mice. (1)Mus (Leggada) bufo Th. shows the primitive complement already detected in other species or subspecies (minutoides ssp ₁,indutus, tenellus, setulosus): 2N=36,N.F.=36, sex chromosomesPR. (2) The deletion of the short arm of oneX-chromosome (X _dc ) was previously observed as heterozygous mutation by 4 in a sample of 7 and 5 . A more important sample (18 , 21 ) gives the following results: 11 X-X, 10 X-X _dc , 18 X-Y. The occurrence of X _dc -X _dc and of X _dc -Y is also very improbable. It is not easy to understand how the chromosomeX _dc may persist in the population if the complementsX _dc -X _dc andX _dc -Y are lethal, which seems to result from these observations.     

Effect of acute administration of Δ1-tetrahydrocannabinol on β-endorphin levels in plasma and brain tissue of the rat

Summary Acute treatment with ¹-tetrahydrocannabinol (¹-THC) elevated the concentration of -endorphin-like immunoreactivity (-ELIR) in plasma and in the hypothalamus, but not in the hippocampus of rats habituated to the injection procedure. These effects were not obtained with the psychotropically inert analog of (¹-THC), cannabidiol. In animals that had not been habituated to the injection procedure, placebo treatment induced a decrease in hippocampal -ELIR.The authors acknowledge the skillful technical assistance of Mrs Willeke Logtenberg.     

Hydrolysis of amino acid β-naphthylamides by aminopeptidases in the parotid gland

Zusammenfassung Die Aktivität der Aminopeptidasen in Ohrspeicheldrüsen wurde gemessen. Glycyl-Prolin-naphthylamid, Alanin-naphthylamid, Leucin-naphthylamid, Methionin-naphthylamid, und Arginin-naphthylamid wurden von der Mikrosomenfraktion und der löslichen Fraktion schnell gespalten. Das Glycyl-Prolin-naphthylamid spaltende Enzym war in Ohrspeicheldrüsen in relativ grösserer Menge vorhanden. Die Aufspaltung von Glycyl-Prolin-naphthylamid in Glycyl-Prolin und-Naphthylamin wurde papierchromatographisch nachgewiesen.     

Zur Synthese des Batrachotoxinins: Synthese von 3β-Acetoxy-16β, 20β-dihydroxy-4′-methyl-18-nor-5β, 14β-pregnano[13,14-f]hexahydro-1′,4'-oxazepin-3′-on(20a)

Summary The synthesis of 3-acetoxy-16, 20-dihydroxy-4-methyl-18-nor-5, 14-pregnano[13,14-f]hexahydro-1, 4-oxazepin-3-one (20a) is described.     

Isomeric homoallylic cations formed from 19-substituted steroids

Zusammenfassung Die Existenz von zwei verschiedenen isomeren Homoallylkationen in der Umlagerung von Steroid- ⁵-19-Methansulfonsäure-Estern zu 5, 19-cyclo-6-hydroxylierten Steroiden und deren Umlagerung zu ⁵(¹⁰)-B-homo-7-hydroxylierten Steroiden wurde bewiesen, und eine neue Art der Homoallylumlagerung eines ⁵(¹⁰)-B-homo-7-hydroxylierten Steroids zum 5, 6-Methano-9-en und zum 5, 6-Methano-10-ol wurde beobachtet.

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This material was presented at theSymposium on Steroids Made Through Intramolecular Functionalization on the C ₁₈-and C ₁₉-Methyl Groups, at the 149th meeting of the American Chemical Society in Detroit (Michigan), on April 7, 1965.     

17β-Hydroxymethyl-Steroide: Darstellung von Derivaten des 17α-Hydroxy-17β-hydroxymethyl-4-androsten-3-ons

Summary Starting from 17-hydroxy-17-hydroxymethyl-4-androsten-3-one, we synthesized 4-chloro-17-hydroxy-17-hydroxymethyl-4-androsten-3-one-17, 20-acetonide and 17-hydroxy-17-hydroxymethyl-1, 4-androstadien-3-one. 11, 17-dihydroxy-17-hydroxymethyl-4-androsten-3-one was obtained from cortisone via methyl-17-hydroxy-3, 11-dioxo-4-etienate.     

DNA synthesis and mitoses in atrial myocytes of rats with aortal stenosis

, . 2- , 1,60 ±0,59% , 0,96 ± 0,44% — . ë . , ³- .     

Protection of chlorophyll a from photo-oxidation byβ-carotene in binary mixture of organic solvents

Zusammenfassung Das photoxytadive Ausbleichen des Chlorophylls a wird durch die Gegenwart des-Carotins gehemmt. Die Hemmwirkung des-Carotins und die Wechselwirkung zwischen Chlorophyll a und-Carotin werden vom Lösungsmittel kontrolliert.     

ω10-Lipoxygenase products of α-linolenic acid are esterified to phospholipids inHydra vulgaris

We have recently reported the occurrence of 9(R)-hydroxy-, 9(R)-hydroperoxy- and 9-keto-octadeca-10E,12Z,15Z-trienoic acids (9-HOTrE, 9-HPOTrE and 9-KOTrE) inHydra vulgaris, and their biosynthesis from -linolenic acid (-LA) through the action of an enantioselective 10(R)-lipoxygenase (10-LO). Here we describe the finding of these -LA metabolites as esters to the 2-position of phosphatidylcholine, phosphatidylethanolamine and, in trace amounts, phosphatidylinositol. Small amounts of a compound co-eluting with an authentic standard of 9(R)-hydroxy-octadeca-10E,12Z-dienoic acid, a metabolite potentially derived from the action of 10-LO on linoleic acid, were also found esterified with phospholipids. Since direct peroxidation of membrane lipids has been described, experiments were aimed at establishing whether -LA metabolite-containing phospholipids could originate, inH. vulgaris, from either spontaneous or 10-LO-catalyzed oxidation of phospholipid-bound -LA. Incubation of either unlabelled or radiolabelled PUFA-containing phosphoglycerides withH. vulgaris 10-LO did not result in their peroxidation. This suggests that -LA and LA metabolites are incorporated into glycerophospholipids after their formation by 10-LO, and that, as in mamals, membrane phospholipids may serve as a reservoir for these bioactive compounds. This is the first example in an invertebrate species of lipoxygenase products esterified to phosphoglycerides.     

Exchange of tritium from randomly tritiated taurocholate by microbial bile salt oxidoreductases

Summary Tritium distribution on randomly labelled taurocholate (TC) was estimated at 28%, 4%, 1% and <0.5% on the hydrogens opposite the 3-, 7- and 12-OH groups and taurine moiety respectively. Anomalously,C. perfringens 3-hydroxysteroid dehydrogenase (3-HSDH) catalyzed tritium loss of 36% on formation of 7-, 12-dihydroxy-3-keto-5-cholanoate, implying additional losses of tritium at other sites by this enzyme.This work is supported by the National Cancer Institute.     

A new antiandrogen. 6α-Bromo-17β-hydroxy-17α-methyl-4-oxa-5α-androstan-3-one

Zusammenfassung Es wird gezeigt, dass 6-Brom-17-hydroxy-17-methyl-4-oxa-5-androstan-3-one beträchtliche antiandrogene Wirkung besitzt. Isomere dieser Verbindung mit verschiedener Konfiguration an C-5 und C-6 wurden als inaktiv befunden.     

Über die Brenzkatechinamine im Froschherzen und in der Froschhaut vor und nach Verabfolgung von α-Methyldopa

Summary (1) The adrenalin of the frog heart was found to be localized mainly in the granular fraction (100,000g). After pretreatment with -methyldopa (-MD), the heart also contained -methyldopamine, -methylnoradrenalin, and -methyladrenalin. (2) -MD caused a maximal expansion of the melanophores. This action was counteracted byl-dopa, which per se caused a contraction of the melanophores. After pretreatment with -MD the skin contained besides adrenalin also -methyldopamine and -methyladrenalin. In addition also 5-hydroxytryptophan expanded the melanophores.     

Carbohydrase and esterase activity in the gut of larvalCallosobruchus maculatus

Summary Carbohydrase activity has been demonstrated in homogenates of the alimentary tracts of late instar larvae ofC. maculatus:-D galactosidase, -D glucosidase and N-acetyl-D glucosaminidase activities were comparable and significantly greater than -D galactosidase,-D glucosidase and -D mannosidase. The effects of pH and substrate concentration are reported. The presence and changes in pattern of non-specific esterase activity in larval and adult gut homogenates is also described.     

Changes in the lumen of coronary vessels under oligemic hypotension

Conclusions The decrease of circulating blood volume, resulting in oligemic hypotension, may evoke in anaesthetized cat the active constrictory coronary vessel responses of 2 types, one occuring immediately after start of the hypotension and the other having a significantly prolonged latency.

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, , , , ( 4 ), ( 45 ).

     

Mass spectrometric determination of the amino acid sequence in arginine-containing peptides

aa, a-a a- a aa - aa a -a .     

Triterpenoid XIII. The constitution of barring-togenol D

Zusammenfassung Die Struktur des aus der Frucht vonBarringtonia acutangula Gaertn. isolierten neuen Triterpenoiden, Barringtogenol D, ist als 3:22oxy-16:22-Oxido-olean-12-en ermittelt worden.     

16-β-methylprednisone from hecogenin

Zusammenfassung Es wird über die Herstellung des 16-Methylprednisons berichtet, welche vom Hecogenin ausgehend über ca. 15 Stufen durchgeführt wird. Als wichtige Zwischenstufe treten 5-Pregn-16-en-3-ol-11, 20-dion-Acetat und 16-Methylen-5-pregnan-3, 17-diol-11, 20-dion auf: letzteres wird durch eine stereospezifische katalytische Reduktion in das entsprechende 16-Methyl-derivat umgewandelt.