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.     

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.     

The distribution of some enzymes involved in the steroidogenesis of hen's ovary

Riassunto È stata studiata con metodi istochimici la distribuzione della ⁵-3-idrossisteroide deidrogenasi ( ⁵-3-HSDH) e delle 17-idrossisteroide deidrogenasi (17-HSDH), DPN- e TPN-dipendenti, nell'ovario di gallina ovulante. Mentre la ⁵-3-HSDH è presente in tutti i tessuti a secrezione steroide dell'ovario, la 17-HSDH è localizzata solo nelle cellule della granulosa.     

Fucosidases du suc digestif d'Helix pomatia

Summary The-d-fucosidase and -l-fucosidase activities of digestive juice ofHelix pomatia have been studied.-d-fucosidase can be separated from-d-galactosidase by heat inactivation.     

The molecular structure of the benzilic acid rearrangement product of 3α, 17β-diacetoxy-11-hydroxy-12-oxo-5β-androst-9(11)-ene

Zusammenfassung Die Struktur desp-Brombenzoates des Benzilsäureumlagerungsproduktes von 3, 17-Diacetoxy-11-hydroxy-12-oxo-5-9(11)-androsten wurde durch dreidimensionale Röntgenstrukturanalyse eines Einkristalls als 3-p-Brombenzoat des 11-Carboxy-3, 11, 17-trihydroxy-13-C-nor-5-androstan 11a, 17-Laktons erkannt.     

17β-Hydroxymethyl-steroide: Darstellung von 17α-Hydroxy-17β-hydroxymethyl-4-androsten-3-on aus Reichsteins Substanz S

Summary The synthesis of 17-hydroxy-17-hydroxymethyl-4-androsten-3-one fromReichsteins compound S is described. Transformation of 3,3-ethylenedioxy-17-hydroxy-17-hydroxymethyl-5-androsten into 17-methyl-isotestosterone demonstrates the configuration of the substituents at C-17.     

Further morphological and biochemical studies on normal and hybrid embryos of sea urchins

Zusammenfassung (1) Es wurde bei den SeeigelartenParacentrotus ,Arbacia undSphaerechinus sowie den drei BastardenPar ×Arb ,Arb ×Par undPar ×Sphaer für eine Reihe von Entwicklungsstadien die Anzahl der Kerne pro Keim bestimmt (Tabelle). Der morphogenetischen Hemmung der Bastarde entsprechen herabgesetzte Kernzahlen und parallel eine Herabsetzung der DNS-Synthese. (2) Es wurde bei den genannten reinen Arten und den Bastarden derUmsatz der RNS bestimmt. Er geht in allen Fällen, bei den reinen Arten wie bei den Bastarden, der DNS- Synthese parallel.

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Our work was supported by a grant from the Schweizerischer Nationalfonds zur Förderung der wissenschaftlichen Forschung. We express our sincere thanks to the Nationalfonds and also to the authorities at the Zoological Station at Naples for generous help and supply of materials and facilities. — This paper is thankfully dedicated byF. Baltzer toF. E. Lehmann for his kind hospitality in the Bernese Institute.     

Synthese von 22,26-Imino-cholestan-Derivaten

Summary 3, 16-diacetoxy-5-pregnane-20-one and the analogue pregn-5-ene derivative have been converted into (22R, 25R)-22, 26-imino-5-cholestane-3, 16-diol. The configuration at C-22 and C-25 was determined by transformation into the known (22R, 25R)-5-solanidane-3-one. Application of the Ruschig method led to (25R)-22,26-imino-5-cholest-22(N)-ene-3, 16-diol.

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Solanum-Alkaloide. XVI. Mitteilung. — XV. Mitteilung:K. Schreiber undH. Ripperger, Tetrahedron Letters Nr.27, 9 (1960).     

Ein neues Verfahren zur Herstellung von 19-Norsteroiden

Summary The new methods for the production of 19-norsteroids described involve the conversion of 5-halogen-6-hydroxy-steroids into the corresponding 5-halogen-6:19-ethers either with lead tetraacetate or by the hypoiodite reaction^8,10. The 6:19-oxygen bridge is then opened reductively either directly or after oxidation of the 6:19-ethers to lactones or preferably after introduction of a ^4,6-3-oxo grouping. Acylolytic cleavage of the ⁴-3-oxo-6:19-ethers followed by alkaline hydrolysis gives ^4,6-3-oxo-19-hydroxy-steroids. The 19-hydroxycompounds formed are easily converted into 19-norsteroids by known methods.

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Über Steroide, 189. (vorläufige) Mitteilung; 188. Mitt. vgl.J. Kalvoda, J. Schmidlin, G. Anner undA. Wettstein, Exper.18, 398 (1962).     

Uptake of D-glucose anomers by rat retina

Summary Uptake ofd-glucose anomers by isolated rat retina was studied. After 3 min incubation at 37°C in the presence of or anomer (750 g/ml), a significantly greater uptake (1.32 mg/g wet tissue) of -anomer was observed compared with that of -d-glucose (1.11 mg/g wet tissue). This result and other data suggest that the carrier ford-glucose transport in the retina prefers the -anomer stereospecifically.Acknowledgment. The authors are grateful to Mr S. Suzuki for his technical assistance.     

Wirkung von 6β-Methoxy-9β,10α-pregna-4,6-dien-3,20-dion

Summary 6-Methoxy-9,10 -pregna-4,6-diene-3,20-dione inhibites the ⁴-3-oxosteroid-5-reduction in microsomes and the ⁴-3-oxosteroid-5-reduction in the soluble fraction of male rat liver. The 3- and 3-hydroxysteroid dehydrogenase are not inhibited by this substance.

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Diese Arbeit wurde von der Firma Hoffmann-La Roche, Basel, unterstützt.     

Steroidal sapogenins. XXX stereochemistry of the side chain

Zusammenfassung Die optischen Drehungen einiger 20, 25d; 20, 25l; 20, 25d; und 20, 25-l-Sapogenine wurden bestimmt. Die ersten drei Serien gaben übereinstimmend linksdrehende Werte, aber die letztere Gruppe erwies sich als rechtsdrehend.Die Struktur der vier Serien der Sapogenine folgte aus der Analyse dieser Befunde. Der mögliche Mechanismus bei der Entstehung dieser Verbindungen aus Pseudosapogeninen wurde besprochen. Die Autoren gelangen zum Schluss, dass sterische Faktoren an C₂₀ und C₂₅ die Richtung der Ringschliessung beeinflussen.

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Steroidal sapogenins. XXX stereochemistry of the side chain

     

The identification of εN-(β-aspartyl)-l-lysine in native and heated keratin

Zusammenfassung Chromatographisch (Ionenaustausch, Papierchromatographie, Dünnschichtchromatographie und Hochspannungselektrophorese) wird nach enzymatischer Hydrolyse von nativem und denaturiertem Wolle-Keratin (-Glutamyl)-lysin und (-Aspartyl)-lysin identifiziert und so die in Proteinen postulierte anomale Peptidverknüpfung nachgewiesen.

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Acknowledgments. The authors would like to thank Dr.B. Milligan for a gift of N(-aspartyl) lysine. They would also like to thank the Wool Industries Research Association for permission to publish this work and for a Post-Doctoral Fellowship to one of them (M.S.O.).     

Arabinose nucleoside triphosphates are no inhibitors for DNA-dependent RNA polymerases

Summary 1--d-arabinofuranosylcytosine-5-triphosphate and 9--d-arabinofuranosyladenosine-5-triphosphate were found to have no inhibitory potency for both mammalian DNA-dependent RNA polymerase II andE. coli DNA-dependent RNA polymerase.     

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.     

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.     

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.     

The characteristic specificity of plasmocytoma lipids concerning their resistance to formdl-fractions with colloidal dextran

Zusammenfassung Papierelektrophoretische Lipiduntersuchungen von- und-Plasmacytom — Paraproteinseren nach Kolloidaldextranbelastung erfassen eine neue, in der Diagnostik des Plasmocytoms verwertbare Eigenschaft: die Paraproteinlipidkomponente (PL) vermag, entgegen den-Lipoproteinen, mit Dextran keine Assoziationsfraktion zu bilden.

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My thanks are due toJosipa Franjkovi for her technical assistance.     

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.