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.     

Synthese von Solanidin aus Demissidin

Summary The steroidal alkaloid solanidine (solanid-5-ene-3-ol, II) which occurs in the potato plantSolanum tuberosum L. has been synthesized from demissidine (5-solanidane-3-ol, I), an alkaloid from the Mexican wild potatoSolanum demissum Lindl. The synthesis involves the following steps: 5-solanidane-3-one, 2,4-dibromo-5-solanidane-3-one, solanid-4-ene-3-one, 3-acetoxy-solanida-3,5-diene, and solanidine (II).

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Solanum-Alkaloide. XVII. Mitteilung. — XVI. Mitteilung:K. Schreiber undG. Adam, Exper.17, 490 (1961).     

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.     

A postsynaptic α, 2-receptor: The alpha-adrenergic receptor of hamster white fat cells

Summary The effects of selected -agonists and -antagonists on theophylline-induced lipolysis were investigate in isolated hamster white fat cells ₂-Agonists (tramazoline, clonidine) inhibited theophylline-induced lipolysis while an ₂-agonist (methoxamine) was without any effect. The inhibitory effect of ₂-agonists was suppressed by yohimbine (₂-antagonist), whereas ₂-antagonists were inefficient. This result implies that the -adrenergic receptor of hamster fat cells is of the ₂-type, although located postsynaptically.Acknowledgments. This work was supported by grants from CNRS (ERA 412) and DGRST (grant No. 787 1078). We thank M. Dauzats for excellent technical assistance. We thank Prof. H. Schmitt for tramazoline and AR-C 239 and for helpful discussion.     

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).     

Deuterium isotope effects in the ninhydrin reaction of primary amines

Summary The rate of development of Ruhemann's purple in the ninhydrin reaction of two deuterated primary amines, -d₂-p-tyramine and -d₂--phenylethylamine, is significantly reduced It appears to be a primary isotope effect and indicates that the cleavage of the carbon-hydrogen bond at the -position is involved in the rate-determining step of the color reaction.Acknowledgements. We thank Dr A.A. Boulton for his advice and encouragement and the Canadian Medical Research Councel and Saskatchewan Health for their continuing financial support.     

Conjugated terpenoid ketones: A new group of plant growth regulators

Summary ,-unsaturated terpenoid ketones have a root-inducing property on the hypocotyl cuttings ofPhaseoulus aureus. Significantly isopathcoulenone, (I) is distinctly more active in causeing rooting over IAA.Acknowledgment. The work was financially supported by the Punjab State Government, India, under the scheme Chemistry of some natural products and their significance in agriculture. The authors thank Dragoco, Holzminden, Federal Republic of Germany, for supplying the samples of monoterpenes.     

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.     

Zur Umsetzung von 3α-Hydroxy-5β-Steroiden mit Blei(IV)-acetat

Summary On treatment of 3-hydroxy-5-steroids with lead tetra-acetate formation of 3, 9-oxides is observed. The yields of this ring closure reaction decrease significantly in the order 11-keto, ^{9, 11}-ene and ring-C saturated compounds.     

Zur Konstitution des Resibufogenins und Artebufogenins

Summary The structure of Resibufogenin is unambiguously shown to be 3-hydroxy-14, 15-oxido-bufadien-(20, 22)-olide on the basis of new degradation work. Artebufogenin A and Artebufogenin B are 3-hydroxy-14-15-keto-bufadien-(20, 22)-olide and 3-Hydroxy-14-14-keto-bufadien-(20, 22)-olide, respectively.     

Subzelluläre Verteilung der Brenzcatechinamine in Herz und Nebennieren von Meerschweinchen nach Vorbehandlung mitl-α-Methyl-Dopa

Summary -Methyl-noradrenalin synthesized after pretreatment of the guinea-pig with -methyl-dopa was found to be localized, like noradrenalin, mainly in the granular fraction 100 000g of the heart and in the fraction of the chromaffin granules of the suprarenal medulla (15000 g). -Methyl-adrenalin could not bo found.

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Ausgeführt mit Unterstützung der Deutschen Forschungsgemeinschaft.     

Identification of 3α, 17α, 21-trihydroxy-5α-pregnane (allotetrahydro-17α-hydroxy-cortexone) and 3α,21-dihydroxy-5α-pregnane (allo-tetrahydro-cortexone) in human urine

Résumé Le 3, 17, 21-trihydroxy 5-pregnane (allo-tétrahydro-17-hydroxy-cortexone) et le 3,21-dihydroxy 5-prégane (allo-tétrahydro-cortexone) ont été identifiés dans l'urine humaine. Ces composés avaient les mêmes migrations chromatographiques avant ou après acétylation ou oxydation que les respectifs stéroïdes de synthèse.     

Age- and sex-related differences in the content of prothymosinα in rat tissues

Differences in the tissue content of prothymosin during the early postnatal development of male and female rats are reported. Thymus and spleen have been found to contain significantly higher amounts of prothymosin in the newborn and prepubertal animals, as compared to adults, whereas liver has been found to contain low levels of prothymosin throughout development. These findings indicate a functional association of prothymosin with the proliferating lymphoid tissues of the young rat.     

Interdependence between locomotor activity and duration of wakefulness in humans during isolation

Summary Locomotor activity was recorded in 14 subjects who lived singly in an isolation unit for 16 to 88 days. Their free-running circadian rhythms had a mean period of 25.9 h, with individual means in the duration of wakefulness () ranging from 12.1 to 22.9 h. Intraindividually, the hourly means of activity were negatively correlated with to such a degree that the total amount of activity per day remained constant irrespective of large variations in .     

Study of the relationship between the magnitude of biological activity and the structure of aliphatic compounds

Zusammenfassung Es wurde festgestellt, dass die experimentellen Daten der sogenannten physikalischen Toxizität von aliphatischen Verbindungen die Gleichung log ( _i/ _Ät)= erfüllen, wo _iund _Ät die Grösse der biologischen Wirkung des i-ten Derivats und des Äthylderivats bezeichnen und und die Konstanten sind. Die Bedeutung der beiden Konstanten wurde erwähnt.     

Metabolism in Porifera XII. Further informations on the biosynthesis of 3β-hydroxymethyl-A-nor-steranes in the spongeAxinella verrucosa

Summary Direct incorporation and cold trap experiments suggest that cholest-4-en-3-one is an intermediate in the conversion of cholesterol into 3-hydroxymethyl-A-nor-cholestane in the marine spongeAxinella verrucosa. Cholest-4-en-3-one is further transformed by the sponge into cholest-4-en-3-ol, 5-cholestan-3-one and 5-cholestan-3-ol; these compounds arise from side reactions, which are not part of the major metabolic route leading to 3-hydroxymethyl-A-norsteranes.     

Effects of injury on the concentration ofα 1 andα 2 in the plasmas of male and female rats

Summary The effects of injury on the concentration of ₁-macroglobulin and ₂-macroglobulin in the plasmas of male and female rats has been investigated. At 5 days after injury to the male rats the ₁-macroglobulin concentration increased to 131% of its preinjury value. The ₂-macroglobulin concentration increased more rapidly to a maximum of 86 times its initial value. In the female rats ₂-macroglobulin increased only slightly and ₁-macroglobulin not at all.     

C16-methyl derivatives of progesterone and 17α-acetoxyprogesterone: Preparation and biological activities

Zusammenfassung Mehrere Derivate des 16-Methyl-progesteron wurden synthetisiert und biologisch geprüft. Die Einführung einer C16-Methylgruppe ergab keine gesteigerte Progesteronaktivität in den getesteten Verbindungen.     

Sur l'interaction de la Protamine avec des protéines sériques

Summary We noticed the formation of a precipitate on adding salmine to dilute aqueous protein solution at pH 6–7. Human and bovine serum albumin, human -globulin, and the perchloro- and sulfosalicylosoluble mucoides do not precipitate in this condition. - and -lipoproteins prepared by floatation and by Sandor's technique gave S-shaped nephelometric titration curves, as did haptoglobin, a mixture of the types Hp II-Hp II and Hp II-Hp I. In sera incubated 24 h at 37°C with protamin, the dextran sulphate test and the cetavlon test show a diminished value for -lipo- and -glucoprotein. Lipoprotein degradation is probably enzymatic in nature.