Partialsynthese des Aldosterons

Summary The preparation of the (18 11)-lactone of ⁵-3-ethylenedioxy-11-hydroxy-21-acetoxy-20-oxo-pregnen-18-oic acid (XV) is reported. Since this compound has previously been transformed into aldosterone, the reactions described represent the first partial synthesis of this important hormone from readily available 18-unsubstituted natural steroids.

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Über Steroide, 163. Mitteilung; 162. Mitteilung vgl.P. Wieland, K. Heusler undA. Wettstein, Helv. chim. Acta43 (1960), im Druck; XV. Mitteilung überSynthesen in der Aldosteron-Reihe; XIV. Mitteilung vgl.J. Schmidlin undA. Wettstein, Helv. chim. Acta42, 2636 (1959).

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Steroide und Sexualhormone, 215, Mitteilung; 214. Mitteilung vgl.B. Kamber, G. Cainelli, D. Arigoni undO. Jeger, Helv. chim. Acta43 (1960), im Druck.     

Konstitution des Cinobufagins

Summary The structure of Cinobufagin is shown to be 3-Hydroxy-14, 15-epoxy-16-acetoxy-5-bufa-20, 22-dienolide.

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Die ausführliche Publikation erscheint demnächst in den Helv. chim. Acta.     

Derivate des 6,11-Dihydrodibenz(b,e)thiepins,eine neue Gruppe von psychotropen Substanzen

Summary Reactions of phthalide and 6-chlorophthalide with sodium salts of thiophenols gaveo-(phenylmercaptomethyl)benzoic acids (III), which were cyclized by the action of polyphosphoric acid to 6, 11-dihydrodibenz(b,e)-thiepin-11-ones (1). These ketones were treated with 3-di-methylaminopropylmagnesium chloride and other basic Grignard reagents and the products (IV) dehydrated to a series of 11-(aminoalkylidene)-6,11-dihydrodibenz(b,e)-thiepins (V), the hydrochlorides of which show psychotropic activity.

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6. Mitt. Synthetische Ataractica, 5. Mitt. siehe eskoslov. farm.11, im Druck (1962).     

Zur Biosynthese des Cantharidins. I

Summary In contrast to the female, the adult males ofLytta vesicatoria (Coleopt. Meloidae) produced radioactive cantharidine on injection with¹⁴C-1-acetate and¹⁴C-2-mevalonate solutions. A partial degradation of the cantharidine showed that in the acetate experiment approximately of the activity occurred at C atoms 2 + 3 whereas with mevalonate approximately of the activity was at C atoms 8 + 9 and at C atoms 10 + 11. These results show that cantharidine is not formed by a tail to tail linkage of 2 isoprene units.

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Wir danken dem Schweizerischen Nationalfonds zur Förderung der wissenschaftlichen Forschung für die Unterstützung dieser Arbeit, Herrn Dr.J. Würsch (Physikalisch-chemische Abteilung der Firma F. Hoffmann-La Roche & Co. AG, Basel) für¹⁴C-2-Mevalolacton und unserer mikroanalytischen Abteilung (LeitungH. Frohofer) für die Aktivitätsbestimmungen.     

Ein Beitrag zur Morphologie des Influenzavirus: Struktur des Influenza-A2-(«Hongkong»)-Virus

Summary The morphology and internal structure of Influenza A₂ (Hongkong) virus is described. This virus has the same morphological characteristics as previously isolated Influenza A₀, A₁; and A₂ strains. Evidence is also presented that this influenza virus appears in a filamentous form in human throat washings. The reasons for the virus to be a filamentous or a spherical particle are discussed.

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Die Arbeit wurde vom Schweiz. Nationalfonds unterstÜtzt.     

Die Synthese des Novobiocins

Summary The synthesis of the antibiotic novobiocin is described. First the essential carbohydrate, the 3-O-carbamoylnoviose was synthesized fromd-glucose. A number of steps (1–6) led to the 3,5,6-tri-O-benzyl-2-O-methyl-d-galactono--lactone (6) which is characterized by the correct array of carbon atoms inherent to the noviose. Further transformations (7–15) finally yielded the carbohydrate. The problem of glycosidation is discussed in some detail. Glycosidation of a suitable aglycon precursor (18) with 2,3-O-carbonyl--noviosyl-chloride (22) proved possible and led to the isolation of an-glycoside (23) which was further transformed (24–28) into novobiocin.

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Chemische Forschungsabteilung der F. Hoffmann-La Roche & Co. AG, Basel.

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Vortrag Dr.B. P. Vaterlaus, gehalten an der Gordon Research Conference on Steroids and other Natural Products, 16.–20. Juli 1962, New Hampton, N.H., USA, und vor der Basler Chemischen Gesellschaft, 8. November 1962. Im Auszug:H. Spiegelberg,Synthèse du 3-O-carbamoylnoviose, sucre de la novobiocine, Symposium international de chimie organique, Bruxelles, 15. Juni 1962;J. Kiss,The Synthesis of Noviose and Allied Compounds, Birkbeck College (Univ. London), 23. Oktober 1962. Der vorliegende Aufsatz ist Gegenstand von Detailpublikationen in den Helv. chim. Acta, in Vorbereitung (1963).     

Isolation of crystalline aldosterone from the urine of patients with congestive heart failure

Zusammenfassung Der Natrium-retinierende Faktor aus dem Urin zweier Patienten mit Stauungs-Herzfehlern wurde in kristallisierter Form isoliert und mit Aldosteron identifiziert.

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Communication No. 137 On Steroids. No. 136 compareA. Wettstein, Exper.11, 465 (1955).     

Steroids and related natural products. 14α-Methyl testosterone

Zusammenfassung Eine Zwanzigstufenumwandlung von Isocholesterol (rohes Lanosterol) zu 14-Methyltestosteron wurde ausgeführt und die Reaktionsfolge von 3-Hydroxy-4,4,14-trimethyl-20-oxo-5-pregnan zu 14-Methyltestosteron beschrieben.

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Part XIV. Part XIII,G. P. Mueller andG. R. Pettit, Exper.18, 404 (1962).

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A preliminary report of this study was presented (August 27, 1962) at The Second International Symposium on the Chemistry of Natural Products, Prague (Czechoslovakia).

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This investigation was supported by PHS Research Grants CY-4074(C3) and CA 04074-05 from the National Cancer Institute, Public Health Service.     

Chemical constituents of the antibiotic fraction ofArnebia nobilis

Zusammenfassung Aus den Wurzeln vonArnebia nobilis wurden 4 antibiotisch wirksame Stoffe isoliert. Die Struktur von dreien wurde aufgeklärt.

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On deputation from the Chemistry Department, Lucknow University.

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To whom enquiries should be made. The isolation of shikonin monoacetate and,-dimethylacrylate fromLithosperm erythrorhizon, I.Morimoto, T.Kishi, S.Ikegana and Y.Hirata, Tetrahedron Lett.4737 (1965), has been brought to our notice since communicating this paper.

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Communication No. 1305 from the Central Drug Research Institute.     

Neue Substitutionsreaktionen bei Steroiden

Summary The intramolecular substitution of the angular methyl groups in steroids by attack of O-radicals derived from 6-, 11, and 20-alcohols is discussed. Irrespective of their genesis, these radicals abstract a hydrogen atom from one of the said methyl groups, suitably oriented in-position. The C-radicals thus formed give different products depending on the neighbouring groups.It is shown that 20-hydroxy-18-C-radicals combine with iodine atoms, to give 18-iodides which can befurther substituted through radicals to give potential 18-oxo-compounds in high yield. In the case of 20-cyanohydrines, the intramolecular reaction of the 18-C-radical with the cyano groups gives rise to the new 18-cyano-20-oxo-steroids.With 6- and 11-O-radicalssingle substitution in 19-position predominates, since the steric arrangement of the primary product favours the intramolecular ether formation over a second substitution reaction.A general reaction scheme for these transformations is proposed.

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Vorgetragen vonCh. Meystre am 23. 9. 61 anlässlich der Sommerversammlung der Schweiz. Chem. Gesellschaft in Biel (vgl. Chimia15, (1961), im Druck).

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Über Steroide 180. Mitteilung. 179. Mitt. vgl.A. Wettstein, Exper.17, 329 (1961).     

Hormonal rupture of larval diapause in the tickRhipicephalus sanguineus (Lat.)

Zusammenfassung Die Diapause von Larven der ZeckeRhipicephalus sanguineus (Lat.) wird durch- and-Ecdyson beendet.

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We would like to thank Dr.J. B. Siddal for generously providing-ecdysone, Dr.T. Takemoto for-ecdysone and Dr.N. Krishnan for the juvenile hormone analogue,trans, trans-10, 11-epoxy faresenic acid methyl ester.     

Conversion of γ-hydroxybutyrate to γ-aminobutyrate by mouse brain in vivo

Zusammenfassung -Hydroxybutyrat wird im Maushirn in-Aminobutyrat und in verschiedene -Aminosäuren umgewandelt.

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Supported by the Medical Research Council of Canada.     

Activité antifibrillante chez l'animal d'un nouveau dérivé de la phényl-éthylamine

Summary A new synthetic phenyl-ethyl-amine derivative, the 2-[N- (3, 4-methylen-dioxyphenylethyl)-methylaminomethyl]-tetrahydrofuran, No. 11 081, exhibits a strong protective effect against cardiac fibrillation and arrhythmias produced by various experimental methods: against fibrillation due to aconitine 3 × 10^–8 on the isolated cat's heart, it is active in a concentration of 10^–6–2 × 10^–6. Against cardiac arrhythmias produced in the cat by adrenaline + CHCl₃ or cyclopropane, it shows a protective effect by 5–10 mg/kg i.v. and even perorally by 50 mg/kg. In these tests, the antifibrillatory activity of the new compound seems to be roughly the same as that of -fagarine, and higher than that of procaine.

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9^e communication sur les dérivés des alcoylène-imines; 8^e communication, cf. Exper.10, 261 (1954).     

Bestimmung des α-2-Makroglobulinumsatzes beim Menschen

Summary The turnover of ₂-macroglobulins was measured by quantitative precipitation of the I¹³¹-marked protein, using a specific antiserum. In 6 normal persons, the half-life was found to be between 192 and 267 h. The catabolic rates in relation to the intravascular pool range between 437 and 703 mg/day

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Mit Unterstützung durch die Deutsche Forschungsgemeinschaft.     

Sesquiterpenoids minor constituents ofPinus parviflora. On the relationship between (−)-δ-cadinol, (+)-δ-cadinol,sesquigoyol, torreyol,and brown alga cadinol

Zusammenfassung 1-Dokosanol, Sesquigoyol,-Sitosterin und 3,5-Dimethoxystilben wurden ausP. formosana isoliert. Es konnte gezeigt werden, dass Sesquigoyol der optische Antipode von (–)--Cadinol ist.

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Sesquiterpenoids II. For the previous paper in this series, seeW. G. Dauben, B. Weinstein, P. Lim, andA. B. Anderson, Tetrahedron15, 217 (1961).

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On leave of absence from the Department of Chemistry, National Taiwan University, Taipei, Taiwan, Republic of China.

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The National Council of Science, Republic of China, is thanked for the award of a fellowship for advanced study to one of us (K.-T.W.).     

The visual response of the purple shore crab,Hemigrapsus nudus,to ionizing and non-ionizing radiations

Zusammenfassung Im Krabbenauge vonHemigrapsus nudus entstehen elektroretinographische Reaktionen (ERG) mit sichtbarem Licht und Röntgenstrahlung, die andeuten, dass dieselben Rhodopsin-Erregunsprozesse mit beiden Strahlungsarten stattfinden. Nach⁹⁰Sr--Strahlung wird angenommen, dass Cerenkov-Effekt- und induzierte Fluoreszenz-Lichterzeugung die-ERG-Reaktion deutlich beeinflussen.

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This research was conducted under a grant from the Environmental Control Administration, CPEHS, U.S. Public Health Service No. EC00119.

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Public Health Service Radiological Health Fellowship No. 97996-06-69.     

Inhibition of steroidΔ 4 reductase by heparin: Studies with desoxycorticosterone,progesterone, androstenedione and testosterone

Zusammenfassung Heparin hemmt die Reduktion der Doppelbindung in 4-Stellung des Rings A einer Reihe von C-11-desoxy, ⁴-4-keto-Steroiden in der Rattenleber. Es scheint, dass Heparin mit NADPH um das Steroid-reduktase-Apoenzym konkurriert.

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This work was supported by grant No. AM-09151 from The National Institutes of Health, U.S.P.H.S.     

1β-Hydroxylation ofd-norgestrel and norethisterone byBotryodiploadi malorum

Zusammenfassung Die mikrobiologische 1-Hydroxylierung vond-Norgestrel und Norethisteron durch den MikroorganismusBotryodiplodia malorum wird beschrieben. Ausserdem wurde 11-Hydroxynorethisteron isoliert und charakterisiert.

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Acknowledgement. The authors want to express their appreciation to Dr.H. Smith for advice and encouragement through the course of this work. We wish to thank Dr.T. Chang, Dr.C. Hetzel and Mr.C. Kuhlman for obtaining and interpreting the mass spectra and Mr.B. Hormann for NMR decoupling experiments and analytical services.     

In vitro and in vivo inhibitory action of 2-amino-4,6-dichloropyrimidine on polio and herpes virus

Résumé La 2-amino-4,6-dichloropyrimidine (Py 11) est capable d'inhiber la réplication du poliovirus et du virusHerpes simplex dans des milieux de culture complète, à condition que la mercaptoéthanolamine y soit aussi présente. Les combinaisons des deux composés sont actives, in vivo contre l'herpes cornealis du lapin.

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This work has been supported by a Grant of the Consiglio Nazionale delle Ricerche, Roma.     

Molekül-Massenspektrographie von Naturstoffen. Steroide

Summary The molecular weight of various steroids (sterols, steroidal sapogenins, and alkaloids) as well as the molecular weight distribution in complex mixtures of similar steroids, has been exactly determined by application of molecule mass spectrography. In this technique, negatively-charged (p – 1) ions are formed, usually without further fragmentation. The advantages and new possibilities of this method are discussed.

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I. Mitteilung.