Über einheitliche Racemate des 1-Oxo-2-methyl-7-methoxy-octahydrophenanthren-2-carbonsäuremethylesters

Summary The racemic mixture of 1-oxo-2-methyl-7-methoxy-octahydrophenanthrene-2-carboxylic acid methyl esters has been separated into three crystalline racemates.     

Die Totalsynthese des natürlichen Östrons

Summary The total synthesis ofd-strone, the natural strogenic hormone, is described.     

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.

---

---

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

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.

---

---

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

---

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

Advances in the field of adrenal cortical hormones

Zusammenfassung Aus den Arbeiten der letzten zwei Jahre auf dem Gebiet der Nebennierenrinden-Hormone stechen — was die Herstellung neuer, hochwirksamer Verbindungen anbetrifft — die Isolierung und Konstitutionsaufkl?rung des natürlichen Hormons Aldosteron und die synthetische Gewinnung der 9α-halogenierten Hydrocortisone hervor. Diese Ergebnisse haben den Weg zu weiteren wesentlichen Entwicklungen eines Gebietes ge?ffnet, das mit Cortison und Hydrocortison abgeschlossen schien. Auf dem Gebiete der Teilsynthese wurde die Herstellung von 11-oxygenierten aus 12-oxygenierten Derivaten und insbesondere aus Verbindungen ohne Sauerstoff im Ring C stark ausgebaut. Bei der letzteren liegen die wichtigsten Befunde wohl in den mikrobiologischen Hydroxylierungen in 11-Stellung und den anschliessenden chemischen Umwandlungen. Erst kürzlich ist es m?glich geworden, auch die typischen Seitenketten durch mikrobiologische Methoden zu gewinnen. Die Totalsynthese der Hormone aus einfachsten chemischen Bausteinen wurde entwickelt und macht rasche Forschritte. Die Auffassungen über die Biosynthese haben konkretere Formen angenommen. Die unz?hligen Arbeiten über Katabolismus und klinische Verwendung der Nebennierenrinden-Hormone konnten im Rahmen dieser übersicht nicht einmal gestreift werden.

---

---

Based on a talk at the Gordon Research Conference on the Chemistry of Steroids, organized by the American Association for the Advancement of Science, New Hampton N.H., August 4, 1954. Communication No. 125 “On Steroids”. No. 124 compareK. Heusler andA. Wettstein, Chem. Ber.87, 1301, 1954.     

Synthetische Versuche in der Doisynolsäurereihe

Summary The amorphous carboxylic acid of the doisynolic acid type, prepared byHunter andHogg according to a new method developed by us, consists presumably of a mixture of products representing different hydrogenation stages.

---

---

54. Mitt. «Über Steroide» sowie XI. Arbeit «Über östrogene Karbonsäuren». Vgl. Exper.2, 408 (1946) und Helv. chim. acta29, 1231 (1946).     

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.

---

---

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).

---

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

Identification of organ-specific glycosylation of a membrane protein in two tissues using lectins

Since glycosylation of proteins is performed by the host cell, and variable sugar groupings can confer heterogeneity on the same polypeptide, we wished to see whether membrane proteins, in particular the ubiquitous transmembrane Na, K-ATPase, could be glycosylated differently in different organs. Using a highly sensitive enzyme-linked antibody detection system of bound digoxigenin-labelled lectins on nitrocellulose sheets containing electroblotted and subunits of kidney and brain Na,K-ATPase, isolated from various rat strains, in combination with isoform-specific immunoblots, we discovered that brain Na,K-ATPase was highly mannosylated in contrast to renal Na,K-ATPase. Thus, we describe the existence of organ-related glycoforms of an integral ubiquitous membrane protein, i.e. diversification of the same polypeptide by organ-typical sugars. At the same time, the presence of the same glycosylation pattern can make distinct protein isoforms occurring in a same organ more homogeneous. Such organ-related glycoforms may serve for tissue identification and as tissue-specific receptors.     

Über eine neue Synthese von 18-Hydroxy- und 18-Oxo-progesteron

Summary 18-Hydroxyprogesterone (VII) and the corresponding 18-aldehyde (IX), hitherto only accessible with difficulty from natural 18-substituted steroids, have been synthesized starting from progesterone.

---

---

Über Steroide, 188. Mitt.

---

187. Mitt. s.Ch. Meystre, K. Heusler, J. Kalvoda, P. Wieland, G. Anner undA. Wettstein, Helv. chim. Acta45, 1317 (1962).