DE1161887B - Process for the preparation of A-nor-B-homo-í¸-oestrenverbindungen - Google Patents
Process for the preparation of A-nor-B-homo-í¸-oestrenverbindungenInfo
- Publication number
- DE1161887B DE1161887B DEL40361A DEL0040361A DE1161887B DE 1161887 B DE1161887 B DE 1161887B DE L40361 A DEL40361 A DE L40361A DE L0040361 A DEL0040361 A DE L0040361A DE 1161887 B DE1161887 B DE 1161887B
- Authority
- DE
- Germany
- Prior art keywords
- general formula
- ozonization
- acetic acid
- estrogen
- performs
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000006385 ozonation reaction Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000262 estrogen Substances 0.000 claims description 6
- 229940011871 estrogen Drugs 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- -1 methanol Chemical compound 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000012024 dehydrating agents Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000003776 cleavage reaction Methods 0.000 claims 2
- 230000007017 scission Effects 0.000 claims 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 150000003431 steroids Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000005949 ozonolysis reaction Methods 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003263 anabolic agent Substances 0.000 description 1
- 229940124325 anabolic agent Drugs 0.000 description 1
- 230000001548 androgenic effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 210000000548 hind-foot Anatomy 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J69/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by contraction of only one ring by one atom and expansion of only one ring by one atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Steroid Compounds (AREA)
Description
Verfahren zur Herstellung von A-nor-B-homo-d5(Io)_östrenverbindungen Die Erfindung betrifft ein Verfahren zur Herstellung von neuen ringmodifizierten Steroiden, und zwar von Verbindungen der allgemeinen Formel I worin R Sauerstoff oder die Gruppe bedeutet. Gewisse Glieder dieser neuen Klasse von Steroiden zeigen eine nützliche physiologische Aktivität, und zwar als Anabolisantien ohne androgene Aktivität. Besonders interessante Vertreter derartiger aktiver Steroide sind die nach dem Verfahren der Erfindung herstellbaren Verbindungen, das 17ß-Acetoxy-3,6-diketo-A-nor-B-homo-45(1o>-östren und das 3,6,17-Triketo-A-nor-B-homo-45(lo»-östren.Process for the production of A-nor-B-homo-d5 (Io) _osterenverbindungen The invention relates to a process for the production of new ring-modified steroids, specifically of compounds of the general formula I. wherein R is oxygen or the group means. Certain members of this new class of steroids exhibit useful physiological activity as anabolic agents devoid of androgenic activity. Particularly interesting representatives of such active steroids are the compounds which can be prepared by the process of the invention, 17β-acetoxy-3,6-diketo-A-nor-B-homo-45 (10> -estren and 3,6,17-triketo -A-nor-B-homo-45 (lo »-östren.
Das erfindungsgemäße Verfahren zur Herstellung dieser neuen Verbindungen der allgemeinen Formel 1 ist in dem Reaktionsschema dargestellt und besteht darin, daß man in an sich bekannter Weise Ozon auf eine 3-Keto-5(10)-dehydroverbindung der allgemeinen Formel 11 worin R die oben angegebene Bedeutung hat, einwirken läßt, das Ozonisationsprodukt reduzierend spaltet und die so erhaltene 5,10-seco-3,5,10-Triketoverbindung der allgemeinen Formel 111 worin R die oben angegebene Bedeutung hat, anschließend mit Hilfe eines Dehydratisierungsmittels cyclisiert.The process according to the invention for the preparation of these new compounds of general formula 1 is shown in the reaction scheme and consists in converting ozone to a 3-keto-5 (10) -dehydro compound of general formula 11 in a manner known per se in which R has the meaning given above, allows it to act, cleaves the ozonization product in a reducing manner and the 5,10-seco-3,5,10-triketo compound of the general formula III obtained in this way wherein R has the meaning given above, then cyclized with the aid of a dehydrating agent.
Die Ausgangsverbindungen der allgemeinen Formel 11 können durch Reduktion der entsprechenden Steroide mit aromatischem Ring A erhalten werden (siehe z. B. B i r c h, J. Chem. Soc., 1950, S. 367, und A. L. W i 1 d s und Mitarbeiter, J. Am. Chefin. Soc., 1953, 75, S. 5366). The starting compounds of the general formula 11 can be obtained by reducing the corresponding steroids with an aromatic ring A (see, for example, Birch, J. Chem. Soc., 1950, p. 367, and AL W i 1 ds and coworkers, J . Am. Chefin. Soc., 1953, 75, p. 5366).
Die Ozonisierungsstufe wird vorteilhafterweise in einem hydroxylgruppenhaltigen Lösungsmittel, beispielsweise in einem niederen Alkohol, wie Methanol oder Äthanol, oder in einer Mischung eines hydroxylgruppenhaltigen Lösungsmittels mit einem anderen unter den Bedingungen dieser Reaktion inerten Lösungsmittel, beispielsweise einem Methanol-Methylenchlorid-Gemisch, durchgeführt. Die Ozonisierung kann aber auch in einer niederen Säure, beispielsweise Essigsäure, durchgeführt werden, was erlaubt, die anschließende Reduktion mit Zink ohne weitere Zugabe von Säure durchzuführen.The ozonization stage is advantageously carried out in a hydroxyl group-containing one Solvent, for example in a lower alcohol such as methanol or ethanol, or in a mixture of one containing hydroxyl groups Solvent with another solvent inert under the conditions of this reaction, for example a methanol-methylene chloride mixture. Ozonization can, however can also be carried out in a lower acid, for example acetic acid, what allows the subsequent reduction with zinc to be carried out without further addition of acid.
Wenn die Ozonisation in einem alkoholischen Lösungsmittel, wie Methanol, durchgeführt wird, kann die Reduktionsstufe sehr vorteilhaft mit Hilfe eines niederen Alkylphosphits, beispielsweise Trimethylphosphit, durchgeführt werden.If ozonization is carried out in an alcoholic solvent such as methanol, is carried out, the reduction stage can be very advantageous with the help of a lower Alkyl phosphites, for example trimethyl phosphite, can be carried out.
Die bei der Reduktion erhaltenen Verbindungen der allgemeinen Formel 111 werden vorzugsweise durch Dehydratisierung in saurem Milieu cyclisiert. Nach einer einfachen und vorteilhaften Verfahrensweise führt man die Cyclisierung in der Hitze in Essigsäure durch.The compounds of general formula III obtained in the reduction are preferably cyclized by dehydration in an acidic medium. According to a simple and advantageous procedure, the cyclization is carried out in the heat in acetic acid.
Die folgenden Beispiele erläutern das erfindungsgemäße Verfahren.The following examples explain the process according to the invention.
Die Schmelzpunkte sind die auf der Koflerbank bestimmten augenblicklichen Schmelzpunkte. Die Temperaturen sind in Celsiusgraden angegeben.The melting points are the instantaneous ones determined on the Kofler bench Melting points. The temperatures are given in degrees Celsius.
Beispiel 1 Herstellung von 17ß-Acetoxy-3,6-diketo-A-nor-B-homo-d5(i0)-östren Stufe A: Ozonolyse Man löst 4,2 g 17ß-Acetoxy-3-keto-d5(i0)-östren in einer Mischung von 17 ccm Methylenchlorid und 20 ccm Methanol, kühlt auf -70° und läßt ungefähr 80 Minuten lang Ozon durch die Lösung perlen. Man verjagt das überschüssige Ozon durch einen Stickstoffstrom und fügt dann tropfenweise 2,1 ccm Trimethylphosphit zu. Anschließend läßt man die Temperatur auf 0° ansteigen, fügt Wasserstoffperoxyd zum Zerstören des Überschusses an Trimethylphosphit und dann 100 ccm Methylenchlorid zu, wäscht mit Wasser, trocknet und dampft im Vakuum zur Trockne ein. Der Rückstand kristallisiert aus Isopropyläther und ergibt 3,670g 17ß-Acetoxy-5,10-seco-3,5,10-triketo-östran vom F. = 142°. [a]ö° = -35° (c = 0,5% Chloroform). Das Produkt ergibt sich in Form von farblosen Prismen, die in Chloroform sehr löslich, in Aceton und Alkohol löslich, in Äther wenig löslich und in Wasser unlöslich sind.Example 1 Preparation of 17β-acetoxy-3,6-diketo-A-nor-B-homo-d5 (i0) -estrous Stage A: Ozonolysis Dissolve 4.2 g of 17β-acetoxy-3-keto-d5 (i0) -East in a mixture of 17 cc of methylene chloride and 20 cc of methanol, cool to -70 ° and let ozone bubble through the solution for about 80 minutes. The excess ozone is driven off by a stream of nitrogen and 2.1 cc of trimethyl phosphite is then added dropwise. The temperature is then allowed to rise to 0 °, hydrogen peroxide is added to destroy the excess trimethyl phosphite and then 100 cc of methylene chloride, washed with water, dried and evaporated to dryness in vacuo. The residue crystallizes from isopropyl ether and gives 3.670 g of 17β-acetoxy-5,10-seco-3,5,10-triketo-estran with a temperature of 142 °. [a] δ ° = -35 ° (c = 0.5% chloroform). The product results in the form of colorless prisms which are very soluble in chloroform, soluble in acetone and alcohol, sparingly soluble in ether and insoluble in water.
Analyse: Berechnet ... C 68,9%, H 8,1%, O 22,9%; gefunden ... C 69,0%, H 8,1%, O 22,8%.Analysis: Calculated ... C 68.9%, H 8.1%, O 22.9%; found ... C 69.0%, H 8.1%, O 22.8%.
Das IR-Spektrum zeigt die Gegenwart der drei Carbonylgruppen durch die Banden bei 1739, 1723 und 1711 cm-i.The IR spectrum shows the presence of the three carbonyl groups through the bands at 1739, 1723 and 1711 cm-i.
Die Verbindung wurde in der Literatur bisher noch nicht beschrieben.The compound has not yet been described in the literature.
Stufe B : Cyclisierung Man gibt unter Stickstoff 3 g 17ß-Acetoxy-5,10-seco-3,5,10-triketo-östran in 12 ccm 90%ige Essigsäure und kocht 15 Minuten unter Rückfuß.Stage B: Cyclization 3 g of 17β-acetoxy-5,10-seco-3,5,10-triketo-estran are added under nitrogen in 12 cc of 90% acetic acid and boil for 15 minutes under the hindfoot.
Dann gießt man in eine Mischung von Eis und Wasser und extrahiert mit Methylenchlorid. Man wäscht die Extrakte mit Wasser, trocknet, behandelt mit Tierkohle, filtriert und dampft unter Vakuum zur Trockne ein. Der Rückstand kristallisiert aus Äther und ergibt 1,3 g (etwa 46%) 17ß-Acetoxy-3,6-diketo-A-nor-B-homo-i95t1o»-östren vom F.=162° und danach 174°. [a]' = +19° (c = 0,5% Chloroform). Das Produkt ergibt sich in Form von hexagonalen Prismen, die in Alkohol, Aceton und Chloroform sehr löslich, in Äther sehr wenig löslich und in Wasser unlöslich sind.Then it is poured into a mixture of ice and water and extracted with methylene chloride. The extracts are washed with water, dried and treated with Animal charcoal, filtered and evaporated to dryness under vacuum. The residue crystallizes from ether and yields 1.3 g (about 46%) of 17β-acetoxy-3,6-diketo-A-nor-B-homo-i95t1o »-estrogen from F. = 162 ° and then 174 °. [a] '= + 19 ° (c = 0.5% chloroform). The product yields themselves in the form of hexagonal prisms that are very present in alcohol, acetone and chloroform soluble, very sparingly soluble in ether and insoluble in water.
Analyse: C2oH2604 = 330,41. Berechnet ... C 72,7%, H 7,9%; gefunden ... C 72,6%, H 7,9%.Analysis: C2oH2604 = 330.41. Calculated ... C 72.7%, H 7.9%; found ... C 72.6%, H 7.9%.
UV-Spektrum in Äthanol: Limas 236 m#L, E = 12 600.UV spectrum in ethanol: Limas 236 m # L, E = 12 600.
Die Verbindung wurde in der Literatur bisher noch nicht beschrieben.The compound has not yet been described in the literature.
Beispiel 2 Herstellung von 3,6,17-Triketo-A-nor-B-homo-d5( i0»-östren Stufe A: Ozonolyse Man suspendiert 1 g 3,17-Diketo-d5(i0)-östren in 10 ccm 85%iger Essigsäure, kühlt in einem Eisbad und läßt 45 Minuten lang Ozon durchperlen. Anschließend verjagt man den Ozonüberschuß durch einen Stickstoffstrom, fügt 1 g Zinkpulver hinzu, rührt einige Minuten, saugt dann vom Zink ab, fügt 50 ccm Methylenchlorid zu, trocknet und' dampft unter Vakuum zur Trockne ein. Der Rückstand kristallisiert aus wäßrigem Essigester und ergibt 440 mg (etwa 40%) 5,10-seco-3,5,10,17-Tetraketo-östran vom F. = 168 bis 170°. [a]2 = +45° (c = 0,5% Chloroform). Das Produkt ergibt sich in Form von Blättchen, die in Chloroform sehr löslich, in Aceton löslich, in Äther wenig löslich und in Wasser unlöslich sind.Example 2 Preparation of 3,6,17-Triketo-A-nor-B-homo-d5 (i0 »-ostren Stage A: Ozonolysis 1 g of 3,17-diketo-d5 (10) oestrene is suspended in 10 cc of 85% strength Acetic acid, cool in an ice bath and bubble with ozone for 45 minutes. Afterward if the excess ozone is chased away by a stream of nitrogen, 1 g of zinc powder is added, stirs for a few minutes, then sucks off the zinc, adds 50 cc of methylene chloride, and dries and 'evaporated to dryness under vacuum. The residue crystallizes from aqueous Ethyl acetate and gives 440 mg (about 40%) 5,10-seco-3,5,10,17-tetraketo-estran vom F. = 168 to 170 °. [a] 2 = + 45 ° (c = 0.5% chloroform). The product results in Form of leaflets that are very soluble in chloroform, soluble in acetone, in ether are sparingly soluble and insoluble in water.
Analyse: Ci8H2404 = 304,37.Analysis: Ci8H2404 = 304.37.
Berechnet ... C 71,0%, H 7,95%, O 21,00%; gefunden ... C 70,70%, H 7,9%, O 21,5%.Calculated ... C 71.0%, H 7.95%, O 21.00%; found ... C 70.70%, H 7.9%, O 21.5%.
Das IR-Spektrum zeigt durch Banden bei 1737, 1720 und 1706 cm -i die Gegenwart der Carbonylgruppen an.The IR spectrum shows the bands at 1737, 1720 and 1706 cm-i Presence of the carbonyl groups.
Die Verbindung wurde in der Literatur bisher noch nicht beschrieben.The compound has not yet been described in the literature.
Stufe B : Cyclisierung Nach der Verfahrensweise der Stufe B des Beispiels 1 wandelt man das 5,10-seco-3,5,10,17-Tetraketo-östran zum 3,6,17-Triketo-A-nor-B-homod5(io)-östren um.Stage B: Cyclization Following the procedure of stage B of the example 1 converts the 5,10-seco-3,5,10,17-tetraketo-estrane to the 3,6,17-triketo-A-nor-B-homod5 (io) -estrogen around.
3 g 5,10-seco-3,5,10,17-Tetraketo-östran ergeben 1,218 g 3,6,7-Triketo-A-nor-B-homo-d5(i0)-östren (Ausbeute 42%). Zur Analyse wird das Produkt aus Äthylacetat umkristallisiert. Es ist in Aceton, Benzol und Chloroform sehr löslich und in Äther und Äthylacetat löslich. F. = 176', [a]-'00 = + 116° (c = 0,5% Chloroform).3 g of 5,10-seco-3,5,10,17-tetraketo-oestrane give 1.218 g of 3,6,7-triketo-A-nor-B-homo-d5 (10) -estrogen (yield 42%). The product is recrystallized from ethyl acetate for analysis. It is very soluble in acetone, benzene and chloroform and soluble in ether and ethyl acetate. M.p. = 176 ', [a] -' 00 = + 116 ° (c = 0.5% chloroform).
Analyse: Ci8H220a = 286,36. Berechnet ... C 75,50/a, H 7,7%; gefunden ... C 74,3%, H 7,5%. IR-Spektrum: Zwei Carbonylbanden bei 1669 und 1609 cm-'. Schulter bei etwa 1740 cm-' (17-Keto). Maximum bei 1722 cm-1.Analysis: Ci8H220a = 286.36. Calculated ... C 75.50 / a, H 7.7%; found ... C 74.3%, H 7.5%. IR spectrum: two carbonyl bands at 1669 and 1609 cm- '. Shoulder at about 1740 cm- '(17-keto). Maximum at 1722 cm-1.
Die Verbindung wurde in der Literatur bisher noch nicht beschrieben.The compound has not yet been described in the literature.
Claims (7)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1161887X | 1960-11-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1161887B true DE1161887B (en) | 1964-01-30 |
Family
ID=9652649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEL40361A Pending DE1161887B (en) | 1960-11-07 | 1961-10-31 | Process for the preparation of A-nor-B-homo-í¸-oestrenverbindungen |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1161887B (en) |
-
1961
- 1961-10-31 DE DEL40361A patent/DE1161887B/en active Pending
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