DE1131667B - Process for the production of 1ª ‡ -methyl steroids of the androstane series - Google Patents
Process for the production of 1ª ‡ -methyl steroids of the androstane seriesInfo
- Publication number
- DE1131667B DE1131667B DESCH28196A DESC028196A DE1131667B DE 1131667 B DE1131667 B DE 1131667B DE SCH28196 A DESCH28196 A DE SCH28196A DE SC028196 A DESC028196 A DE SC028196A DE 1131667 B DE1131667 B DE 1131667B
- Authority
- DE
- Germany
- Prior art keywords
- androstane
- steroids
- methyl
- methylene
- production
- 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 11
- 150000001441 androstanes Chemical class 0.000 title description 4
- 238000004519 manufacturing process Methods 0.000 title description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 4
- 125000000468 ketone group Chemical group 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- -1 1,2-methylene steroids Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- QZLYKIGBANMMBK-UGCZWRCOSA-N 5α-Androstane Chemical compound C([C@@H]1CC2)CCC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CCC[C@@]2(C)CC1 QZLYKIGBANMMBK-UGCZWRCOSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 230000001195 anabolic effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- 238000006049 ring expansion reaction Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- WSSZZUWWCXSGKJ-WFDUKQKSSA-N (8s,9s,10r,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-1,2,3,4,5,7,8,9,11,12,14,15,16,17-tetradecahydrocyclopenta[a]phenanthren-6-one Chemical compound C1C(=O)C2CCCC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 WSSZZUWWCXSGKJ-WFDUKQKSSA-N 0.000 description 1
- PAFPYXSFFACISZ-UHFFFAOYSA-N 3,5-cyclocholestan-6-one Chemical compound C1CC2(C)C3CCC4(C)C(C(C)CCCC(C)C)CCC4C3CC(=O)C32C1C3 PAFPYXSFFACISZ-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- WAAWMJYYKITCGF-WTPIMUJOSA-N 5alpha-ergostane Chemical compound C([C@@H]1CC2)CCC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@H](C)CC[C@H](C)C(C)C)[C@@]2(C)CC1 WAAWMJYYKITCGF-WTPIMUJOSA-N 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical group C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- 238000006036 Oppenauer oxidation reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000001548 androgenic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J7/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms
-
- 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
- C07J75/00—Processes for the preparation of steroids in general
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Steroid Compounds (AREA)
Description
Verfahren zur Herstellung von 1 a-Methylsteroiden der Androstanreihe In der deutschen Auslegeschrift 1122 944 ist bereits vorgeschlagen, den Cyclopropanring von 1,2a-Methylen-3-ketosteroiden mit Halogenwasserstoff zu öffnen und die dabei entstehenden la-Halogenmethylverbindungen mit Hydrierungsmitteln zu den la-Methyl-3-ketosteroiden zu enthalogenieren.Process for the preparation of 1 a-methyl steroids of the androstane series In the German Auslegeschrift 1 122 944 it has already been proposed to open the cyclopropane ring of 1,2a-methylene-3-keto steroids with hydrogen halide and to convert the la-halomethyl compounds formed with hydrogenating agents to the la- To dehalogenate methyl-3-keto steroids.
Ebenfalls sind auch Hydrierungsverfahren mit Steoridverbindungen, die einen Cyclopropanring im Molekül enthalten, bekannt. So entstehen z. B. bei der Hydrierung von 3,5-Cyclocholestan-6-on unter Ringerweiterung 6-Cholestanon und aus 3,5-Cyclo-_96.2`=-ergostadien auch unter Ringerweiterung Ergostan.Hydrogenation processes with steroid compounds, which contain a cyclopropane ring in the molecule are known. So arise z. B. at the hydrogenation of 3,5-Cyclocholestan-6-one with ring expansion 6-Cholestanone and from 3,5-Cyclo-_96.2` = -ergostadien also with ring expansion ergostane.
Es wurde nun gefunden, daß man la-Methylsteroide der Androstanreihe aus den entsprechenden 1,2a-Methylensteroiden dadurch erhält, daß man den in 1,2-Stellung ankondensierten Ccylopropanring mit katalytisch angeregtem Wasserstoff, vorzugsweise in Gegenwart von Platinkatalysatoren in Eisessig, unter Bildung der entsprechenden 1 a-Methylsteroide öffnet und gegebenenfalls gleichzeitig anwesende Hydroxylgruppen, die z. B. im Ausgangsprodukt als Ketogruppen vorlagen und während der Umsetzung ebenfalls zu a- und/oder fl-ständigen Hydroxylgruppen reduziert wurden, in an sich bekannter 2o Weise, z. B. mittels Chromsäure oder nach der Oppenauer-Methode, zu Ketogruppen zurückoxydiert. Das erfindungsgemäße Verfahren verläuft nach folgendem allgemeinen Schema: Geeignete Ausgangsstoffe für das erfindungsgemäße Verfahren sind unter anderem nach den Verfahren gemäß des deutschen Patents 1072 991 und der deutschen Auslegeschrift 1096 353 erhältlich.It has now been found that la-methyl steroids of the androstane series are obtained from the corresponding 1,2a-methylene steroids in that the cyclopropane ring condensed in the 1,2-position is obtained with catalytically excited hydrogen, preferably in the presence of platinum catalysts in glacial acetic acid, with formation of the corresponding 1 a-methyl steroids opens and optionally simultaneously present hydroxyl groups which z. B. were present as keto groups in the starting product and were also reduced to a- and / or fl-hydroxyl groups during the reaction, in a manner known per se, eg. B. by means of chromic acid or by the Oppenauer method, back-oxidized to keto groups. The process according to the invention proceeds according to the following general scheme: Suitable starting materials for the process according to the invention are obtainable, inter alia, by the process according to German patent 1072 991 and German Auslegeschrift 1096 353.
Eine andere Quelle für die hierfür benötigten Ausgangsstoffe sind die Verfahren gemäß der deutschen Patentschrift 1023764 und der deutschen Patentanmeldung Sch 27090 IV b / 12o, bei denen durch thermische Zersetzung der Diazomethananlagerungsprodukte von J1-3-Ketosteroiden neben den als Hauptprodukt gewonnenen 1-Methyl-11-3-ketosteroiden 1,2-Methylen-3-ketosteroide in nicht unerheblicher Menge als Nebenprodukte anfallen. Mit dem erfindungsgemäßen Verfahren ist es ebenfalls möglich, diese Nebenprodukte einer nutzbringenden technischen Verwertung zugänglich zu machen.Another source for the starting materials required for this are the processes according to German patent specification 1023764 and German patent application Sch 27090 IV b / 12o, in which the thermal decomposition of the diazomethane addition products of J1-3-keto steroids in addition to the 1-methyl-11 obtained as the main product -3-ketosteroids 1,2-methylene-3-ketosteroids occur in not inconsiderable amounts as by-products. With the process according to the invention it is also possible to make these by-products available for useful industrial utilization.
Die nach dem erfindungsgemäßen Verfahren dargestellten la-Methyl-3-ketosteroide der Androstanreihe sind als Heilmittel, z. B. la-Methylandrostan-17f-'-ol-3-on-17-acetat, als sehr stark androgene und gleichzeitig stark anabolische Wirksubstanz oder als Zwischenprodukte zur Herstellung solcher Heilmittel, wie z. B. dem stark anabolisch wirksamen 1-Methyl-11-androsten-17ß-ol-3-on, technisch verwertbar. Beispiel 1 344 mg 1,2a-Methylen-androstan-17ß-ol-3-on-17-acetat werden in 10 ml Eisessig gelöst und dann bei Zimmertemperatur unter Zusatz von 100 mg Platinoxyd bis zur Aufnahme von 2 Moläquivalenten Wasserstoff hydriert. Danach wird vom Katalysator abfiltriert, in Eiswasser eingerührt, mit Methylenchlarid extrahiert und die Methylenchloridphase mit Natriumhydrogencarbonatlösung sowie mit Wasser gewaschen. Nach dem Trocknen über Natriumsulfat wird im Vakuum zur Trockne eingeengt.The la-methyl-3-ketosteroids prepared by the process according to the invention the androstane series are used as remedies, e.g. B. la-Methylandrostan-17f -'-ol-3-one-17-acetate, as a very strong androgenic and at the same time strong anabolic active substance or as Intermediate products for the manufacture of such remedies, such as. B. the strongly anabolic effective 1-methyl-11-androsten-17ß-ol-3-one, technically usable. Example 1 344 mg of 1,2a-methylen-androstane-17ß-ol-3-one-17-acetate are dissolved in 10 ml of glacial acetic acid and then at room temperature with the addition of 100 mg of platinum oxide until absorption hydrogenated by 2 molar equivalents of hydrogen. The catalyst is then filtered off, stirred into ice water, extracted with methylene chloride and the methylene chloride phase washed with sodium hydrogen carbonate solution and with water. After drying It is concentrated to dryness in vacuo over sodium sulfate.
Der Rückstand wird mit 17 ml absolutem Toluol und 3,7 ml Cyclohexanon versetzt. Dann werden einige Millimeter Lösungsmittel zur Beseitigung vorhandener Feuchtigkeit abdestilliert und schließlich 186 mg Aluminiumisopropylat in 1,9 ml Toluol innerhalb von 5 Minuten hinzugefügt. Das Reaktionsgemisch wurde nun unter langsamem teilweisem Abdestillieren des Lösungsmittels 45 Minuten erhitzt. Es wird dann mit Methylenchlorid verdünnt, mit 2 n-Schwefelsäure und mit Wasser gewaschen. Die Methylenchloridphase wird wasserdampfdestilliert. Der Rückstand der Wasserdampfdestillation wird in Methylenchlorid aufgenommen, die organische Phase über Natriumsulfat getrocknet, anschließend durch Abfiltrieren vom Trockenmittel im Vakuum eingeengt und der Rückstand aus Hexan umkristallisiert. Man erhält la-Methyl-androstan-17ß-ol-3-on-17-acetat. F.=169 bis 170° C; [a] ö = -I-16,7° (CHC13 c=0,88). An Stelle der Oppenauer-Oxydation mit Aluminiumisopropylat ist auch die Oxydation mit Chromsäure möglich.The residue is mixed with 17 ml of absolute toluene and 3.7 ml of cyclohexanone offset. Then a few millimeters of solvent are used to remove any existing Moisture distilled off and finally 186 mg of aluminum isopropoxide in 1.9 ml toluene added within 5 minutes. The reaction mixture was now 45 minutes, with partial removal of the solvent by distillation heated. It is then diluted with methylene chloride, with 2N sulfuric acid and with Water washed. The methylene chloride phase is steam distilled. The residue the steam distillation is taken up in methylene chloride, the organic Phase dried over sodium sulfate, then by filtering off the desiccant concentrated in vacuo and the residue recrystallized from hexane. La-methyl-androstane-17ß-ol-3-one-17-acetate is obtained. M.p. = 169 to 170 ° C; [a] δ = -I-16.7 ° (CHCl13 c = 0.88). Instead of the Oppenauer oxidation Oxidation with chromic acid is also possible with aluminum isopropylate.
Beispiel 2 2 g 1,2a-Methylen-androstan-17ß-ol-3-on-17-acetat werden in 58 ml Eisessig gelöst und dann bei Zimmertemperatur unter Zusatz von 500 mg Platinoxyd mit Wasserstoff hydriert. Wenn kein Wasserstoff mehr aufgenommen wird, filtriert man vom Katalysator ab, rührt in Eiswasser ein und filtriert das ausgefallene Produkt ab. Es wird bei 70° C im Vakuum getrocknet. Man erhält so 1,88 g eines rohen 1a-Methyl-androstan-3,17ß-diol-17-acetats, die in 30 ml Aceton, gelöst mit 1,3 ml Chromsäurelösung (Chromsäurelösung: 267 g Chromtrioxyd, 230 ml konzentrierte Schwefelsäure, 400 ml Wasser auf 11 auffüllen), unter Rühren versetzt werden. Es wird in Eiswasser eingerührt, das ausgefallene Produkt abgesaugt, gewaschen, getrocknet und aus Hexan umkristallisiert. Man erhält 1,27 g la-Methyl-androstan-17ß-ol-3-on-17-acetat. F.=169 bis 169,5° C.Example 2 2 g of 1,2a-methylene-androstane-17β-ol-3-one-17-acetate are used dissolved in 58 ml of glacial acetic acid and then at room temperature with the addition of 500 mg of platinum oxide hydrogenated with hydrogen. If no more hydrogen is absorbed, filter the catalyst is removed, stirred into ice water and the precipitated product is filtered off away. It is dried at 70 ° C. in a vacuum. This gives 1.88 g of a crude 1a-methyl-androstane-3,17ß-diol-17-acetate, those in 30 ml of acetone, dissolved with 1.3 ml of chromic acid solution (chromic acid solution: 267 g Chromium trioxide, 230 ml concentrated sulfuric acid, 400 ml water make up to 11), are added with stirring. It is stirred into ice water, the precipitated Sucked off product, washed, dried and recrystallized from hexane. You get 1.27 g of la-methyl-androstane-17ß-ol-3-one-17-acetate. F. = 169 to 169.5 ° C.
Claims (2)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DESCH28196A DE1131667B (en) | 1960-07-21 | 1960-07-21 | Process for the production of 1ª ‡ -methyl steroids of the androstane series |
| CH1191565A CH414610A (en) | 1960-07-21 | 1961-03-11 | Process for the production of 1a-methyl steroids |
| CH295861A CH408911A (en) | 1960-04-06 | 1961-03-11 | Process for the production of 1a-methyl steroids |
| GB9933/61A GB977082A (en) | 1960-04-06 | 1961-03-17 | 1ª-methyl-steroids and a process for their manufacture |
| BE602281A BE602281A (en) | 1960-04-06 | 1961-04-06 | 1-Methylsteroid. |
| FR867038A FR1293M (en) | 1960-04-06 | 1961-07-05 | Drug based on 1 α-methyl-testosterone, usable as anabolic. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DESCH28196A DE1131667B (en) | 1960-07-21 | 1960-07-21 | Process for the production of 1ª ‡ -methyl steroids of the androstane series |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1131667B true DE1131667B (en) | 1962-06-20 |
Family
ID=7431041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DESCH28196A Pending DE1131667B (en) | 1960-04-06 | 1960-07-21 | Process for the production of 1ª ‡ -methyl steroids of the androstane series |
Country Status (2)
| Country | Link |
|---|---|
| CH (1) | CH414610A (en) |
| DE (1) | DE1131667B (en) |
-
1960
- 1960-07-21 DE DESCH28196A patent/DE1131667B/en active Pending
-
1961
- 1961-03-11 CH CH1191565A patent/CH414610A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CH414610A (en) | 1966-06-15 |
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