DE1091565B - Process for the preparation of 2ª ‡ -Methyl-9ª ‡ -fluoro-4-pregnene derivatives - Google Patents
Process for the preparation of 2ª ‡ -Methyl-9ª ‡ -fluoro-4-pregnene derivativesInfo
- Publication number
- DE1091565B DE1091565B DEA27771A DEA0027771A DE1091565B DE 1091565 B DE1091565 B DE 1091565B DE A27771 A DEA27771 A DE A27771A DE A0027771 A DEA0027771 A DE A0027771A DE 1091565 B DE1091565 B DE 1091565B
- Authority
- DE
- Germany
- Prior art keywords
- methyl
- fluoro
- pregnen
- preparation
- derivatives
- 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 8
- 238000002360 preparation method Methods 0.000 title description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 206010003246 arthritis Diseases 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 206010006811 Bursitis Diseases 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- 208000006673 asthma Diseases 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- JYGXADMDTFJGBT-VWUMJDOOSA-N hydrocortisone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 JYGXADMDTFJGBT-VWUMJDOOSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 208000017520 skin disease Diseases 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- FUFLCEKSBBHCMO-UHFFFAOYSA-N 11-dehydrocorticosterone Natural products O=C1CCC2(C)C3C(=O)CC(C)(C(CC4)C(=O)CO)C4C3CCC2=C1 FUFLCEKSBBHCMO-UHFFFAOYSA-N 0.000 description 1
- MFYSYFVPBJMHGN-ZPOLXVRWSA-N Cortisone Chemical compound O=C1CC[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 MFYSYFVPBJMHGN-ZPOLXVRWSA-N 0.000 description 1
- MFYSYFVPBJMHGN-UHFFFAOYSA-N Cortisone Natural products O=C1CCC2(C)C3C(=O)CC(C)(C(CC4)(O)C(=O)CO)C4C3CCC2=C1 MFYSYFVPBJMHGN-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 206010041277 Sodium retention Diseases 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- 229960004544 cortisone Drugs 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 208000030533 eye disease Diseases 0.000 description 1
- 239000003862 glucocorticoid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229960000890 hydrocortisone Drugs 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004810 partition chromatography Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- MUUHXGOJWVMBDY-UHFFFAOYSA-L tetrazolium blue Chemical compound [Cl-].[Cl-].COC1=CC(C=2C=C(OC)C(=CC=2)[N+]=2N(N=C(N=2)C=2C=CC=CC=2)C=2C=CC=CC=2)=CC=C1[N+]1=NC(C=2C=CC=CC=2)=NN1C1=CC=CC=C1 MUUHXGOJWVMBDY-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J5/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane and substituted in position 21 by only one singly bound oxygen atom, i.e. only one oxygen bound to position 21 by a single bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Verfahren zur Herstellung von 2 a-Methyl-9 a-fluor-4-pregnenderivaten Die Erfindung betrifft ein Verfahren zur Herstellung von 2a-Methyl-9a-fluor-4-pregnenderivaten.Process for the preparation of 2a-methyl-9a-fluoro-4-pregnancy derivatives The invention relates to a process for the preparation of 2a-methyl-9a-fluoro-4-pregnancy derivatives.
Die erfindungsgemäß herstellbaren Verbindungen entsprechen der allgemeinen Formel in der X den 2wertigen Rest = C H O H oder > C = O bedeutet. Diese Verbindungen werden durch Umsetzung von 2a-Methyl-9ß,11ß-oxido-4-pregnen-16a,17a,21-triol-3,20-dion-16a,21-dialkanoaten mit einem Fluorwasserstoff in einem Lösungsmittel, an die sich gegebenenfalls die Oxydation des gebildeten 9a-Fluor-4-pregnen-llß-olderivats zum 11-Keton anschließt, und Verseifung der erhaltenen Verbindungen mit Alkali zu den 2a-Methyl-9a-fluor-4-pregnen-11ß,16a,17a,21-tetraol-3,20-dionen bzw. -16a,17a,21-triol-3,11,20-trionen hergestellt.The compounds which can be prepared according to the invention correspond to the general formula in which X is the divalent radical = CHOH or> C = O. These compounds are prepared by reacting 2a-methyl-9ß, 11ß-oxido-4-pregnen-16a, 17a, 21-triol-3,20-dione-16a, 21-dialkanoates with a hydrogen fluoride in a solvent, to which optionally the oxidation of the 9a-fluoro-4-pregnen-11ß-older derivative formed to the 11-ketone follows, and saponification of the compounds obtained with alkali to give 2a-methyl-9a-fluoro-4-pregnen-11ß, 16a, 17a, 21- tetraol-3,20-dione or -16a, 17a, 21-triol-3,11,20-trione.
Verbindungen der angegebenen allgemeinen Formel weisen eine glucocorticoide Wirksamkeit auf, die der des Hydrocortisons ähnlich ist, und sind als entzündungshemmende Mittel bei Arthritis, Haut- und Augenkrankheiten, Asthma, Verbrennungen, Schleimbeutelentzündung u. dgl. mit gutem Erfolg verwendbar.Compounds of the given general formula have a glucocorticoid Effectiveness that is similar to that of hydrocortisone and are considered to be anti-inflammatory Remedy for arthritis, skin and eye diseases, asthma, burns, bursitis and the like usable with good success.
Dienachdemerfindungsgemäßen Verfahrenherstellbaren Verbindungen können oral, in Form von Tabletten oder Kapseln u. dgl., parenteral, in Suspension oder Lösung oder örtlich in Ölen, Cremen und Salben u. dgl. angewendet weiden.The compounds which can be prepared by the process according to the invention can orally, in the form of tablets or capsules and the like, parenterally, in suspension or Solution or applied topically in oils, creams and ointments and the like.
Ferner können die nach dem erfindungsgemäßen Verfahren erhältlichen 2a-Methyl-9a-halogen-4-pregnen-16a,17a-diolderivate zur Linderung und Behebung von Arthritis, Dermatosen, Asthma, Bursitis und ähnlichen Erkrankungen genauso wie die bekannten 9a-Halogenderivate des Hydrocortisons und Cortisons angewandt werden, ohne jedoch wie letztere zu Störungen des Elektrolythaushalts zu führen. Unter Störung des Elektrolythaushalts wird die Erscheinung verstanden, daß die zulässige Natriumkonzentration in der Zelle überschritten wird, wodurch die Zelle übernormale Mengen an Wasser speichert, da der Organismus das Bestreben hat, die durch die Natriumretention bewirkte Konzentrationserhöhung durch Eintritt weiteren Wassers in die Zelle zu senken. Die Störung des Elektrolythaushalts führt zu einer Verminderung der Herzleistung und zu Ödemen, die es erforderlich machen, die Behandlung vorzeitig, d. h. vor der Behebung der zu bekämpfenden Erkrankungen abzubrechen. Bei der Behandlung von Arthritis u. dgl. mit den nach dem vorliegenden Verfahren erhältlichen Substanzen ist eine derartige Unterbrechung nicht erforderlich, da sie von den unerwünschten Wirkungen der bekannten Substanzen praktisch frei sind.Furthermore, those obtainable by the process according to the invention can 2a-methyl-9a-halogen-4-pregnen-16a, 17a-diol derivatives to alleviate and remedy Arthritis, dermatoses, asthma, bursitis and similar diseases as well as that known 9a-halogen derivatives of hydrocortisone and cortisone are used, but without leading to disturbances of the electrolyte balance like the latter. Under disturbance of the electrolyte balance is understood the phenomenon that the permissible sodium concentration in the cell is exceeded, causing the cell to have abnormal amounts of water stores as the organism has the aspiration brought about by the sodium retention Increase in concentration by entering more water into the cell. the Disturbance of the electrolyte balance leads to a reduction in cardiac output and to edema, which makes it necessary to premature treatment, d. H. before fixing of the diseases to be combated. In the treatment of arthritis and the like The like. With the substances obtainable by the present process is one such Interruption not required as it is known from the undesirable effects of the Substances are practically free.
Das folgende Beispiel erläutert das erfindungsgemäße Verfahren.The following example explains the method according to the invention.
Beispiel Eine Lösung von 0,10g 2a-Methyl-9ß,llß-oxido-4-pregnen-16a,17a,21-triol-3,20-dion-16a,21-diacetat in 25 ml Chloroform (alkoholfrei) wird auf -5°C abgekühlt und dann mit 1 ml wasserfreiem Fluorwasserstoff versetzt. Das Reaktionsgemisch wird 2 Stunden bei - 5'C auf einer mechanischen Schüttelvorrichtung geschüttelt, in Eiswasser gegossen und mit Natriumbicarbonat neutralisiert. Danach extrahiert man mehrere Male mit Chloroform und wäscht die vereinigten Extrakte mit Wasser bis zur Neutralität. Der nach dem Trocknen über Natriumsulfat und Eindampfen zur Trockne erhaltene Rückstand wird in 5 ml Pyridin gelöst und mit 1,0 ml Essigsäureanhydrid versetzt. Die gebildete Lösung wird 16 Stunden bei Zimmertemperatur stehengelassen. Danach wird sie in Wasser gegossen und mehrmals mit Essigsäureäthylester extrahiert. Die vereinigten Extrakte weiden mit Wasser neutral gewaschen, über Natriumsulfat getrocknet und zur Trockne eingedampft. Man erhält ein Öl, das der Verteilungschromatographie an Diatomeenerde unterworfen wird. Das dabei verwendete Lösungsmittelsystem besteht aus 3 Teilen Essigsäureäthylester, 2 Teilen Petroläther (Siedepunkt 90 bis 100°C), 3 Teilen Methanol und 2 Teilen Wasser. Die obere Phase dieses Lösungsmittelgemisches wird als mobile Phase und die untere Phase als stationäre Phase verwendet. Das aus der Säule austretende Eluat wird in einem Beckman-Spektrophotometer, dessen automatischer Ableser auf 240 m#t eingestellt «-orden war, laufend untersucht. Die Ablesevorrichtung läßt vier deutliche Spitzen erkennen, und die dazugehörigen Fraktionen werden jeweils gesondert behandelt. Die letzte dieser Fraktionen (etwa 2 Säulenvolumina) wird zur Trockne eingedampft und liefert 13,0 mg eines Öls, das aus Aceton-Petroläther umkristallisiert wird. Man erhält 5,5 mg 2a-Methyl-9a-fluor-4-pregnen-llß,16a,17a, 21-tetraol-3,20-dion-16a, 21-diacetat (XII) vom F. = 140 bis 200°C. Eine Kristallisation aus Aceton-Petroläther liefert 3,0 mg Substanz von unverändertem Schmelzpunkt. Der Ketoltest mit Tetrazoliumblau ist positiv. Auf dem Papierchromatogram erscheint ein Flecken.Example A solution of 0.10 g of 2a-methyl-9ß, llß-oxido-4-pregnen-16a, 17a, 21-triol-3,20-dione-16a, 21-diacetate in 25 ml of chloroform (alcohol-free) is cooled to -5 ° C and then with 1 ml of anhydrous Hydrogen fluoride added. The reaction mixture is 2 hours at -5'C on a mechanical shaker, poured into ice water and sprinkled with sodium bicarbonate neutralized. Then extracted several times with chloroform and washed combined extracts with water until neutral. The one after drying over Sodium sulfate and evaporation to dryness obtained residue is dissolved in 5 ml of pyridine dissolved and with 1.0 ml of acetic anhydride offset. The educated The solution is left to stand at room temperature for 16 hours. After that she is in water poured and extracted several times with ethyl acetate. The combined extracts willow washed neutral with water, dried over sodium sulfate and dried to dryness evaporated. An oil is obtained which is compatible with partition chromatography on diatomaceous earth is subjected. The solvent system used consists of 3 parts Ethyl acetate, 2 parts of petroleum ether (boiling point 90 to 100 ° C.), 3 parts of methanol and 2 parts of water. The upper phase of this solvent mixture is called mobile Phase and the lower phase used as the stationary phase. The one emerging from the column Eluate is in a Beckman spectrophotometer whose automatic reader is on 240 m # t discontinued "order was continuously examined. The reading device leaves recognize four distinct peaks, and the associated fractions are each treated separately. The last of these fractions (about 2 column volumes) is used for Evaporated to dryness and gives 13.0 mg of an oil which recrystallizes from acetone-petroleum ether will. 5.5 mg of 2a-methyl-9a-fluoro-4-pregnen-11ß, 16a, 17a, 21-tetraol-3,20-dione-16a, 21-diacetate (XII), mp = 140 to 200 ° C. A crystallization from acetone-petroleum ether provides 3.0 mg of substance with an unchanged melting point. The ketol test with tetrazolium blue is positive. A spot appears on the paper chromatogram.
Analyse: C26Ha20sF (491,52). Berechnet ... F 3,87; gefunden..... F 4,47.Analysis: C26Ha20sF (491.52). Calculated ... F 3.87; found ..... F 4.47.
Durch Verseifen von 2-Methyl-9a-fluor-4-pregnenllß, 16a,17a, 21-tetraol-3,20-dion-16a,21-diacetat mit Natrium- oder Kaliumhydroxyd erhält man 2a-Methyl-9a-fluor-4-pregnen-llß,16a,17a, 21-tetraol-3,20-dion. F. =228,5 bis 231°C; @m",x 237 bis 238 m#t; 8 = 15300; [a]ä5 105° (Pyridin); IRma."3,380; 1,712; 1,660 und 1,633 cm-r.By saponifying 2-methyl-9a-fluoro-4-pregnenllß, 16a, 17a, 21-tetraol-3,20-dione-16a, 21-diacetate with sodium or potassium hydroxide, 2a-methyl-9a-fluoro-4 is obtained -pregnen-llß, 16a, 17a, 21-tetraol-3,20-dione. M.p. = 228.5 to 231 ° C; @m ", x 237 to 238 m # t; 8 = 15300; [a] - 5 105 ° (pyridine); IRma."3.380;1.712; 1.660 and 1.633 cm r.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1091565XA | 1956-08-24 | 1956-08-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1091565B true DE1091565B (en) | 1960-10-27 |
Family
ID=22326102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEA27771A Pending DE1091565B (en) | 1956-08-24 | 1957-08-23 | Process for the preparation of 2ª ‡ -Methyl-9ª ‡ -fluoro-4-pregnene derivatives |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1091565B (en) |
-
1957
- 1957-08-23 DE DEA27771A patent/DE1091565B/en active Pending
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