CH333079A - Process for the preparation of 11-epi-corticosterone acetate - Google Patents
Process for the preparation of 11-epi-corticosterone acetateInfo
- Publication number
- CH333079A CH333079A CH333079DA CH333079A CH 333079 A CH333079 A CH 333079A CH 333079D A CH333079D A CH 333079DA CH 333079 A CH333079 A CH 333079A
- Authority
- CH
- Switzerland
- Prior art keywords
- epi
- ether
- acetate
- progesterone
- preparation
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 8
- 229960003387 progesterone Drugs 0.000 claims description 6
- 239000000186 progesterone Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 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 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000003776 cleavage reaction Methods 0.000 claims description 3
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 claims description 3
- 230000007017 scission Effects 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- RJKFOVLPORLFTN-LEKSSAKUSA-N Progesterone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 RJKFOVLPORLFTN-LEKSSAKUSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000026045 iodination Effects 0.000 description 2
- 238000006192 iodination reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 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
- 229960004544 cortisone Drugs 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 description 1
- HWJHWSBFPPPIPD-UHFFFAOYSA-N ethoxyethane;propan-2-one Chemical compound CC(C)=O.CCOCC HWJHWSBFPPPIPD-UHFFFAOYSA-N 0.000 description 1
- 210000002837 heart atrium Anatomy 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- -1 oxalic acid diester Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 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
-
- 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 11-epi-Corticosteronacetat Gegenstand des Hauptpatentes ist ein Ver fahren zur Herstellung von Desoxvcortico- steronaeetat, das dadurch gekennzeichnet ist, dass man Progesteron in Gegenwart eines Na- triumalkoholates mit einem Oxalsäurediester in 21-Stellung kondensiert, auf das erhaltene Progesteron - 21- oxalesternatriumenolat Jod einwirken lässt,
das Jodierungsprodukt einer Säurespaltung unterwirft und das gewonnene 21-Jod-progesteron mit Kaliumaeetat umsetzt.
Gegenstand der vorliegenden Erfindung ist. ein Verfahren zur Herstellung von 11-epi- Corticosteronaceta.t, das dadurch gekennzeich net ist, dass man 11-a-Oxy-progesteron in Gegenwart eines -2\atriumalkoholates mit. Oxal- säurediäthylester in 21-Stellung kondensiert.
auf das erhaltene 11-a-Oxy-progesteron-21.- oxalesterna.triumenolat Jod einwirken lässt, das Jodierungsprodukt einer Säurespaltung unterwirft und die erhaltene 21.-Jodverbin- dung mit Kaliumacetat umsetzt.
Das nach der Erfindung erhaltene 11-epi- Corticosteronacetat ist eine beispielsweise aus dem Werk von Fieser und Fieser Natural. produets related to phenanthrene , New York (19.10), Seite 109, bekannte Verbindung und stellt ein wertvolles Zwischenprodukt zur Her stellung pharmazeutisch wichtiger Verbin dungen, beispielsweise von Cortison, dar.
<I>Beispiel</I> Eine Lösung von 103 mg Natrium in 1,3 cm3 absolutem Methanol wird zu 7,5 cm3 Benzol und 0,2 cm-3 Äthanol zuigefügt,, die Mischung auf 213 des Gesamtvolumens einge engt und mit 0,89 em3 Oxalsäurediäthylester versetzt. Zu der klaren, gelben Lösung gibt man 1,26 g 11-a-Oxy-progesteron in 15 cm3 absolutem Benzol. Es fällt sofort ein dichter gelber Niederschlag aus.
Nach 85 Minuten langem Rühren versetzt man mit 20 cm3 Äther, nach weiteren 60 Minuten mit weiteren 50 cm3 Äther. Der gelbe Natriumoxalester-Nieder- schlag wird abfiltriert, mit Äther gut ausge waschen und über Schwefelsäure getrocknet. Die Ausbeute beträgt 1,625 g.
Der Niederschlag ist leicht löslich in Ätha- nol und zeigt stark positive Eisenchlorid- reaktion. Aus der ätherischen Mutterlauge werden durch Verdampfen des Lösungsmittels 415 mg des Ausgangsmaterials zurückgewon nen.
1,62 g des erhaltenen 21-Oxalesternatrium- enolates werden bei -22 in 17 em3 absolu tem Methanol gelöst und, wie im Beispiel des Hauptpatentes beschrieben, mit 0,9 g Jod, ge löst. in 22 em3 absolutem Methanol, und 1,03 cm3 3,4n-Natrium-methylatlösung behan delt. Nach portionsweiser Zugabe von 120 cm3 Wasser versetzt man die erhaltene Emulsion mit 25 g Kochsalz, wobei sich ein flockiger Niederschlag abscheidet, der abfiltriert und mit Nasser gewaschen wird.
1,08 g des erhaltenen 21-Jodderivates wer den, wie im Beispiel des Hauptpatentes be schrieben, mit einer Mischung von 30 cm3 Wasser, 1,5 g wasserfreiem Kaliumacetat, 1,35 em3 Eisessig und 116 cm3 Aceton 5 Stun den zum Sieden erhitzt. Das nach dem Ver dampfen des Acetons zurüekbleibende gelbe öl wird nach dem Abdekantieren und Wa- sehen mit.
Wasser bei 30 im Vakuum getrock net, in etwa 10 cm3 Aceton aufgenommen, mit 40 em3 Äther versetzt und von den ausge schiedenen braunen Flocken abfiltriert. Nach abermaligem Eindampfen im Vakuum zur Trockne löst man das harzartige Rohprodukt in 7,5 cm3 Benzol, versetzt es mit 2,5 em3 Petroläther und absorbiert es an einer Säule aus 20 g saurem Aluminiumoxyd. Die Elution wird nacheinander mit Mischungen von Ben zol, Benzol mit 4' /o Äther, Benzol-Äther 2: 1, 1 :1, Äther-Aceton vorgenommen.
Die Eluate mit Benzol-Äther 2: 1 und Benzol-Äther 1 :1 werden vereinigt, das Lösungsmittelgemiseh abdestilliert und der Rückstand aus wenig Essigester-Äther-Gemisch (1 :1) durch An spritzen mit Petroläther umkristallisiert. Das erhaltene 11-epi-Corticosteronacetat besitzt einen Schmelzpunkt von 118 (korr.); (a)D = + 176 40 in Aceton.
Beim langsamen Sehnielzen la-ern sich die Kristalle in eine polymorphe Modifikation von) Schmelzpunkt 161 um. Sie stellt die stabile Modifikation dar und entsteht. auch in den meisten Fällen direkt beim Kristallisieren aus Lösungsmitteln, z. B. auch aus Essigester- Petroläther.
Zur Charakterisierung werden 60 in- des oben erhaltenen 11.-epi-Cortieosteronaeetats nach einer von Shoppee und Reichstein gege benen Vorschrift (Helvetiea Chiiniea Aeta Band 26, Seite 1316 [1943]) in Eisessig mit Chromtrioxy d oxydiert. Man erhält. 50 mg Dehvdro-eorticosteronacetat, das nach Um kristallisieren aus wenig Aeeton und Äther einen Schmelzpunkt von 182 (korr.) zeigt.
Process for the production of 11-epi-corticosterone acetate The subject of the main patent is a process for the production of Desoxvcortico- steronaeetat, which is characterized in that progesterone is condensed in the presence of a sodium alcoholate with an oxalic acid diester in the 21-position onto the progesterone obtained - 21- oxalester sodium enolate lets iodine act,
subjects the iodination product to acid cleavage and converts the 21-iodine-progesterone obtained with potassium acetate.
The subject of the present invention is. a process for the production of 11-epi- Corticosteronaceta.t, which is characterized in that one 11-a-oxy-progesterone in the presence of a -2 \ atrium alcoholate with. Oxalic acid diethyl ester condensed in the 21-position.
letting iodine act on the 11-α-oxy-progesterone-21-oxalesterna.trium enolate obtained, subjecting the iodination product to acid cleavage and converting the 21-iodine compound obtained with potassium acetate.
The 11-epi-corticosterone acetate obtained according to the invention is one, for example, from the work of Fieser and Fieser Natural. produets related to phenanthrene, New York (19.10), page 109, known compound and is a valuable intermediate for the production of pharmaceutically important compounds, for example cortisone.
<I> Example </I> A solution of 103 mg of sodium in 1.3 cm3 of absolute methanol is added to 7.5 cm3 of benzene and 0.2 cm-3 of ethanol. The mixture is concentrated to 213 of the total volume and marked with 0 89 cm3 of diethyl oxalate were added. 1.26 g of 11-a-oxy-progesterone in 15 cm3 of absolute benzene are added to the clear, yellow solution. A dense yellow precipitate immediately separates out.
After stirring for 85 minutes, 20 cm3 of ether are added, and after a further 60 minutes a further 50 cm3 of ether are added. The yellow sodium oxalate precipitate is filtered off, washed well with ether and dried over sulfuric acid. The yield is 1.625 g.
The precipitate is easily soluble in ethanol and shows a strongly positive iron chloride reaction. 415 mg of the starting material are recovered from the essential mother liquor by evaporation of the solvent.
1.62 g of the 21-oxalester sodium enolate obtained are dissolved in 17 em3 absolute methanol at -22 and, as described in the example of the main patent, dissolved with 0.9 g of iodine. treated in 22 em3 of absolute methanol and 1.03 cm3 of 3.4N sodium methylate solution. After adding 120 cm3 of water in portions, the emulsion obtained is mixed with 25 g of sodium chloride, a flocculent precipitate separating out, which is filtered off and washed with water.
1.08 g of the 21-iodine derivative obtained who, as described in the example of the main patent, are heated to boiling for 5 hours with a mixture of 30 cm3 of water, 1.5 g of anhydrous potassium acetate, 1.35 em3 of glacial acetic acid and 116 cm3 of acetone . The yellow oil that remains after the acetone has evaporated is also seen after decanting and washing.
Water dried at 30 in a vacuum, taken up in about 10 cm3 of acetone, mixed with 40 cm3 of ether and filtered off from the brown flakes which separated out. After repeated evaporation to dryness in vacuo, the resinous crude product is dissolved in 7.5 cm3 of benzene, 2.5 cm3 of petroleum ether is added and it is absorbed on a column of 20 g of acidic aluminum oxide. The elution is carried out successively with mixtures of benzene, benzene with 4% ether, benzene-ether 2: 1, 1: 1, ether-acetone.
The eluates with benzene-ether 2: 1 and benzene-ether 1: 1 are combined, the solvent mixture is distilled off and the residue is recrystallized from a little ethyl acetate-ether mixture (1: 1) by spraying with petroleum ether. The 11-epi-corticosterone acetate obtained has a melting point of 118 (corr.); (a) D = + 176 40 in acetone.
In the case of slow sehnielzen, the crystals transform into a polymorphic modification with a melting point of 161. It represents the stable modification and arises. also in most cases directly when crystallizing from solvents, e.g. B. also from ethyl acetate petroleum ether.
For characterization, 60 in of the 11th epi-Cortieosteronaeetats obtained above are oxidized in glacial acetic acid with chromium trioxide according to a procedure given by Shoppee and Reichstein (Helvetiea Chiiniea Aeta Volume 26, page 1316 [1943]). You get. 50 mg Dehvdro-eorticosterone acetate, which after crystallization from a little acetone and ether shows a melting point of 182 (corr.).
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE333079X | 1951-09-28 | ||
| CH310364T | 1952-09-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH333079A true CH333079A (en) | 1958-09-30 |
Family
ID=25735697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH333079D CH333079A (en) | 1951-09-28 | 1952-09-27 | Process for the preparation of 11-epi-corticosterone acetate |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH333079A (en) |
-
1952
- 1952-09-27 CH CH333079D patent/CH333079A/en unknown
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