DE1297604B - Process for the preparation of delta 4, 16-pregnadien-20-ol-3-one - Google Patents
Process for the preparation of delta 4, 16-pregnadien-20-ol-3-oneInfo
- Publication number
- DE1297604B DE1297604B DESCH35728A DESC035728A DE1297604B DE 1297604 B DE1297604 B DE 1297604B DE SCH35728 A DESCH35728 A DE SCH35728A DE SC035728 A DESC035728 A DE SC035728A DE 1297604 B DE1297604 B DE 1297604B
- Authority
- DE
- Germany
- Prior art keywords
- pregnen
- pregnadien
- iso
- preparation
- iodine
- 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
- 238000002360 preparation method Methods 0.000 title claims description 5
- HLTFEHHQTSKBRU-VGEGYJBVSA-N (8r,9s,10r,13s,14s)-17-(1-hydroxyethyl)-10,13-dimethyl-1,2,6,7,8,9,11,12,14,15-decahydrocyclopenta[a]phenanthren-3-one Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC=C(C(O)C)[C@@]1(C)CC2 HLTFEHHQTSKBRU-VGEGYJBVSA-N 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Substances [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- AYGFEWYXKDFVIQ-NWSAAYAGSA-N pregn-4-en-3-one Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](CC)[C@@]1(C)CC2 AYGFEWYXKDFVIQ-NWSAAYAGSA-N 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 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 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- OILXMJHPFNGGTO-UHFFFAOYSA-N (22E)-(24xi)-24-methylcholesta-5,22-dien-3beta-ol Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(C)C(C)C)C1(C)CC2 OILXMJHPFNGGTO-UHFFFAOYSA-N 0.000 description 1
- RQOCXCFLRBRBCS-UHFFFAOYSA-N (22E)-cholesta-5,7,22-trien-3beta-ol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CCC(C)C)CCC33)C)C3=CC=C21 RQOCXCFLRBRBCS-UHFFFAOYSA-N 0.000 description 1
- VRRHHTISESGZFN-RKFFNLMFSA-N 16,17-didehydroprogesterone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC=C(C(=O)C)[C@@]1(C)CC2 VRRHHTISESGZFN-RKFFNLMFSA-N 0.000 description 1
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- OQMZNAMGEHIHNN-UHFFFAOYSA-N 7-Dehydrostigmasterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CC(CC)C(C)C)CCC33)C)C3=CC=C21 OQMZNAMGEHIHNN-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DNVPQKQSNYMLRS-NXVQYWJNSA-N Ergosterol Natural products CC(C)[C@@H](C)C=C[C@H](C)[C@H]1CC[C@H]2C3=CC=C4C[C@@H](O)CC[C@]4(C)[C@@H]3CC[C@]12C DNVPQKQSNYMLRS-NXVQYWJNSA-N 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- DNVPQKQSNYMLRS-SOWFXMKYSA-N ergosterol Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H](CC[C@]3([C@H]([C@H](C)/C=C/[C@@H](C)C(C)C)CC[C@H]33)C)C3=CC=C21 DNVPQKQSNYMLRS-SOWFXMKYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000003944 halohydrins Chemical class 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Steroid Compounds (AREA)
Description
Die vorliegende Erfindung betrifft ein besonders vorteilhaftes Verfahren zur Herstellung von zl4'16-Pregnadien-20-ol-3-on, dadurch gekennzeichnet, daß man den Oxidoring in 17,20-Oxido-zl4-pregnen-3-on mit Jodwasserstoffsäure spaltet und das erhaltene Πβ-Jod-/J4-17-iso-pregnen-20-ol-3-on mit einem niederen Alkohol, insbesondere Methanol, gegebenenfalls in Gegenwart basischer Reagenzien, insbesondere von Alkali- oder Erdalkalihydroxyden oder von Kalium-, Natrium- oder Ammoniumacetat, umsetzt.The present invention relates to a particularly advantageous process for the preparation of zl 4 '16 -pregnadien-20-ol-3-one, characterized in that the oxidizing ring is converted into 17,20-oxido-zl 4 -pregnen-3-one with hydroiodic acid cleaves and the Πβ-iodine / I 4 -17-iso-pregnen-20-ol-3-one obtained with a lower alcohol, in particular methanol, optionally in the presence of basic reagents, in particular of alkali or alkaline earth metal hydroxides or of potassium, Sodium or ammonium acetate.
Das erfindungsgemäße Verfahren ist also durch folgendes Reaktionsschema charakterisiert:The process according to the invention is thus characterized by the following reaction scheme:
Das erfindungsgemäß als Ausgangsverbindung eingesetzte 17,20-Oxido-zJ*-pregnen-3-on (I) ist an sich bekannt. Auf Grund der Untersuchungen von L. Ruzicka (HeIv. 25, 1680/1942) ist weiter bekannt, daß diese Verbindung I gegen saure Reagenzien äußerst empfindlich ist. So lagert I beispielsweise in essigsaurer Lösung zu Π fr- Methyl -18- nor- <d4-13(14)-17a-pregnadien-20-ol-3-on um. Auf Grund ergänzender eigener Versuche wurde festgestellt, daß die beschriebene Umlagerung auch mit anderen Säuren, wie beispielsweise p-Toluolsulfonsäure, Schwefelsäure und Dimethylsulfoxyd, stattfindet. Es war somit nicht voraussehbar, daß sich 17,20-Oxidozd4-pregnen-3-on durch Spaltung des 17,20-Oxidoringes mit Jodwasserstoffsäure in das bisher nicht beschriebene Π β - Jod - J4 -17 - iso - pregnen - 20 - ol-3-on (II) überführen läßt.The 17,20-oxido-zJ * -pregnen-3-one (I) used according to the invention as the starting compound is known per se. On the basis of the investigations by L. Ruzicka (HeIv. 25, 1680/1942) it is also known that this compound I is extremely sensitive to acidic reagents. For example, I rearranges in acetic acid solution to Π fr- methyl -18- nor- <d 4 - 13 (14) -17a-pregnadien-20-ol-3-one. On the basis of additional own experiments it was found that the described rearrangement also takes place with other acids such as p-toluenesulfonic acid, sulfuric acid and dimethyl sulfoxide. It was therefore not foreseeable that 17,20-Oxidozd 4 -pregnen-3-one would result in splitting of the 17,20-Oxidoringes with hydriodic acid into the previously unknown Π β - iodine - I 4 -17 - iso - 20 - Can transfer ol-3-one (II).
Die Weiterverarbeitung von II zu d4ll6-Pregnadien-20-ol-3-on erfolgt vorzugsweise in einem niederen Alkohol, ζ. Β. Methanol. Schon durch bloßes Stehenlassen bei Raumtemperatur erfolgt die Eliminierung des 17-Jodatoms als HJ unter Bildung der entsprechenden d16-Verbindung (III). Die Umsetzung kann durch Erhöhen der Reaktionstemperatur und/ oder durch Zusatz solcher Reagenzien, die dem Fachmann zur Epoxyringbildung aus Halogenhydrinen als geeignet bekannt sind, wie z. B. Alkali- oder Erdalkalihydroxyde oder deren Salze oder Kaliumacetat, Ammoniumacetat oder Aluminiumoxyd, beschleunigt werden.The further processing of II to d 4ll6 -pregnadien-20-ol-3-one is preferably carried out in a lower alcohol, ζ. Β. Methanol. Simply by leaving it to stand at room temperature, the 17-iodine atom is eliminated as HJ with the formation of the corresponding d 16 compound (III). The reaction can be carried out by increasing the reaction temperature and / or by adding such reagents which are known to the person skilled in the art to be suitable for forming epoxy rings from halohydrins, such as, for. B. alkali or alkaline earth metal hydroxides or their salts or potassium acetate, ammonium acetate or aluminum oxide, are accelerated.
Die Umsetzung II —> III gemäß oben gekennzeichnetem Reaktionsschema war ebenfalls überraschend, nachdem durch N. L. Wendler (Tetrahedron 3,144 [1958]) bekannt ist, daß 17-Brom-20-olsteroide durch Behandlung mit Alkali in 17,20-Oxidosteroide übergeführt werden.The implementation II -> III according to the reaction scheme indicated above was also surprising, after it is known by N. L. Wendler (Tetrahedron 3,144 [1958]) that 17-bromo-20-olsteroide by treatment with alkali into 17,20-oxidosteroids be transferred.
In dem erfindungsgemäßen Verfahren sind, wie oben dargelegt, auch die einzelnen Stufen erfinderisch, weshalb für die Stufen I —* II und II —> III Elementenschutz beansprucht wird.In the process according to the invention, as set out above, the individual stages are also inventive, which is why element protection is claimed for stages I - * II and II -> III.
Das für das erfindungsgemäße Verfahren als Ausgangsprodukt benutzte 17,20 - Oxido - Δ4 - pregnen-3 - on (I) wurde bisher aus der entsprechenden ΑίΊ(20)-Verbindung nach an sich bekannten Methoden hergestellt, wobei die erzielte Ausbeute jedoch unbefriedigend ist, weil die gleichfalls anwesende konjugierte ^-Doppelbindung, insbesondere bei Anwendung eines Überschusses an Epoxydierungsreagenz, z. B. Monoperphthalsäure oder Benzoepersäure, in mehr oder minder starkem Maße ebenfalls epoxydiert wird. Nachdem kürzlich vorgeschlagen wurde, die gewünschte 17(20)-Epoxydierung besonders vorteilhaft mittels m - Chlorperbenzoesäure durchzuführen, weil dieses Reagenz die zl17(20)-Doppelbindung selektiv in praktisch quantitativer Ausbeute epoxydiert, besitzt das vorliegende erfindungsgemäße Verfahren besonderes technisches Interesse, weil es somit möglich wird, z. B. Ergosterinabbauprodukte, wie ./J4-3-Keto-bisnorcholensäure, über die entsprechenden 20 - Halogen-, 17,20 - en - Verbindungen, das 17,20-Epoxyd I und unter Mitbenutzung des erfindungsgemäßen Verfahrens in einfacher Weise in das erfindungsgemäß herstellbare zJ4>16-Pregnadien-20-ol-3-on zu überführen. Letzteres dient schließlich als Ausgangsprodukt zur Darstellung von z.B. 16-Dehydroprogesteron, das seinerseits bekanntermaßen ein wichtiges Ausgangsprodukt zur Partialsynthese von wirksamen Hormonsubstanzen, z. B. 17a-Hyrlroxy-progesteron und deren Ester, ist. The 17,20 - oxido - Δ 4 - pregnen-3 - one (I) used as starting material for the process according to the invention was previously prepared from the corresponding Α ίΊ (20) - compound by methods known per se, but the yield achieved was unsatisfactory is because the conjugated ^ double bond also present, especially when using an excess of epoxidation reagent, e.g. B. monoperphthalic acid or benzoic acid, is also epoxidized to a greater or lesser extent. After it was recently proposed to carry out the desired 17 (20) -epoxidation particularly advantageously by means of m-chloroperbenzoic acid, because this reagent epoxidizes the zl 17 (20) double bond selectively in practically quantitative yield, the present process according to the invention is of particular technical interest because it thus becomes possible, e.g. B. ergosterol degradation products, such as ./J 4 -3-keto-bisnorcholenic acid, via the corresponding 20 - halogen, 17.20 - en - compounds, the 17,20-epoxide I and using the method according to the invention in a simple manner in the zJ 4> 16 -pregnadien-20-ol-3-one which can be prepared according to the invention. The latter ultimately serves as the starting product for the preparation of, for example, 16-dehydroprogesterone, which in turn is known to be an important starting product for the partial synthesis of active hormone substances, e.g. B. 17a-Hyrlroxy-progesteron and its esters.
Für die Herstellung des Ausgangsmaterials wird im Rahmen der vorliegenden Erfindung Schutz nicht begehrt.For the production of the starting material, protection is not given in the context of the present invention desired.
17,20-Oxido-,d4-pregnen-3-on wird in 500 ml Tetrahydrofuran bei 00C unter Stickstoffatmosphäre und Rühren gelöst. Innerhalb von 30 Minuten werden 14,3 g konstant siedende Jodwasserstoffsäure hinzugetropft und die Lösung noch weitere 30 Minuten bei 00C gerührt. Danach wird die Reaktionslösung in 1500 ml Eiswasser eingegossen. Die dabei ausgefallene und abgetrennte Substanz besteht aus einem Gemisch von 17/J-Jod-J4-17-iso-pregnen-20-ol-3-on und zl4>16-Pregnadien-20-ol-3-on. Das mit Wasser gewaschene und getrocknete Substanzgemisch wird in 250 ml Methanol gelöst, mit 20 g Kaliumacetat versetzt und über Nacht bei Raumtemperatur gerührt. Die Reaktionslösung wird in 2500 ml Eiswasser eingetragen und der dabei gebildete Niederschlag abfiltriert, gewaschen und getrocknet. Man erhält so 18,6 g zl4>16-Pregnadien-20-ol-3-on, das nach Umkristallisieren aus Aceton bei 186 bis 188° C schmilzt.17,20-oxido, d 4 -pregnen-3-one is dissolved in 500 ml of tetrahydrofuran at 0 0 C under nitrogen atmosphere and stirring. 14.3 g of constant-boiling hydriodic acid are added dropwise over the course of 30 minutes and the solution is stirred at 0 ° C. for a further 30 minutes. The reaction solution is then poured into 1500 ml of ice water. The substance precipitated and separated off consists of a mixture of 17 / I-iodine-I 4 -17-iso-pregnen-20-ol-3-one and zl 4> 16 -pregnadien-20-ol-3-one. The substance mixture, washed with water and dried, is dissolved in 250 ml of methanol, mixed with 20 g of potassium acetate and stirred overnight at room temperature. The reaction solution is introduced into 2500 ml of ice water and the precipitate formed is filtered off, washed and dried. This gives 18.6 g of 4> 16 -pregnadien-20-ol-3-one which, after recrystallization from acetone, melts at 186 to 188.degree.
14,3 g 17y3-Jod-/d4-17-iso-pregnen-20-ol-3-on im Gemisch mit J446-Pregnadien-20-ol-3-on, hergestellt, wie im Beispiel 1 beschrieben, werden in 200 ml14.3 g of 17y3-iodine / d 4 -17-iso-pregnen-20-ol-3-one in a mixture with J 446 -pregnadien-20-ol-3-one, prepared as described in Example 1 in 200 ml
Butanöl gelöst und 1 Stunde erhitzt. Danach wird die Reaktionslösung im Vakuum eingeengt. Man erhält 11,8 g zl446-Pregnadien-20-ol-3-on, das nach Umkristallisieren aus Aceton bei 186 bis 188° C schmilzt.Dissolved butane oil and heated for 1 hour. The reaction solution is then concentrated in vacuo. 11.8 g of zl 446- Pregnadien-20-ol-3-one are obtained, which, after recrystallization from acetone, melts at 186 to 188 ° C.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DESCH35728A DE1297604B (en) | 1964-09-03 | 1964-09-03 | Process for the preparation of delta 4, 16-pregnadien-20-ol-3-one |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DESCH35728A DE1297604B (en) | 1964-09-03 | 1964-09-03 | Process for the preparation of delta 4, 16-pregnadien-20-ol-3-one |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1297604B true DE1297604B (en) | 1969-06-19 |
Family
ID=7433603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DESCH35728A Pending DE1297604B (en) | 1964-09-03 | 1964-09-03 | Process for the preparation of delta 4, 16-pregnadien-20-ol-3-one |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1297604B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4189430A (en) * | 1978-07-31 | 1980-02-19 | The Upjohn Company | Epoxide process |
-
1964
- 1964-09-03 DE DESCH35728A patent/DE1297604B/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4189430A (en) * | 1978-07-31 | 1980-02-19 | The Upjohn Company | Epoxide process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1297604B (en) | Process for the preparation of delta 4, 16-pregnadien-20-ol-3-one | |
| DE2110140C3 (en) | ||
| DE2256911C2 (en) | Digoxigenin-12 formate and process for its preparation | |
| DE1618808B1 (en) | Process for the preparation of the 10,11-lactone 5, the 3-ethylene dioxy-11Beta, 17Alfa-dihydroxy-20-oxo-19-nor-Delta5-pregnen-10Beta-carboxylic acid | |
| DD160418A1 (en) | PROCESS FOR PREPARING 17ALPHA SUBSTITUTED GONA-4,9-DIENES | |
| DE1120447B (en) | Process for the preparation of 17ª-oxy-16-methylenepregn-4-en-3, 20-dione or its acyl derivatives | |
| DE1643028C3 (en) | New 1,2 alpha -methylene steroids, processes for their production and agents containing them | |
| AT220298B (en) | Process for the production of new 6β-methyl-3-oxo-Δ <4> -steroids | |
| AT253138B (en) | Process for the preparation of 19-nor-steroid compounds | |
| DE1468894C3 (en) | Process for the preparation of optically active 3-oxo-i 3beta-ethyl-17beta-hydroxy-17alpha-ethinyl-5 (10) gonen or 3-oxo-i 3beta-ethyl-17betahydroxy-17alpha-äthinyl-4-gonen | |
| DE870694C (en) | Process for the preparation of 17-ethynyl compounds of the androstane series and their stereoisomers | |
| DE1129481B (en) | Process for preparing 17ª‡-oxy-6ª‡-methyl-16-methylenepregn-4-ene-3,20-dione or its acyl derivatives | |
| DE1468887B1 (en) | Process for the production of delta? -20-oximido-steroids of the pregnancy series | |
| DE2011559B2 (en) | PROCESS FOR THE PREPARATION OF 9ALPHA-CHLORINE-11BETA-HYDROXYSTEROIDS | |
| DE1134986B (en) | Process for the production of cyclic 16 alpha, 17 alpha acetals and ketals of the 6 alpha-methylpregnane series. | |
| DE1186056B (en) | Process for the production of 19-nor-steroids | |
| DE1161267B (en) | Process for the preparation of 17ª ‡ -Aethynyl-17ª ‰ -hydroxy-3, 6-dioxo-A-nor-B-homo-5ªš, 10ªš-oestrane or its enolic forms | |
| DE1030340B (en) | Process for the preparation of in 2-oxy-3-ketosteroids | |
| DE1136331B (en) | Process for the production of 4-chloro- or 4-bromine í¸-3-ketones of the androstane or pregnane series | |
| DE1094258B (en) | Process for the preparation of fluorinated 16-methyl steroids | |
| DE1272289B (en) | Process for the preparation of 19-hydroxy-androst-4-en-3, 17-dione | |
| DE1148547B (en) | Process for the preparation of 16ª ‡ -Methylpregnan-3 ª ‡ -ol-11, 20-dione-3-acetate or. its 3-alcohol | |
| DE1142362B (en) | Process for the preparation of enol acylates of 16ª ‡ -alkyl-20-ketosteroids of the pregnan and allopregnan series | |
| DE1251757B (en) | Process for the production of 3 keto-zl5 (10) 19 nor 9/6 on drosten or pregnancies | |
| DE1036853B (en) | Process for the preparation of pregnane compounds unsaturated in the 14-position |