DE1021844B - Process for the preparation of steroid ketone oil esters - Google Patents
Process for the preparation of steroid ketone oil estersInfo
- Publication number
- DE1021844B DE1021844B DEN12858A DEN0012858A DE1021844B DE 1021844 B DE1021844 B DE 1021844B DE N12858 A DEN12858 A DE N12858A DE N0012858 A DEN0012858 A DE N0012858A DE 1021844 B DE1021844 B DE 1021844B
- Authority
- DE
- Germany
- Prior art keywords
- preparation
- ketene
- oil esters
- steroid ketone
- steroid
- 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
- -1 steroid ketone Chemical class 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 8
- 150000002148 esters Chemical class 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 4
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 claims description 11
- 230000010933 acylation Effects 0.000 claims description 8
- 238000005917 acylation reaction Methods 0.000 claims description 8
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 7
- PESKGJQREUXSRR-UXIWKSIVSA-N 5alpha-cholestan-3-one Chemical compound C([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@H](C)CCCC(C)C)[C@@]2(C)CC1 PESKGJQREUXSRR-UXIWKSIVSA-N 0.000 description 6
- PESKGJQREUXSRR-UHFFFAOYSA-N 5beta-cholestanone Natural products C1CC2CC(=O)CCC2(C)C2C1C1CCC(C(C)CCCC(C)C)C1(C)CC2 PESKGJQREUXSRR-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NNMJHVBZUSISMC-GCGMMPITSA-N [(3r,8s,9s,10s,13s,14s,17s)-17-acetyl-10,13-dimethyl-11-oxo-1,2,3,4,5,6,7,8,9,12,14,15,16,17-tetradecahydrocyclopenta[a]phenanthren-3-yl] acetate Chemical compound C1C(=O)[C@@H]2[C@@]3(C)CC[C@@H](OC(=O)C)CC3CC[C@H]2[C@@H]2CC[C@H](C(C)=O)[C@]21C NNMJHVBZUSISMC-GCGMMPITSA-N 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 238000004816 paper chromatography Methods 0.000 description 2
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical class CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 2
- DUHUCHOQIDJXAT-ALVDYUIISA-N (8s,9s,10s,13s,14s,17s)-17-acetyl-3-hydroxy-10,13-dimethyl-1,2,3,4,5,6,7,8,9,12,14,15,16,17-tetradecahydrocyclopenta[a]phenanthren-11-one Chemical compound C1CC2CC(O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2=O DUHUCHOQIDJXAT-ALVDYUIISA-N 0.000 description 1
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- RSRDWHPVTMQUGZ-OZIWPBGVSA-N 1-[(8r,9s,10s,13s,14s,17s)-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]ethanone Chemical class C1CC2CCCC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 RSRDWHPVTMQUGZ-OZIWPBGVSA-N 0.000 description 1
- 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
- 229930194542 Keto Natural products 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- GFHOQCXDABGYAL-TXXKDTCUSA-N [(3R,8R,9S,10S,13S,14S,17S)-17-acetyl-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yl] acetate Chemical compound C(C)(=O)O[C@H]1CC2CC[C@H]3[C@@H]4CC[C@H](C(C)=O)[C@]4(CC[C@@H]3[C@]2(CC1)C)C GFHOQCXDABGYAL-TXXKDTCUSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229960004544 cortisone Drugs 0.000 description 1
- 150000001887 cortisones Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- NFDFQCUYFHCNBW-SCGPFSFSSA-N dienestrol Chemical compound C=1C=C(O)C=CC=1\C(=C/C)\C(=C\C)\C1=CC=C(O)C=C1 NFDFQCUYFHCNBW-SCGPFSFSSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- ZWOHWBKRLSTQLX-UHFFFAOYSA-N heptane;propane-1,2-diol Chemical compound CC(O)CO.CCCCCCC ZWOHWBKRLSTQLX-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 238000003786 synthesis reaction 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Steroid Compounds (AREA)
Description
Verfahren zur Darstellung von Steroidketonenolestern Die Erfindung bezieht sich auf ein Verfahren zur Darstellung von Steroidketonenolestern, insbesondere solcher von 20-Ketosteroiden.Method for the preparation of steroid ketone oil esters The invention relates to a method for the preparation of steroid ketone oil esters, in particular those of 20-keto steroids.
Bekanntlich kann man Enolacylierungen in Gegenwart eines Acylierungskatalysators in einem sehr großen 1Jberschuß des zur Acylierung verwendeten Carbonsäureanhydrids durchführen, wobei dieses langsam abdestilliert wird. Gemäß J. Am. Chem. Soc., 70, S. 1838 (1948), verwendet man 75 cm3 Essigsäureanhydrid zur Darstellung von Enolacetaten von 20-Ketopregnanderivaten auf 2 Millimol Keton.It is known that enol acylations can be carried out in the presence of an acylation catalyst in a very large excess of the carboxylic acid anhydride used for the acylation perform, this is slowly distilled off. According to J. Am. Chem. Soc., 70, S. 1838 (1948), 75 cm3 of acetic anhydride are used to prepare enol acetates of 20-ketopregnane derivatives to 2 millimoles of ketone.
Es wurde festgestellt, daß bei Veresterung mittels eines Säureanhydrids in Gegenwart eines Ketens bedeutend weniger Säureanhydrid erforderlich ist, um mindestens gleich gute Ergebnisse zu erzielen, wahrscheinlich weil das Keten die bei der Veresterung gebildete Carbonsäure wieder in das Säureanhydrid überführt.It was found that when esterified by means of an acid anhydride in the presence of a ketene, significantly less acid anhydride is required by at least achieve equally good results, probably because the ketene is involved in the esterification The carboxylic acid formed is converted back into the acid anhydride.
Erfindungsgemäß führt man die Enolveresterung eines Steroidketons mit einem Carbonsäureanhydrid und einem Acylierungskatalysator in Gegenwart eines Ketens im Reaktionsgemisch durch.According to the invention, the enol esterification of a steroid ketone is carried out with a carboxylic anhydride and an acylation catalyst in the presence of a Ketene in the reaction mixture.
Das Keten kann man auf verschiedene Weise in das Reaktionsgemisch einbringen, z. B. indem man es in Gasform einleitet. Man kann auch das Reaktionsgemisch unter Rückfluß kochen und ein Keten zu dem in dem Rückflußkühler gebildeten Kondensat geben, bevor man dieses in den Reaktionsraum zurückleitet, wodurch das Kondensat das Keten mit sich führt.The ketene can be added to the reaction mixture in various ways bring in, z. B. by introducing it in gaseous form. You can also use the reaction mixture reflux and add a ketene to the condensate formed in the reflux condenser give before this is fed back into the reaction chamber, creating the condensate that Keten carries with him.
Obwohl es im allgemeinen empfehlenswert ist, ein dem Anhydrid entsprechendes Keten zu verwenden, ist dies nicht notwendig, wenn der Enolester nur als Zwischenprodukt Bedeutung hat und in der Folge weiterverarbeitet wird, möglicherweise ohne vorher isoliert zu werden. In diesem Fall nämlich ist gegen die Bildung eines Gemisches verschiedener Ester nichts einzuwenden, die prinzipiell möglich ist, wenn man das Säureanhydrid mit einem nicht entsprechenden Keten regeneriert.Although it is generally advisable to use one equivalent to the anhydride To use ketene, this is not necessary if the enol ester is only an intermediate Has meaning and is subsequently processed, possibly without first to be isolated. In this case it is against the formation of a mixture different esters, which is possible in principle if you do that Acid anhydride regenerated with an unsuitable ketene.
Die Acylierung nach der Erfindung kann man grundsätzlich mit jedem Carbonsäureanhydrid durchführen. Vorzugsweise verwendet man Essigsäureanhydrid.The acylation according to the invention can in principle with anyone Carboxylic acid anhydride carry out. Acetic anhydride is preferably used.
Geeignete Acylierungskatalysatoren sind z. B. Chlorwasserstoffsäure, Schwefelsäure, p-Toluolsulfonsäure, Überchlorsäure oder N atriumacetat.Suitable acylation catalysts are, for. B. hydrochloric acid, Sulfuric acid, p-toluenesulfonic acid, hyperchloric acid or sodium acetate.
Das Verfahren nach der Erfindung besitzt besondere Bedeutung für die Bildung von Enolestern von 20-Ketosteroiden. Beispiele von Ketosteroiden, die man erfindungsgemäß mit hoher Ausbeute unter Verwendung einer verhältnismäßig geringen Menge von Säureanhydrid acylieren kann, sind 3a-Acetoxy-11,20-diketopregnan, 3ß-Acetoxy-5,6-dichlor-20-ketopregnan, 3a-Acetoxy-20-ketopregnan, 3ß Acetoxy-20-ketoallopregnan, Cholestanon und Coprostanon.The method according to the invention has particular importance for Formation of enol esters of 20-keto steroids. Examples of keto steroids that you can according to the invention with high yield using a relatively low one Amount of acid anhydride that can acylate are 3a-acetoxy-11,20-diketopregnan, 3ß-acetoxy-5,6-dichloro-20-ketopregnan, 3a-acetoxy-20-ketopregnan, 3ß-acetoxy-20-ketoallopregnan, cholestanone and coprostanone.
Insbesondere besitzt die Acetylierung von 3a-Acetoxy-11,20-diketopregnan für die Synthese von Cortison und Cortisonestern große Bedeutung.In particular, the acetylation of 3a-acetoxy-11,20-diketopregnane possesses of great importance for the synthesis of cortisone and cortisone esters.
Aus J. Am. Chem. Soc., 74, S. 485 (1952), ist die Darstellung von 3a,17a-Dihydroxypregnan-11,20-dion durch Triacetylierung von 3-Hydroxy-11,20-diketopregnan in Gegenwart von p-Toluolsulfonsäure unter Bildung von do(ll),1'(2°)-Pregnadien-3a,11,20-triol-triacetat, Umwandlung dieses Triacetats mit einer Persäure in 17a(20)-Epoxy-d 9(11)-pregnen-3a,11,20-triol-triacetat und schließlich Verseifen dieser Verbindung bekannt. Die Ausbeute dieses dreistufigen Verfahrens beträgt nur etwa 700/,.From J. Am. Chem. Soc., 74, p. 485 (1952) is the representation of 3a, 17a-dihydroxypregnane-11,20-dione by triacetylation of 3-hydroxy-11,20-diketopregnane in the presence of p-toluenesulfonic acid with formation of do (II), 1 '(2 °) -Pregnadiene-3a, 11,20-triol-triacetate, Conversion of this triacetate with a peracid into 17a (20) -epoxy-d 9 (11) -pregnen-3a, 11,20-triol-triacetate and finally saponifying this compound known. The yield of this three-stage Procedure is only about 700 / ,.
Erfindungsgemäß ist es nun gelungen, diese Ausbeute auf etwa 850/, zu erhöhen, indem man die Acetylierung in Gegenwart von Keten vornimmt, wobei man nur 5 kg Essigsäureanhydrid auf 1 kg Steroid und eine entsprechend geringere Menge p-Toluolsulfonsäure verwendet.According to the invention, it has now been possible to increase this yield to about 850 % by carrying out the acetylation in the presence of ketene, using only 5 kg of acetic anhydride per 1 kg of steroid and a correspondingly smaller amount of p-toluenesulfonic acid.
Beispiel 1 100 g 3a-Acetoxy-11,20-diketopregiian und 5 g p-Toluolsulfonsäure «erden in 500 cm3 Essigsäureanhydrid gelöst, und das Reaktionsgemisch wird zum Sieden gebracht. Nach etwa 5stündigem Kochen am Rückfluß, während dem ein Strom von etwa 7 1 Keten je Stunde durch das Reaktionsgemisch geleitet wird, ist die Umsetzung vollständig. Das abgekühlte Reaktionsgemisch wird in 2,5 1 Eiswasser gegossen, mit Chloroform extrahiert und der Extrakt mit verdünnter Natriumbicarbonatlösung und Wasser bis zur neutralen Reaktion gewaschen. Nach Verdampfen des Lösungsmittels im Vakuum kann das rohe 4.9(11)17-3a,11,20-Triacetoxytripregnadien weiter zu dem 3a,17a-Dihydroxy-3,11-diketcipregnan verarbeitet werden. In dem rohen A9(I1)11-3a, 11,20-Triacetoxypregnadien kann man mittels Papierchromatographie (Propylenglykol-Heptan) kein Ausgangsmaterial nachweisen, was darauf hindeutet, daß die Umsetzung praktisch quantitativ erfolgt ist. Das reine Dienol-Triacetat kann man aus dem Rohprodukt nach Entfärben mit A120.. und Umkristallisieren aus Essigsäureäthylester isolieren. Schmelzpunkt 199 bis 201'; Via] D = -I- 105°.Example 1 100 g of 3a-acetoxy-11,20-diketopregiian and 5 g of p-toluenesulfonic acid are dissolved in 500 cm3 of acetic anhydride, and the reaction mixture is brought to the boil. After refluxing for about 5 hours, during which a current of about 7 liters of ketene per hour is passed through the reaction mixture, the reaction is complete. The cooled reaction mixture is poured into 2.5 l of ice water, extracted with chloroform and the extract is washed with dilute sodium bicarbonate solution and water until it reacts neutral. After evaporation of the solvent in vacuo, the crude 4.9 (11) 17-3a, 11,20-triacetoxytripregnadiene can be further processed to the 3a, 17a-dihydroxy-3,11-diketcipregnan. No starting material can be detected in the crude A9 (I1) 11-3a, 11,20-triacetoxypregnadiene by means of paper chromatography (propylene glycol heptane), which indicates that the reaction has taken place practically quantitatively. The pure dienol triacetate can be isolated from the crude product after decolorization with A120 .. and recrystallization from ethyl acetate. Melting point 199 to 201 '; Via] D = -I- 105 °.
Beispiel 2 10 g 3ß-Acetoxy-5,6-dichlor-20-ketopregnan werden in 50 cm3 Essigsäureanhydrid gelöst. Nach Zugabe von 0,5 g p-Toluolsulfonsäure erwärmt man das Reaktionsgemisch auf 20' und leitet etwa 1 1 Keten je Stunde hindurch. Nach 5 Stunden ist die Reaktion vollständig, was mittels Papierchromatographie festgestellt wird. Das Verfahren wird, wie im Beispiel 1 beschrieben, durchgeführt. Das reine d 17-3ß,20-Diacetoxy-5,6-dichlorpregnen schmilzt bei etwa 155'.Example 2 10 g of 3β-acetoxy-5,6-dichloro-20-ketopregnane are in 50 cm3 of acetic anhydride dissolved. After adding 0.5 g of p-toluenesulfonic acid, it is heated the reaction mixture is reduced to 20 'and about 1 1 ketene is passed through it per hour. To The reaction is complete in 5 hours, which was determined by means of paper chromatography will. The procedure is as described in Example 1, carried out. The pure d 17-3β, 20-diacetoxy-5,6-dichloropregnene melts at about 155 '.
In gleicher Weise wurden die Enolacetate von Cholestanon und Coprostanon dargestellt.In the same way, the enol acetates were made by cholestanone and coprostanone shown.
Das sich ergebende Enolacetat von Cholestanon schmilzt bei 89 bis 90' und hat eine spezifische Drehung von @al-D = -!- 5 7 . Das entstandene Enolacetat von Coprostanon schmilzt bei 80 bis 82° und hat eine spezifische Drehung von ja] n =- -i-- 37°.The resulting enol acetate of cholestanone melts at 89 to 90 'and has a specific rotation of @ al-D = -! - 5 7 . The resulting enol acetate of coprostanone melts at 80 to 82 ° and has a specific rotation of ja] n = - -i-- 37 °.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1021844X | 1955-10-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1021844B true DE1021844B (en) | 1958-01-02 |
Family
ID=19867139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEN12858A Pending DE1021844B (en) | 1955-10-20 | 1956-10-19 | Process for the preparation of steroid ketone oil esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1021844B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9446719B2 (en) | 2014-11-19 | 2016-09-20 | Hon Hai Precision Industry Co., Ltd. | Holder for mobile device and vehicle seat employing same |
-
1956
- 1956-10-19 DE DEN12858A patent/DE1021844B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9446719B2 (en) | 2014-11-19 | 2016-09-20 | Hon Hai Precision Industry Co., Ltd. | Holder for mobile device and vehicle seat employing same |
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