DE1129952B - Process for the preparation of 3 ª ‡ -acetoxy-20ªŠ-hydroperoxy-20-methoxy-pregnan-11-one - Google Patents
Process for the preparation of 3 ª ‡ -acetoxy-20ªŠ-hydroperoxy-20-methoxy-pregnan-11-oneInfo
- Publication number
- DE1129952B DE1129952B DEL35609A DEL0035609A DE1129952B DE 1129952 B DE1129952 B DE 1129952B DE L35609 A DEL35609 A DE L35609A DE L0035609 A DEL0035609 A DE L0035609A DE 1129952 B DE1129952 B DE 1129952B
- Authority
- DE
- Germany
- Prior art keywords
- acetoxy
- hydroperoxy
- pregnan
- compound
- methoxy
- 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 10
- 238000002360 preparation method Methods 0.000 title description 6
- 150000001875 compounds Chemical class 0.000 claims description 10
- -1 20-methylene-3a-acetoxy-pregnan-11-one Chemical compound 0.000 claims description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- CGRJOQDFNTYSGH-UHFFFAOYSA-N tritylphosphane Chemical class C=1C=CC=CC=1C(C=1C=CC=CC=1)(P)C1=CC=CC=C1 CGRJOQDFNTYSGH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005949 ozonolysis reaction Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- YSULOORXQBDPCU-UHFFFAOYSA-N 2-(trimethylazaniumyl)ethanehydrazonate;hydrochloride Chemical compound [Cl-].C[N+](C)(C)CC(=O)NN YSULOORXQBDPCU-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001867 hydroperoxy group Chemical group [*]OO[H] 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000003285 pharmacodynamic effect Effects 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 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
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ADZJWYULTMTLQZ-UHFFFAOYSA-N tritylphosphane;hydrobromide Chemical compound [Br-].C=1C=CC=CC=1C(C=1C=CC=CC=1)([PH3+])C1=CC=CC=C1 ADZJWYULTMTLQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Steroid Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von 3 a-Acetoxy-20 s-hydroperoxy-20-methoxy-pregnan-11-on Die Erfindung betrifft ein Verfahren zur Herstellung des 3x-Acetoxy-ll-keto-20e-hydroperoxy-20-methoxypregnans der nachstehend angegebenen Formel III. Diese Hydroxyperoxysteroidverbindung kann nach dem von Rieche und Schmitz (Chem. Berichte, Bd. 90 [1957], S. 1099) angegebenen Verfahren in das Bishydroperoxyd von 3a-Acetoxypregnan-11,20-dion umgewandelt werden. Diese Verbindung hat sich als kardiotonisch wirksam erwiesen (vgl. C. Plotka, R. Jequier und L. Velluz [Compt. Rend. Ac. Sei., Bd. 244 (1957), S. l22]). Sie kann in der Human- oder Veterinärmedizin als Medikament Verwendung finden, da das Vorliegen einer Hydroperoxygruppe keine Steigerung der Toxizität bewirkt, dagegen die pharmakodynamischen Eigenschaften des Ausgangsketosteroids modifizieren kann. Die neue Verbindung kann auch auf Grund der Leichtigkeit ihrer Umwandlung unter sehr milden Bedingungen als Zwischenprodukt verwendet werden.Process for the preparation of 3 a-acetoxy-20 s-hydroperoxy-20-methoxy-pregnan-11-one The invention relates to a process for the preparation of 3x-acetoxy-II-keto-20e-hydroperoxy-20-methoxypregnans formula III given below. This hydroxyperoxysteroid compound can according to that given by Rieche and Schmitz (Chem. Reports, Vol. 90 [1957], p. 1099) Process can be converted into the bishydroperoxide of 3a-acetoxypregnan-11,20-dione. This compound has proven to be cardiotonically effective (cf. C. Plotka, R. Jequier and L. Velluz [Compt. Rend. Ac. Sci., Vol. 244 (1957), p. 122]). she can in human or veterinary medicine as a drug use, since the presence a hydroperoxy group does not cause an increase in toxicity, whereas the pharmacodynamic one does Can modify properties of the starting keto steroid. The new connection can also because of the ease of their transformation under very mild conditions as Intermediate can be used.
Nach dem erfindungsgemäßen Verfahren zur Herstellung der neuen Hydroperoxysteroidverbindung der Formel III führt man zunächst 3x-Acetoxypregnan-11,20-dion (I) nach der Reaktion von Wittig in an sich bekannter Weise in 3oc-Acetoxy-20-methylenpregnan-11-on (II) über, indem man z. B. ein Triphenylmethylphosphoniumsalz in Gegenwart einer Alkyl- oder Aryllithiumverbindung mit der Verbindung der Formel I umsetzt. Die Ketogruppe in 11-Stellung ist gegenüber diesem Reagens inert, und man erhält nach erneuter Acetylierung in 3-Stellung und üblicher Aufarbeitung die 20-Methylensteroidverbindung der Formel Il. Überraschenderweise wurde nun gefunden, daß die Behandlung dieser Verbindung mit Ozon in Gegenwart von Methanol bei niedriger Temperatur, die in an sich bekannter Weise vorgenommen wird, keine Ketonbildung hervorruft, sondern nach dem folgenden Schema in ausgezeichneten Ausbeuten zu der gesuchten Hydroperoxysteroidverbindung der Formel III führt: Das folgende Beispiel erläutert das erfindungsgemäße Verfahren.According to the process according to the invention for the preparation of the new hydroperoxysteroid compound of the formula III, 3x-acetoxypregnan-11,20-dione (I) is first converted into 3oc-acetoxy-20-methylenpregnan-11-one (I) after the reaction of Wittig in a manner known per se ( II) over by z. B. reacts a triphenylmethylphosphonium salt with the compound of formula I in the presence of an alkyl or aryllithium compound. The keto group in the 11-position is inert towards this reagent, and after renewed acetylation in the 3-position and conventional work-up, the 20-methylene steroid compound of the formula II is obtained. Surprisingly, it has now been found that the treatment of this compound with ozone in the presence of methanol at low temperature, which is carried out in a manner known per se, does not cause ketone formation, but leads to the desired hydroperoxysteroid compound of the formula III in excellent yields according to the following scheme: The following example explains the method according to the invention.
Beispiel a) Herstellung von 20-Methylen-3cc-acetoxy-11-keto-pregnan (1I) Man bringt 24 g Triphenylmethylphosphoniumbromid in 260 ccm Benzol ein, destilliert 20 ccm Lösungsmittel ab, setzt 48 ccm einer 11%igen Lösung von Phenyllithium in Äther zu und erhitzt 11/2 Stunden unter Rückfluß. Dann gibt man eine Lösung von 5 g 3a-Acetoxy-11,20-diketo-pregnan in 25 ccm wasserfreiem Benzol zu und erhitzt 11/2 Stunden unter Rückfluß. Nach Abkühlen auf 20°C versetzt man mit Wasser, säuert mit 2n-Schwefelsäure bis zu einem pH-Wert von 5 an, trennt das Benzol ab, extrahiert die wäßrige Phase mit Methylenchlorid, wäscht den Extrakt mit Wasser und mit Natriumbicarbonatlösung, trocknet über Magnesiumsulfat und dampft zur Trockne ein. Den Rückstand nimmt man in 100 ccm Äther auf, trennt unlösliche Bestandteile ab und dampft die Ätherlösung im Vakuum zur Trockne ein. Man löst den Rückstand in einer Mischung von 10 ccm Pyridin und 8 ccm Essigsäureanhydrid und läßt 16 Stunden bei 20°C stehen. Dann. setzt man dem Reaktionsgemisch Wasser zu, extrahiert mit Methylenchlorid, wäscht mit Wasser, trocknet über Magnesiumsulfat und dampft im Vakuum zur Trockne ein. Den Rückstand nimmt man in 100 ccm Petroläther auf, filtriert und chromatographiert an 250 g neutralem Aluminiumoxyd. Man wäscht die Säule mit Petroläther, eluiert mit Methylenchlorid und erhält so 4,1g Rohprodukt, das nach Verdampfen des Lösungsmittels in Form eines Harzes vorliegt. Man nimmt in 41 ccm Äthanol auf und versetzt mit 4,1 ccm Essigsäure und 4,1 g Girardreagens T. Man erhitzt 1 Stunde unter Rückfluß, kühlt in Eis, gießt auf 6 ccm 10 n-Natronlauge in Eis, extrahiert mit Äther, wäscht die nicht ketonischen Extrakte mit Natriumbicarbonatlösung und mit Wasser, trocknet über Magnesiumsulfat und dampft im Vakuum zur Trockne ein. Der Rückstand von 3,94 g wird aus Petroläther umkristallisiert. Man erhält so in einer Ausbeute von 3,08 g (610/0) 20-Methylen-3a-acetoxy-11-keto-pregnan. Die Verbindung der Formel II, die in der Literatur bis jetzt noch nicht beschrieben wurde, bildet kleine ungefärbte Prismen vom F. = 108 bis 1 L0° C und [a]" = +61' (c = 0,501, in Chloroform), die in Wasser unlöslich und in Alkohol, Äther, Aceton und Chloroform löslich sind. Analyse: C24H3603 = 372,5.Example a) Preparation of 20-methylene-3cc-acetoxy-11-keto-pregnane (1I) 24 g of triphenylmethylphosphonium bromide in 260 cc of benzene are introduced, 20 cc of solvent is distilled off, and 48 cc of an 11% solution of phenyllithium is added to ether and heated 11/2 hours under reflux. A solution of 5 g of 3a-acetoxy-11,20-diketo-pregnane in 25 cc of anhydrous benzene is then added and the mixture is refluxed for 11/2 hours. After cooling to 20 ° C., water is added, the mixture is acidified with 2N sulfuric acid to pH 5, the benzene is separated off, the aqueous phase is extracted with methylene chloride, the extract is washed with water and with sodium bicarbonate solution and dried over magnesium sulfate and evaporates to dryness. The residue is taken up in 100 cc of ether, insoluble constituents are separated off and the ether solution is evaporated to dryness in vacuo. The residue is dissolved in a mixture of 10 cc of pyridine and 8 cc of acetic anhydride and left to stand at 20 ° C. for 16 hours. Then. water is added to the reaction mixture, extracted with methylene chloride, washed with water, dried over magnesium sulfate and evaporated to dryness in vacuo. The residue is taken up in 100 cc of petroleum ether, filtered and chromatographed on 250 g of neutral aluminum oxide. The column is washed with petroleum ether and eluted with methylene chloride, giving 4.1 g of crude product which, after evaporation of the solvent, is in the form of a resin. It is taken up in 41 cc of ethanol and treated with 4.1 cc of acetic acid and 4.1 g of Girard's reagent T. The mixture is heated under reflux for 1 hour, cooled in ice, poured onto 6 cc of 10N sodium hydroxide solution in ice, extracted with ether, washed the non-ketonic extracts with sodium bicarbonate solution and with water, dried over magnesium sulfate and evaporated to dryness in vacuo. The 3.94 g residue is recrystallized from petroleum ether. This gives a yield of 3.08 g (610/0) of 20-methylene-3a-acetoxy-11-keto-pregnane. The compound of the formula II, which has not yet been described in the literature, forms small, uncolored prisms with a temperature of m.p. = 108 to 10 ° C. and [a] "= +61 '(c = 0.501, in chloroform), the are insoluble in water and soluble in alcohol, ether, acetone and chloroform Analysis: C24H3603 = 372.5.
" Berechnet ... C 77,37, H 9,74, O 12,88 %; gefunden .-. . C 77,9, H 9,7, O 12,90/0. b) Herstellung von 3a-Acetoxy-20e-hydroperoxy-20-methoxy-pregnän-11-on(III) 500 mg der gemäß a) hergestellten Verbindung II werden in der Wärme in 5 ccm warmem Methanol gelöst. Man kühlt in Eis und bringt dann die Temperatur der Lösung durch Außenklihlung auf -75°C. Das zunächst gelöste Produkt beginnt in.feiner Form auszukristallisieren. Man leitet einen Ozonstrom ein und stellt fest, daß nach 10 Minuten eine vollständige Lösung des Produkts eingetreten ist. Man leitet noch weitere 10 Minuten Ozon ein. Die Hydroperoxyver-'bindung III :kristallisiert aus, und die Lösung wird durch Auflösung .überschüssigen Ozons blau. Man leitet das Gas noch 10 Minuten ein, läßt die Temperatur auf -20°C ansteigen, saugt ab, wäscht die Hydroperoxyverbindung III mitMethanol und trocknet im Vakuum. Man erhält so 384 mg der Verbindung III vom F. = 170°C (Zersetzung), was einer Ausbeute von 670/0 entspricht. Durch Eindampfen der Mutterlaugen im Vakuum unter Stickstoff bei einer Temperatur unterhalb 0°C bis zu einem kleinen Volumen erhält man eine zweite Fraktion des Produkts, wodurch die Gesamtausbeute auf 80 0/0 erhöht wird."Calculated ... C 77.37, H 9.74, O 12.88%; found -.. C 77.9, H 9.7, O 12.90 / 0. b) Preparation of 3a-acetoxy-20e-hydroperoxy-20-methoxy-pregnan-11-one (III) 500 mg of the compound II prepared according to a) are heated in 5 ccm Dissolved methanol. Cool in ice and then bring the temperature of the solution through Outside cooling to -75 ° C. The initially dissolved product begins to crystallize in fine form. A stream of ozone is introduced and it is found that after 10 minutes a complete Solution of the product has occurred. Ozone is introduced for a further 10 minutes. The hydroperoxy compound III: crystallizes out and the solution becomes by dissolution .excess ozone blue. The gas is passed in for a further 10 minutes and the temperature is left rise to -20 ° C, suction off, wash the hydroperoxy compound III with methanol and dries in a vacuum. This gives 384 mg of compound III with a melting point of 170 ° C (decomposition), which corresponds to a yield of 670/0. By evaporating the mother liquors in vacuo under nitrogen at a temperature below 0 ° C to a small volume a second fraction of the product is obtained, bringing the overall yield to 80% 0/0 is increased.
Die Hydroperoxyverbindung III ist in der Wärme wenig stabil. Zur Analyse kristallisiert man aus Methanol um, wobei man die zur Auflösung erforderliche Zeit auf ein Minimum beschränkt und sogleich kühlt. Der Schmelzpunkt bleibt unverändert. Die Verbindung ist wenig löslich in Äther und löslich in Aceton und Chloroform. Analyse: C24H3808 = 422,5.The hydroperoxy compound III is not very stable when heated. For analysis recrystallized from methanol, taking the time required for dissolution limited to a minimum and instantly cools. The melting point remains unchanged. The compound is sparingly soluble in ether and soluble in acetone and chloroform. Analysis: C24H3808 = 422.5.
Berechnet ... C 68,22, H 9,07, O 22,710/0; gefunden ... C 68,9, H 8,9, O 23,10/0. Die Verbindung ist in der Literatur noch nicht beschrieben.Calculated ... C 68.22, H 9.07, O 22.710 / 0; found ... C 68.9, H 8.9, O 23.10 / 0. The connection has not yet been described in the literature.
Verfahrensgemäß kann man gewisse Arbeitsbedingungen, insbesondere die zur Extraktion der Methylenverbindung oder zur Reaktion nach Wittig verwendeten Lösungsmittel in bekannter Weise variieren. Die zur Behandlung mit Ozon erforderliche Temperatur liegt vorzugsweise zwischen -30 und -90°C.According to the method, certain working conditions, in particular those used to extract the methylene compound or to react according to Wittig Vary solvents in a known manner. The one required for treatment with ozone The temperature is preferably between -30 and -90 ° C.
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1129952X | 1959-03-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1129952B true DE1129952B (en) | 1962-05-24 |
Family
ID=9637207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEL35609A Pending DE1129952B (en) | 1959-03-27 | 1960-03-14 | Process for the preparation of 3 ª ‡ -acetoxy-20ªŠ-hydroperoxy-20-methoxy-pregnan-11-one |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1129952B (en) |
-
1960
- 1960-03-14 DE DEL35609A patent/DE1129952B/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| None * |
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