CH616437A5 - Process for the preparation of 3,20-diketopregnenes having an 11beta-acetal group and their derivatives - Google Patents
Process for the preparation of 3,20-diketopregnenes having an 11beta-acetal group and their derivatives Download PDFInfo
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- CH616437A5 CH616437A5 CH1133976A CH1133976A CH616437A5 CH 616437 A5 CH616437 A5 CH 616437A5 CH 1133976 A CH1133976 A CH 1133976A CH 1133976 A CH1133976 A CH 1133976A CH 616437 A5 CH616437 A5 CH 616437A5
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J71/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton is condensed with a heterocyclic ring
- C07J71/0005—Oxygen-containing hetero ring
- C07J71/0026—Oxygen-containing hetero ring cyclic ketals
- C07J71/0031—Oxygen-containing hetero ring cyclic ketals at positions 16, 17
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
Abstract
Description
Le but de la présente invention est la préparation de stéroïdes ayant une activité anti-inflammatoire locale et générale et pouvant être facilement mis en composition dans des solvants légèrement polaires tels que l'huile de ricin ou le carbonate de propylène. The object of the present invention is the preparation of steroids having local and general anti-inflammatory activity and which can be easily composed in slightly polar solvents such as castor oil or propylene carbonate.
Pour atteindre ce but, l'invention propose le procédé défini dans la revendication 1. To achieve this object, the invention provides the method defined in claim 1.
En particulier, le procédé selon l'invention permet de préparer les stéroïdes de formule: In particular, the process according to the invention makes it possible to prepare the steroids of formula:
Le terme «halogène» utilisé ici se rapporte au fluor, au chlore, au brome et à l'iode. The term "halogen" used here refers to fluorine, chlorine, bromine and iodine.
Le terme «acyloxy» utilisé ici se rapporte à des groupes où le fragment acyle est un reste d'acide physiologiquement acceptable dérivant d'un acide organique. Des exemples d'acides monocarboxyliques sont ceux de formule Y—COOH dans laquelle Y est un groupe alcoyle, cyclo-alcoyle ayant de 3 à 6 atomes de carbone, arylalcoyle ou aryle; par exemple les acides acétique, propionique, valérique, cyclohexane carboxyli-que, phénylacétique, benzoïque et toluïque. Des exemples d'acides polycarboxyliques sont les acides malonique, succini-que, glutarique, adipique, pimelique etphtalique. The term "acyloxy" used herein refers to groups where the acyl moiety is a physiologically acceptable acid residue derived from an organic acid. Examples of monocarboxylic acids are those of the formula Y-COOH in which Y is an alkyl, cycloalkyl group having 3 to 6 carbon atoms, arylalkyl or aryl; for example acetic, propionic, valeric, cyclohexane carboxylic, phenylacetic, benzoic and toluic acids. Examples of polycarboxylic acids are malonic, succinic, glutaric, adipic, pimelic and phthalic acids.
Le terme «aryle» utilisé ici se rapporte à un groupe phényle ou phényle substitué par 1 ou 2 groupes alcoyle, alcoxy ou atomes d'halogène. The term "aryl" used herein refers to a phenyl or phenyl group substituted by 1 or 2 alkyl groups, alkoxy or halogen atoms.
Le terme «alcoxy» utilisé ici se rapporte à un groupe de formule alcoyl-O- où le groupe alcoyle a la signification ci-dessus. The term "alkoxy" used herein refers to a group of the formula alkyl-O- where the alkyl group has the above meaning.
Les stéroïdes du présent procédé sont des substances physiologiquement actives qui possèdent une activité glucocorti- The steroids of the present process are physiologically active substances which have glucocorticidal activity.
616437 616437
4 4
coïde et anti-inflammatoire et qu'on peut donc utiliser à la place des glucocorticoïdes connus pour le traitement de la polyarthrite évolutive chronique, et dans ce but on peut les administrer comme l'hydrocortisone, en ajustant la dose par exemple suivant le pouvoir relatif du stéroïde particulier. En outre les stéroïdes du présent procédé peuvent être utilisés localement à la place de glucocorticoïdes connus pour le traitement d'états de la peau tel qu'une dermatite, le psoriasis, les coups de soleil, une neurodermatite, l'eczema et le prurite anogénital. cooid and anti-inflammatory and which can therefore be used in place of the glucocorticoids known for the treatment of chronic progressive polyarthritis, and for this purpose they can be administered like hydrocortisone, by adjusting the dose for example according to the relative power of the particular steroid. Furthermore, the steroids of the present method can be used locally in place of glucocorticoids known for the treatment of skin conditions such as dermatitis, psoriasis, sunburn, neurodermatitis, eczema and anogenital pruritis. .
Lorsqu'on les administre par voie orale les présents composés peuvent être utilisés à une dose quotidienne de 0,1 à 200 mg/70 kg et de préférence 0,3 à 100 mg/70 kg. Si on les administre localement on peut utiliser les présents composés à raison de 0,01 à 5,0% en poids et de préférence 0,05 à 2,0% en poids dans une crème ou une lotion classique. When administered orally the present compounds can be used at a daily dose of 0.1-200 mg / 70 kg and preferably 0.3-100 mg / 70 kg. If administered locally, the present compounds can be used in an amount of 0.01 to 5.0% by weight and preferably 0.05 to 2.0% by weight in a conventional cream or lotion.
Les 3,20-dicétopregnènes de formule III sont préparés en faisant réagir un l^-hydroxy-3,20-dicétopregnène, c'est-à-dire la contre-partie llß-hydroxy du stéroïde de formule III, avec un 1-alcoxybenzocyclobutène de formule: The 3,20-diketopregnenes of formula III are prepared by reacting a 1-hydroxy-3,20-diketopregnene, that is to say the 11β-hydroxy counterpart of the steroid of formula III, with a 1- alkoxybenzocyclobutene of formula:
OR. GOLD.
II II
\R \ R
dans laquelle R'2 est un atome d'hydrogène ou un groupe alcoyle ayant de 1 à 7 atomes de carbone. La réaction, qui est nouvelle, peut être conduite en des conditions neutres dans un solvant aprotique par exemple un hydrocarbure tel que le benzène ou le toluène. Bien que les conditions réactionnelles ne soient pas critiques, on conduit de préférence la réaction à la température de reflux du solvant ou voisine de celle-ci. in which R'2 is a hydrogen atom or an alkyl group having from 1 to 7 carbon atoms. The reaction, which is new, can be carried out under neutral conditions in an aprotic solvent, for example a hydrocarbon such as benzene or toluene. Although the reaction conditions are not critical, the reaction is preferably carried out at the reflux temperature of the solvent or close to it.
Cette réaction est utile non seulement pour la préparation des présents stéroïdes mais aussi pour la préparation d'autres stéroïdes contenant un groupe llß-hydroxy qui doit être protégé pendant des synthèses à plusieurs étapes. Le groupe de blocage peut être facilement enlevé par hydrolyse acide. This reaction is useful not only for the preparation of the present steroids but also for the preparation of other steroids containing an 11β-hydroxy group which must be protected during multistage syntheses. The blocking group can be easily removed by acid hydrolysis.
Diverses variantes et modifications du présent procédé seront claires pour ceux du métier. Par exemple, lorsque le llß-hydroxy-3,20-dicétopregnène utilisé pour préparer les présents stéroïdes contient des groupes hydroxyles supplémentaires, il faut les protéger avant de poursuivre les réactions décrites plus haut. Various variants and modifications of the present process will be clear to those in the art. For example, when the 11β-hydroxy-3,20-diketopregnene used to prepare the present steroids contains additional hydroxyl groups, they must be protected before continuing the reactions described above.
Les exemples suivants illustrent l'invention. The following examples illustrate the invention.
Exemple 1 Example 1
21-Chloro-l 1 ß-[ethoxy(2-n^thylplwnyl)n^thoxy]-9-fluoro-2',2'-diméthylpregn-4-éno[ 16 a, 17-d] -[ 1,3]dioxolane-3,20-dione 21-Chloro-1 1 ß- [ethoxy (2-n ^ thylplwnyl) n ^ thoxy] -9-fluoro-2 ', 2'-dimethylpregn-4-eno [16 a, 17-d] - [1,3 ] dioxolane-3,20-dione
On chauffe à reflux une suspension de 684 mg de 21-chloro-9-fluoro-l 1 ß-hydroxy-2',2/-diméthylpregn-4-éno-[16a,17-d][l,3]dioxolane-3,20-dione dans 17 ml de toluène anhydre contenant 444 mg de l-éthoxy-l,2-dihydrobenzocy-s clobutène dans une atmosphère d'azote. Après quelques minutes on obtient une solution homogène. Après environ 6 h on refroidit la solution puis on l'absorbe sur une colonne de 20 mg de silicagel. L'élution de la colonne avec un mélange 1:4 de chloroforme-hexane donne du l-éthoxy-l,2-dihydro-10 benzocyclobutène n'ayant pas réagi. Une nouvelle élution de la colonne avec des mélanges 1:4 et 1:1 de chloroforme-hexane donne le produit sous forme de 0,90 g d'une mousse. On dissout celle-ci dans la quantité minimum d'éther, on dilue avec 10 ml d'hexane et on maintient à une température d'environ is 5°C pour obtenir 355 mg d'une substance solide qui fond à 171-180°C. La recristallisation de cette substance à partir d'un mélange d'acétate d'éthyle-hexane donne 205 mg du composé désiré qui fond à 182-185°C. A suspension of 684 mg of 21-chloro-9-fluoro-1 1 ß-hydroxy-2 ', 2 / -dimethylpregn-4-eno- [16a, 17-d] [1,3] dioxolane is heated to reflux. 3.20-dione in 17 ml of anhydrous toluene containing 444 mg of l-ethoxy-1,2-dihydrobenzocy-s clobutene in a nitrogen atmosphere. After a few minutes a homogeneous solution is obtained. After approximately 6 h the solution is cooled and then it is absorbed on a column of 20 mg of silica gel. Elution from the column with a 1: 4 mixture of chloroform-hexane gives unreacted 1-ethoxy-1,2-dihydro-10-benzocyclobutene. Further elution of the column with 1: 4 and 1: 1 mixtures of chloroform-hexane gives the product in the form of 0.90 g of a foam. This is dissolved in the minimum amount of ether, diluted with 10 ml of hexane and maintained at a temperature of approximately 5 ° C to obtain 355 mg of a solid substance which melts at 171-180 ° vs. Recrystallization of this substance from a mixture of ethyl acetate-hexane gives 205 mg of the desired compound which melts at 182-185 ° C.
20 Exemple 2 20 Example 2
21 - (Acétyloxy) -11 ß- [éthoxy (2-méthylphényl)méthoxy] -9-fluoro-2/,2'-diméthylpregna-l,4-diéno[16a,17-d] [l,3]dioxolane-3,20-dione On dissout 1,0 g de 21-acétate de triamcinolone-acétonide 25 dans 37 ml de xylènes anhydres dans un bain d'huile maintenu à environ 125°C dans une atmosphère d'azote. On ajoute 1,11 g de 1-éthoxybenzocyclobutène et après 18 h, la réaction est incomplète. On ajoute les nouvelles quantités suivantes de 1-éthoxybenzocyclobutène aux intervalles de temps indiqués: 21 - (Acetyloxy) -11 ß- [ethoxy (2-methylphenyl) methoxy] -9-fluoro-2 /, 2'-dimethylpregna-1, 4-dieno [16a, 17-d] [l, 3] dioxolane- 3.20-dione 1.0 g of 21-triamcinolone-acetonide acetate is dissolved in 37 ml of anhydrous xylenes in an oil bath maintained at about 125 ° C in a nitrogen atmosphere. 1.11 g of 1-ethoxybenzocyclobutene are added and after 18 h the reaction is incomplete. The following new amounts of 1-ethoxybenzocyclobutene are added at the indicated time intervals:
30 30
35 35
0,3 ml 0,3 ml 0,3 ml 0,3 ml 0,3 ml 0.3 ml 0.3 ml 0.3 ml 0.3 ml 0.3 ml
(21 h) (24 h) (28 h) (46 h) et (48 h) (9 p.m.) (24 h) (28 h) (46 h) and (48 h)
40 40
45 45
50 50
On évapore la solution et on dissout le résidu dans le chloroforme et on Chromatographie sur une colonne de 25 mg de silicagel. L'élution de la colonne avec des mélanges 1:4 à 1:1 de chloroforme-hexane enlève les impuretés non-stéroïdes. Une nouvelle élution avec un mélange 4:1 de chloroforme-hexane et du chloroforme donne 0,8 g de la substance désirée. On sèche la substance solide pour obtenir le composé désiré qui fond à 105-110°C. The solution is evaporated and the residue is dissolved in chloroform and chromatographed on a 25 mg column of silica gel. Eluting the column with 1: 4 to 1: 1 mixtures of chloroform-hexane removes non-steroid impurities. Further elution with a 4: 1 mixture of chloroform-hexane and chloroform gives 0.8 g of the desired substance. The solid is dried to obtain the desired compound which melts at 105-110 ° C.
Exemples 3-6 Examples 3-6
En procédant comme dans l'exemple 1 mais en substituant le stéroïde indiqué dans la colonne I à la 21-chloro-9-fluoro-l^-hydroxy-2',2'-diméthylpregn-4-éno[16a, 17-d][l,3]dioxo-lane-3,20-dione, et le composé indiqué dans la colonne II au 1-éthoxy-l,2-dihydrobenzocyclobutène on obtient le stéroïde indiqué dans la colonne III. By proceeding as in Example 1 but by substituting the steroid indicated in column I for 21-chloro-9-fluoro-1 ^ -hydroxy-2 ', 2'-dimethylpregn-4-eno [16a, 17-d ] [l, 3] dioxo-lane-3,20-dione, and the compound indicated in column II with 1-ethoxy-1,2-dihydrobenzocyclobutene, the steroid indicated in column III is obtained.
Colonne I Column I
Colonne II Column II
Colonne III Column III
2,21 -dichloro-11 ß-hydroxy-2 ', 2 ' - 2,21 -dichloro-11 ß-hydroxy-2 ', 2' -
diméthylpregna-l,4-diéno[16a, 17-d]- dimethylpregna-1,4-dieno [16a, 17-d] -
[l,3]dioxolane-3,20-dione [l, 3] dioxolane-3,20-dione
11 ß-hydroxy-2', 2'-diméthylpregna- 11 ß-hydroxy-2 ', 2'-dimethylpregna-
l,4,6-triéno[16a,17-d][l,3]dioxolane- l, 4,6-trieno [16a, 17-d] [l, 3] dioxolane-
3,20-dione 3.20-dione
21 -chloro-1 lß-hydroxy-2,2' ,2 '-tri- 21 -chloro-1 lß-hydroxy-2,2 ', 2' -tri-
méthylpregna-1,4-diéno[ 16a, 17-d] - methylpregna-1,4-dieno [16a, 17-d] -
[l,3]dioxolane-3,20-dione [l, 3] dioxolane-3,20-dione
21 -(benzoyloxy)-11 ß-hydroxy-2 ', 2 ' - 21 - (benzoyloxy) -11 ß-hydroxy-2 ', 2' -
diphénylpregna-l,4-diéno[16a,17-d]- diphenylpregna-1,4-dieno [16a, 17-d] -
[l,3]dioxolane-3,20-dione l-éthoxy-2-méthyl- [1,3] dioxolane-3,20-dione l-ethoxy-2-methyl-
1,2-dihydrobenzocyclo- 1,2-dihydrobenzocyclo-
butène butene
1 -propoxy-2-éthyl-1,2- 1 -propoxy-2-ethyl-1,2-
dihydrobenzocyclo- dihydrobenzocyclo-
butène l-éthoxy-l,2-dihydro-benzocyclobutène butene l-ethoxy-l, 2-dihydro-benzocyclobutene
1 -éthoxy-1,2- dihydro-benzocyclobutène 1-ethoxy-1,2- dihydro-benzocyclobutene
2,21 -dichloro-1 lß-[éthoxy (2-éthylphényl)- 2,21 -dichloro-1 lß- [ethoxy (2-ethylphenyl) -
méthoxy]-2',2'-diméthylpregna-l,4-diéno- methoxy] -2 ', 2'-dimethylpregna-l, 4-dieno-
[16a,17-d][l,3]dioxolane-3,20-dione lip-[propoxy(2-propylphényl)méthoxy]-2',2'- [16a, 17-d] [l, 3] dioxolane-3,20-dione lip- [propoxy (2-propylphenyl) methoxy] -2 ', 2'-
diméthylpregna-l,4,6-triéno[16a,17-d][l,3]- dimethylpregna-1,4,6-trieno [16a, 17-d] [1,3] -
dioxolane-3,20-dione dioxolane-3,20-dione
21 -chloro-11 ß- [éthoxy (2-méthylphényl)méthoxy]- 21 -chloro-11 ß- [ethoxy (2-methylphenyl) methoxy] -
2,2',2'-triméthylpregna-l,4-diéno[16a,17-d]- 2,2 ', 2'-trimethylpregna-1,4-dieno [16a, 17-d] -
[l,3]dioxolane-3,20-dione [l, 3] dioxolane-3,20-dione
21 -(benzoyloxy)-11 ß- [éthoxy(2-méthylphényl)- 21 - (benzoyloxy) -11 ß- [ethoxy (2-methylphenyl) -
méthoxy]-2 ',2 ' -diphénylpregna-1,4-diéno- methoxy] -2 ', 2' -diphenylpregna-1,4-dieno-
[16a,17-d][l,3]dioxolane-3,20-dione [16a, 17-d] [l, 3] dioxolane-3,20-dione
B B
Claims (12)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/610,955 US3976637A (en) | 1975-09-08 | 1975-09-08 | 3,20-Diketopregnenes having an 11β-acetal group |
US66817776A | 1976-03-18 | 1976-03-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
CH616437A5 true CH616437A5 (en) | 1980-03-31 |
Family
ID=27086400
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CH1133976A CH616437A5 (en) | 1975-09-08 | 1976-09-07 | Process for the preparation of 3,20-diketopregnenes having an 11beta-acetal group and their derivatives |
CH626779A CH618186A5 (en) | 1975-09-08 | 1979-07-04 | Process for the preparation of 3,20-diketopregnenes having a 11beta-acetal group. |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CH626779A CH618186A5 (en) | 1975-09-08 | 1979-07-04 | Process for the preparation of 3,20-diketopregnenes having a 11beta-acetal group. |
Country Status (13)
Country | Link |
---|---|
JP (1) | JPS5233664A (en) |
AU (1) | AU506546B2 (en) |
BE (1) | BE845943A (en) |
CA (1) | CA1058161A (en) |
CH (2) | CH616437A5 (en) |
DE (1) | DE2640490A1 (en) |
DK (1) | DK402676A (en) |
FR (1) | FR2322607A1 (en) |
GB (1) | GB1544512A (en) |
IE (1) | IE44534B1 (en) |
NL (1) | NL7609912A (en) |
NO (2) | NO144491C (en) |
SE (1) | SE7609884L (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1285770B1 (en) | 1996-10-04 | 1998-06-18 | Nicox Sa | CORTICOID COMPOUNDS |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3976637A (en) * | 1975-09-08 | 1976-08-24 | E. R. Squibb & Sons, Inc. | 3,20-Diketopregnenes having an 11β-acetal group |
-
1976
- 1976-08-31 CA CA260,229A patent/CA1058161A/en not_active Expired
- 1976-08-31 IE IE1942/76A patent/IE44534B1/en unknown
- 1976-09-02 AU AU17384/76A patent/AU506546B2/en not_active Expired
- 1976-09-06 GB GB36853/76A patent/GB1544512A/en not_active Expired
- 1976-09-07 DK DK402676A patent/DK402676A/en unknown
- 1976-09-07 NL NL7609912A patent/NL7609912A/en not_active Application Discontinuation
- 1976-09-07 CH CH1133976A patent/CH616437A5/en not_active IP Right Cessation
- 1976-09-07 NO NO76763060A patent/NO144491C/en unknown
- 1976-09-07 SE SE7609884A patent/SE7609884L/en unknown
- 1976-09-08 DE DE19762640490 patent/DE2640490A1/en not_active Withdrawn
- 1976-09-08 FR FR7627002A patent/FR2322607A1/en active Granted
- 1976-09-08 JP JP51108717A patent/JPS5233664A/en active Pending
- 1976-09-08 BE BE170429A patent/BE845943A/en not_active IP Right Cessation
-
1979
- 1979-07-04 CH CH626779A patent/CH618186A5/en not_active IP Right Cessation
-
1981
- 1981-01-27 NO NO81810271A patent/NO145919C/en unknown
Also Published As
Publication number | Publication date |
---|---|
AU506546B2 (en) | 1980-01-10 |
NO763060L (en) | 1977-03-09 |
FR2322607A1 (en) | 1977-04-01 |
IE44534L (en) | 1977-03-08 |
IE44534B1 (en) | 1981-12-30 |
SE7609884L (en) | 1977-03-09 |
NO810271L (en) | 1977-03-09 |
JPS5233664A (en) | 1977-03-14 |
NO145919B (en) | 1982-03-15 |
GB1544512A (en) | 1979-04-19 |
CH618186A5 (en) | 1980-07-15 |
NL7609912A (en) | 1977-03-10 |
DK402676A (en) | 1977-03-09 |
NO145919C (en) | 1982-06-30 |
NO144491C (en) | 1981-09-09 |
BE845943A (en) | 1977-03-08 |
CA1058161A (en) | 1979-07-10 |
FR2322607B1 (en) | 1979-02-23 |
AU1738476A (en) | 1978-03-09 |
NO144491B (en) | 1981-06-01 |
DE2640490A1 (en) | 1977-03-10 |
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