DE2137546C3 - Verfahren zur Herstellung von 17alpha Athjnyl, Methyl und Vinyl 17beta Acetyloxysteroiden der Androstan bzw Ostranreihe - Google Patents
Verfahren zur Herstellung von 17alpha Athjnyl, Methyl und Vinyl 17beta Acetyloxysteroiden der Androstan bzw OstranreiheInfo
- Publication number
- DE2137546C3 DE2137546C3 DE2137546A DE2137546A DE2137546C3 DE 2137546 C3 DE2137546 C3 DE 2137546C3 DE 2137546 A DE2137546 A DE 2137546A DE 2137546 A DE2137546 A DE 2137546A DE 2137546 C3 DE2137546 C3 DE 2137546C3
- Authority
- DE
- Germany
- Prior art keywords
- ethynyl
- methyl
- reaction
- carried out
- acylation
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- QZLYKIGBANMMBK-UGCZWRCOSA-N 5α-Androstane Chemical compound C([C@@H]1CC2)CCC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CCC[C@@]2(C)CC1 QZLYKIGBANMMBK-UGCZWRCOSA-N 0.000 title 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title 1
- 229920002554 vinyl polymer Polymers 0.000 title 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 72
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 20
- 239000011541 reaction mixture Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000004043 oxo group Chemical group O=* 0.000 claims description 10
- 235000005074 zinc chloride Nutrition 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 10
- 230000021736 acetylation Effects 0.000 claims description 9
- 238000006640 acetylation reaction Methods 0.000 claims description 9
- 150000002085 enols Chemical class 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 230000010933 acylation Effects 0.000 claims description 6
- 238000005917 acylation reaction Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000007086 side reaction Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical class Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical class Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- TUCNEACPLKLKNU-UHFFFAOYSA-N acetyl Chemical group C[C]=O TUCNEACPLKLKNU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- XEHVFKKSDRMODV-UHFFFAOYSA-N ethynyl Chemical compound C#[C] XEHVFKKSDRMODV-UHFFFAOYSA-N 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical compound C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 3
- 150000008065 acid anhydrides Chemical class 0.000 claims 2
- 230000004071 biological effect Effects 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 claims 2
- YSGQGNQWBLYHPE-CFUSNLFHSA-N (7r,8r,9s,10r,13s,14s,17s)-17-hydroxy-7,13-dimethyl-2,6,7,8,9,10,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-one Chemical compound C1C[C@]2(C)[C@@H](O)CC[C@H]2[C@@H]2[C@H](C)CC3=CC(=O)CC[C@@H]3[C@H]21 YSGQGNQWBLYHPE-CFUSNLFHSA-N 0.000 claims 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims 1
- 150000007514 bases Chemical class 0.000 claims 1
- 125000005605 benzo group Chemical group 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 230000003054 hormonal effect Effects 0.000 claims 1
- 238000001953 recrystallisation Methods 0.000 claims 1
- 125000002345 steroid group Chemical group 0.000 claims 1
- 150000003431 steroids Chemical class 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 238000002560 therapeutic procedure Methods 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 27
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- 229960000583 acetic acid Drugs 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000012362 glacial acetic acid Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 15
- 239000000725 suspension Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000005457 ice water Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 238000009739 binding Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- TWAOQVMPIYQPKG-UHFFFAOYSA-N ethanone Chemical compound C[C+]=O TWAOQVMPIYQPKG-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J21/00—Normal steroids containing carbon, hydrogen, halogen or oxygen having an oxygen-containing hetero ring spiro-condensed with the cyclopenta(a)hydrophenanthrene skeleton
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HURI000399 | 1970-07-29 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE2137546A1 DE2137546A1 (de) | 1972-02-17 |
| DE2137546B2 DE2137546B2 (de) | 1973-04-05 |
| DE2137546C3 true DE2137546C3 (de) | 1973-11-08 |
Family
ID=11000843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2137546A Expired DE2137546C3 (de) | 1970-07-29 | 1971-07-27 | Verfahren zur Herstellung von 17alpha Athjnyl, Methyl und Vinyl 17beta Acetyloxysteroiden der Androstan bzw Ostranreihe |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US3761496A (enExample) |
| JP (1) | JPS538695B1 (enExample) |
| CA (1) | CA937232A (enExample) |
| CH (1) | CH606088A5 (enExample) |
| CS (1) | CS164763B2 (enExample) |
| DE (1) | DE2137546C3 (enExample) |
| DK (1) | DK132282C (enExample) |
| ES (1) | ES393516A1 (enExample) |
| FR (1) | FR2100963B1 (enExample) |
| IL (1) | IL37255A (enExample) |
| NL (1) | NL174553C (enExample) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7816546B2 (en) * | 2003-06-30 | 2010-10-19 | Richter Gedeon Vegyeszeti Gyar Rt. | Process for the synthesis of high purity d-(17α)-13-ethyl-17-hydroxy-18,19-dinorpregn-4-ene-20-yn-3-one-oxime |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1434518A (fr) * | 1964-04-03 | 1966-04-08 | Farmaceutici Italia | Procédé de préparation d'esters. 17 alpha de céto.3 hydroxy. 17 alpha delta4 prégnènes |
| US3471531A (en) * | 1966-04-07 | 1969-10-07 | Herchel Smith | Synthesis of gona-3,5-dienes |
| US3515719A (en) * | 1967-03-15 | 1970-06-02 | Upjohn Co | 7-methyl-6,19-epoxy steroids of the androstane series |
| FI45552C (fi) * | 1967-12-08 | 1972-07-10 | Searle & Co | Menetelmä 17alfa-asyylioksi-11beta-metyyli-19-norpregn-4-eeni-3,20-dio nien ja niiden johdannaisten valmistamiseksi. |
| US3691212A (en) * | 1970-04-24 | 1972-09-12 | British Drug Houses Ltd | 17alpha-(1',3'-alkadiynyl)-17beta-acyloxy(17beta-aroyloxy) steroids |
-
1971
- 1971-06-28 CH CH948571A patent/CH606088A5/xx not_active IP Right Cessation
- 1971-06-29 CA CA116932A patent/CA937232A/en not_active Expired
- 1971-07-06 US US00160085A patent/US3761496A/en not_active Expired - Lifetime
- 1971-07-07 IL IL37255A patent/IL37255A/xx unknown
- 1971-07-22 ES ES393516A patent/ES393516A1/es not_active Expired
- 1971-07-26 CS CS5456A patent/CS164763B2/cs unknown
- 1971-07-27 DE DE2137546A patent/DE2137546C3/de not_active Expired
- 1971-07-28 FR FR7127716A patent/FR2100963B1/fr not_active Expired
- 1971-07-28 DK DK370271A patent/DK132282C/da active
- 1971-07-28 JP JP5607771A patent/JPS538695B1/ja active Pending
- 1971-07-29 NL NLAANVRAGE7110487,A patent/NL174553C/xx not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2100963A1 (enExample) | 1972-03-24 |
| DK132282C (da) | 1976-04-26 |
| NL174553B (nl) | 1984-02-01 |
| DE2137546B2 (de) | 1973-04-05 |
| CH606088A5 (enExample) | 1978-10-13 |
| CA937232A (en) | 1973-11-20 |
| JPS538695B1 (enExample) | 1978-03-31 |
| CS164763B2 (enExample) | 1975-11-28 |
| DK132282B (da) | 1975-11-17 |
| ES393516A1 (es) | 1973-08-16 |
| FR2100963B1 (enExample) | 1975-08-01 |
| IL37255A0 (en) | 1971-10-20 |
| NL7110487A (enExample) | 1972-02-01 |
| NL174553C (nl) | 1984-07-02 |
| DE2137546A1 (de) | 1972-02-17 |
| IL37255A (en) | 1975-05-22 |
| US3761496A (en) | 1973-09-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) | ||
| E77 | Valid patent as to the heymanns-index 1977 | ||
| 8339 | Ceased/non-payment of the annual fee |