GB888165A - Improvements in or relating to 4-methyl-3-oxo-í~-steroids - Google Patents
Improvements in or relating to 4-methyl-3-oxo-í~-steroidsInfo
- Publication number
- GB888165A GB888165A GB37287/58A GB3728758A GB888165A GB 888165 A GB888165 A GB 888165A GB 37287/58 A GB37287/58 A GB 37287/58A GB 3728758 A GB3728758 A GB 3728758A GB 888165 A GB888165 A GB 888165A
- Authority
- GB
- United Kingdom
- Prior art keywords
- methyl
- hydroxy
- acetoxy
- dione
- methylpregn
- 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
- 150000003431 steroids Chemical class 0.000 abstract 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 3
- 239000003638 chemical reducing agent Substances 0.000 abstract 3
- 230000007062 hydrolysis Effects 0.000 abstract 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract 3
- 238000000034 method Methods 0.000 abstract 3
- 238000002360 preparation method Methods 0.000 abstract 3
- VFWYHGLPLLLMDD-SZGKAOMTSA-N (2R,8'R,9'S,10'R,13'S,14'S)-3,4',10',13'-tetramethylspiro[1,4-dioxane-2,17'-2,6,7,8,9,11,12,14,15,16-decahydro-1H-cyclopenta[a]phenanthrene]-3'-one Chemical compound C1OC(C)[C@]2(CC[C@H]3[C@@H]4CCC5=C(C(CC[C@]5(C)[C@H]4CC[C@]23C)=O)C)OC1 VFWYHGLPLLLMDD-SZGKAOMTSA-N 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 abstract 2
- 150000002148 esters Chemical class 0.000 abstract 2
- ZALBIEJCFBSSHX-OFLOQBSOSA-N (1R,2S,10R,11S,14S,15R)-10-hydroxy-9,11,15,19-tetramethyl-5,8-dioxapentacyclo[12.8.0.02,11.04,10.015,20]docos-19-en-18-one Chemical compound C1OC(C)[C@]2(C(C[C@H]3[C@@H]4CCC5=C(C(CC[C@]5(C)[C@H]4CC[C@]23C)=O)C)OC1)O ZALBIEJCFBSSHX-OFLOQBSOSA-N 0.000 abstract 1
- SODPIMGUZLOIPE-UHFFFAOYSA-N (4-chlorophenoxy)acetic acid Chemical compound OC(=O)COC1=CC=C(Cl)C=C1 SODPIMGUZLOIPE-UHFFFAOYSA-N 0.000 abstract 1
- MEMGUVRVJGYLPA-KBBKRBAUSA-N (8R,9S,10R,13S,14S,17S)-17-hydroxy-10,13-dimethyl-4-(phenylsulfanylmethyl)-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-3-one Chemical compound C1(=CC=CC=C1)SCC1=C2CC[C@@H]3[C@H](CC[C@@]4([C@H](CC[C@H]43)O)C)[C@]2(CCC1=O)C MEMGUVRVJGYLPA-KBBKRBAUSA-N 0.000 abstract 1
- ISTFVSGVYPSGKE-QGQWSAILSA-N (8S,9S,10R,13S,14S,17S)-17-acetyl-4,10,13-trimethyl-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-3-one Chemical compound CC1=C2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@]2(CCC1=O)C)C)C(C)=O ISTFVSGVYPSGKE-QGQWSAILSA-N 0.000 abstract 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 abstract 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 abstract 1
- VWIGOBCYZDKRDK-UHFFFAOYSA-N 4,10,13-trimethyl-17-(6-methylheptan-2-yl)-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-3-one Chemical compound C1CC2=C(C)C(=O)CCC2(C)C2C1C1CCC(C(C)CCCC(C)C)C1(C)CC2 VWIGOBCYZDKRDK-UHFFFAOYSA-N 0.000 abstract 1
- 239000007868 Raney catalyst Substances 0.000 abstract 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical group [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 abstract 1
- 229910000564 Raney nickel Inorganic materials 0.000 abstract 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- FTWFWIYWVOBQQG-LQUXNCDFSA-N [(8r,9s,10r,13s,14s,17s)-4,10,13-trimethyl-3-oxo-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl] acetate Chemical compound C1CC2=C(C)C(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](OC(=O)C)[C@@]1(C)CC2 FTWFWIYWVOBQQG-LQUXNCDFSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 125000002252 acyl group Chemical group 0.000 abstract 1
- 125000004423 acyloxy group Chemical group 0.000 abstract 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract 1
- 125000005530 alkylenedioxy group Chemical group 0.000 abstract 1
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000032050 esterification Effects 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 125000004494 ethyl ester group Chemical group 0.000 abstract 1
- OSVMTWJCGUFAOD-KZQROQTASA-N formestane Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1O OSVMTWJCGUFAOD-KZQROQTASA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 238000005907 ketalization reaction Methods 0.000 abstract 1
- GSOQEUYHQOEZLX-UHARQNSMSA-N methyl (4R)-4-[(8S,9S,10R,13R,14S,17R)-4,10,13-trimethyl-3-oxo-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl]pentanoate Chemical compound COC(CC[C@@H](C)[C@H]1CC[C@H]2[C@@H]3CCC4=C(C(CC[C@]4(C)[C@H]3CC[C@]12C)=O)C)=O GSOQEUYHQOEZLX-UHARQNSMSA-N 0.000 abstract 1
- 229960004719 nandrolone Drugs 0.000 abstract 1
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical compound OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 abstract 1
- 229960003387 progesterone Drugs 0.000 abstract 1
- 239000000186 progesterone Substances 0.000 abstract 1
- 125000006239 protecting group Chemical group 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
Classifications
-
- 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
- C07J75/00—Processes for the preparation of steroids in general
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Steroid Compounds (AREA)
Abstract
The invention comprises (1) a process for the preparation of 4-methyl-3-oxo-D 4-steroids by reacting a 4-organo-thiomethyl-3-oxo-D 4-steroid with a reducing agent; and (2) as new steroids, 2a : 4- and 4 : 6a -dimethyltestosterones and their acyl esters; 17a -acetoxy-4 : 6a -dimethylprogesterone; 4 : 16a -dimethylprogesterone; 4-methyl-17a - acetoxy - 16 - methylene - progesterone; 4 : 17a -dimethyl-9a -fluoro-11b : 17b -dihydroxyandrost-4-en-3-one; 4-methyl-11a - and -11b -hydroxy - 17b - hydroxyandrost - 4 - en - 3 - ones; 4-methylandrost-4-ene-3 : 11 : 17-trione; and 11b -hydroxy-17a : 20 : 20 : 21-bis-methylenedioxy - 4 - methylpregn - 4 - en - 3 - one. The preferred reducing agent is Raney nickel, which is desirably deactivated by a preliminary heating in a ketonic solvent, the organothiomethyl steroid then being added to the resulting suspension. Alternatively, zinc dust and an alkali metal hydroxide may be used as reducing agent. Readily oxidizable hydroxy groups may be protected prior to the desulphurization reaction by esterification, and subsequently regenerated by hydrolysis; and a 17-ketol side-chain may be protected by 20-ketalization or conversion of the side-chain into the bis-methylenedioxy derivative, the protecting groups subsequently being removed. The process may be applied to any of the organothiomethyl steroids described in Specification 862,621. In examples the preparation of all the above-mentioned steroids and of 4-methyl-testosterone acetate and other esters, 4 : 17a -dimethyl-testosterone, 17a -ethyl-4-methyltestosterone, 4-methyl- and 4 : 6a -dimethylandrost-4-ene-3 : 17-diones, 4-methyl-progesterone, 4-methylpregna-4 : 9(11)-diene-3 : 20-dione, 17a -acetoxy-4-methylprogesterone and other esters, 17a : 20 : 20 : 21-bismethylenedioxy-4-methylpregna-4-ene-3 : 11-dione, 4-methyl-25D - spirost - 4 - en - 3 - one, 17b - acetoxy - 4 - methylandrosta-4 : 6-dien-3-one, 4-methyl-D-homotestosterone acetate, 4 : 6-dimethyl-androsta-4 : 6-diene-3 : 17-dione, 4-methyl-cholest-4-en-3-one, 4-methyl-stigmasta-4 : 22-dien-3-one, 4-methylergosta-4 : 7 : 22-trien-3-one, methyl 3-oxo-4-methylchol-4-en-24-oate, 4 : 7b -dimethyltestosterone acetate, 4-methyl-16a : 17a -dimethylmethylenedioxy-progesterone, 4-methypregna-4 : 11-diene-3 : 20-dione, 4-methyl- and 1 : 4-dimethyl-19-nor-testosterone acetates, 9a -fluoro-17a : 20 : 20 : 21-bis methylenedioxy-4-methylpregn-4-ene-3 : 11-dione, 4 : 14a -dimethyl-17a : 20 : 20 : 21-bismethylenedioxypregn-4-ene-3 : 11-dione, 4 : 14a -dimethylcortisone acetate, 20#x-acetoxy-4-methylpregn-4-en-3-one, 21-acetoxy-4-methylpregna-4 : 17(20)-dien-3-one, 3-oxo-4-methylpregna-4 : 17(20)-dien-21-oic acid and its ethyl ester, 14a -hydroxy-4-methylprogesterone, 17a : 20 : 20 : 21-bismethylenedioxy-4-methylpregna-4 : 14-diene-3 : 11-dione, 11b -hydroxy-4 : 11a -dimethyltestosterone-17-acetate, 20 : 20-ethylenedioxy - 4 - methylpregn - 4 - en - 3 - one, 11a - hydroxy - 4 - methyl - progesterone, 4 - methyl-pregn-4-ene-3 : 11 : 20-trione, 16a : 17b -diacetoxy-4-methylandrost-4-en-3-one, 16a : 17a -benzylidenedioxy-4-methylprogesterone, 20 : 20-ethylenedioxy - 17a - hydroxy - 4 - methylpregn - 4-en-3-one, 4 : 7 : 7-trimethylcholest-4-en-3-one and 21-acetoxy-20 : 20-ethylenedioxy-4-methylpregn-4-en-3-one by the process of the invention is described. The hydrolysis of the last named compound to the 21-hydroxy compound and then to 21-hydroxy-4-methylpregn-4-ene-3 : 20-dione. and the reacetylation of this also is described, as is the hydrolysis of many of the other acyloxy and alkylenedioxy products. 4-Phenylthiomethyltestosterone b -phenyl propionate, phenoxyacetate and p-chlorophenoxyacetate are all prepared from the free ol and the appropriate acid chloride. The Provisional Specification refers also to reduction with Raney cobalt and to the preparation of 6a -fluoro-4-methyl-testosterone acetate, 16a : 17a -dihydroxy - 4 - methyl - progesterone and 11a -acetoxy-4-methylprogesterone.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB37287/58A GB888165A (en) | 1958-11-19 | 1958-11-19 | Improvements in or relating to 4-methyl-3-oxo-í~-steroids |
| BE584788A BE584788A (en) | 1958-11-19 | 1959-11-18 | Steroid compounds and their preparation |
| CH8079159A CH380112A (en) | 1958-11-19 | 1959-11-19 | Verfahren zur Herstellung von Steroidverbindungen |
| FR837321A FR534M (en) | 1958-11-19 | 1960-08-31 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB37287/58A GB888165A (en) | 1958-11-19 | 1958-11-19 | Improvements in or relating to 4-methyl-3-oxo-í~-steroids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB888165A true GB888165A (en) | 1962-01-24 |
Family
ID=10395256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB37287/58A Expired GB888165A (en) | 1958-11-19 | 1958-11-19 | Improvements in or relating to 4-methyl-3-oxo-í~-steroids |
Country Status (4)
| Country | Link |
|---|---|
| BE (1) | BE584788A (en) |
| CH (1) | CH380112A (en) |
| FR (1) | FR534M (en) |
| GB (1) | GB888165A (en) |
-
1958
- 1958-11-19 GB GB37287/58A patent/GB888165A/en not_active Expired
-
1959
- 1959-11-18 BE BE584788A patent/BE584788A/en unknown
- 1959-11-19 CH CH8079159A patent/CH380112A/en unknown
-
1960
- 1960-08-31 FR FR837321A patent/FR534M/fr active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CH380112A (en) | 1964-07-31 |
| FR534M (en) | 1961-05-23 |
| BE584788A (en) | 1960-05-18 |
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