DE655458T1 - Neues Verfahren zur Herstellung von Finasteriden. - Google Patents
Neues Verfahren zur Herstellung von Finasteriden.Info
- Publication number
- DE655458T1 DE655458T1 DE0655458T DE95200270T DE655458T1 DE 655458 T1 DE655458 T1 DE 655458T1 DE 0655458 T DE0655458 T DE 0655458T DE 95200270 T DE95200270 T DE 95200270T DE 655458 T1 DE655458 T1 DE 655458T1
- Authority
- DE
- Germany
- Prior art keywords
- halide
- ester
- butylaminomagnesium
- alkyl
- bromide
- 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 abstract 15
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- -1 magnesium halide salt Chemical class 0.000 claims abstract 16
- 150000002148 esters Chemical class 0.000 claims abstract 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract 6
- 239000011777 magnesium Substances 0.000 claims abstract 6
- DBEPLOCGEIEOCV-WSBQPABSSA-N finasteride Chemical compound N([C@@H]1CC2)C(=O)C=C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)NC(C)(C)C)[C@@]2(C)CC1 DBEPLOCGEIEOCV-WSBQPABSSA-N 0.000 claims abstract 5
- 229960004039 finasteride Drugs 0.000 claims abstract 5
- 239000003960 organic solvent Substances 0.000 claims abstract 5
- 150000004792 aryl magnesium halides Chemical class 0.000 claims abstract 4
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 5
- 150000004820 halides Chemical class 0.000 claims 5
- 125000004122 cyclic group Chemical group 0.000 claims 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 3
- 150000001649 bromium compounds Chemical group 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 claims 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 150000005840 aryl radicals Chemical class 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- XEHVFKKSDRMODV-UHFFFAOYSA-N ethynyl Chemical group C#[C] XEHVFKKSDRMODV-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000012442 inert solvent Substances 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Chemical group 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P13/00—Drugs for disorders of the urinary system
- A61P13/08—Drugs for disorders of the urinary system of the prostate
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
- A61P17/10—Anti-acne agents
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P5/00—Drugs for disorders of the endocrine system
- A61P5/24—Drugs for disorders of the endocrine system of the sex hormones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J73/00—Steroids in which the cyclopenta[a]hydrophenanthrene skeleton has been modified by substitution of one or two carbon atoms by hetero atoms
- C07J73/001—Steroids in which the cyclopenta[a]hydrophenanthrene skeleton has been modified by substitution of one or two carbon atoms by hetero atoms by one hetero atom
- C07J73/005—Steroids in which the cyclopenta[a]hydrophenanthrene skeleton has been modified by substitution of one or two carbon atoms by hetero atoms by one hetero atom by nitrogen as hetero atom
-
- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N5/00—Details of television systems
- H04N5/74—Projection arrangements for image reproduction, e.g. using eidophor
- H04N5/7416—Projection arrangements for image reproduction, e.g. using eidophor involving the use of a spatial light modulator, e.g. a light valve, controlled by a video signal
- H04N5/7458—Projection arrangements for image reproduction, e.g. using eidophor involving the use of a spatial light modulator, e.g. a light valve, controlled by a video signal the modulator being an array of deformable mirrors, e.g. digital micromirror device [DMD]
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pharmacology & Pharmacy (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Multimedia (AREA)
- Signal Processing (AREA)
- Diabetes (AREA)
- Endocrinology (AREA)
- Urology & Nephrology (AREA)
- Dermatology (AREA)
- Steroid Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Confectionery (AREA)
- Dental Preparations (AREA)
- Seasonings (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
Claims (16)
1. Ein Verfahren zur Herstellung von Finasterid 2
jyje CONHtBu
worin R lineares, verzweigtes oder cyclisches C,-C10-A!kyl ist, das unsubstituiert
oder mit einem oder mehreren Phenyl-Resten substituiert ist, umfassend die
Schritte:
Schritte:
(1) inkontaktbringen des Esters _L mit t-Butyiaminomagnesiumhalogenid,
wobei das M &ogr; !verhältnis von t-Butylaminomagnesiumhalogenid zu Ester
wenigstens etwa 2:1 ist, in einem inerten organischen Lösungsmittel unter einer inerten Atmosphäre,
wobei das M &ogr; !verhältnis von t-Butylaminomagnesiumhalogenid zu Ester
wenigstens etwa 2:1 ist, in einem inerten organischen Lösungsmittel unter einer inerten Atmosphäre,
(2) Halten der Reaktionsmischung bei einer Temperatur von wenigstens 1O°C
und
(3) Gewinnen des Produkts Finasterid 2.
2. Das Verfahren nach Anspruch 1, ferner umfassend den Schritt, t-Butylamin
und ein aliphatisches Magnesiumhalogenid oder ein
Arylmagnesiumhalogenid in einem inerten organischen Lösungsmittel
umzusetzen, um das t-Butylaminomagnesiumhalogenid vor dem Kontakt mit dem Ester 1 zu bilden.
Arylmagnesiumhalogenid in einem inerten organischen Lösungsmittel
umzusetzen, um das t-Butylaminomagnesiumhalogenid vor dem Kontakt mit dem Ester 1 zu bilden.
3. Das Verfahren nach Anspruch 2, ferner umfassend den Schritt, den Ester
JL mit einem aliphatischen Magnesiumhalogenid oder einem Aryimagnesium-
0655
halogenid in dem Bereich von -2O°C bis 300C in einem inerten organischen
Lösungsmittel umzusetzen, um das Magnesiumhalogenidsalz des Esters 1 vor
dem Kontakt mit dem t-Butylaminomagnesiumhalogenid zu bilden.
4. Das Verfahren nach Anspruch 1, worin das Halogenid aus Bromid und Chlorid
ausgewählt ist.
5. Das Verfahren nach Anspruch 2, worin das aüphatische Magnesiumhalogenid/Arylmagnesiumhaiogenid
einen linearen, verzweigten oder cyclischen C1-C18-AIRyI-, Benzyl-, Allyl-, Vinyl- oder Ethinylrest enthält, und der Arylrest
Phenyl oder Phenyl, das mit 1-3 C1-C4-AIkYl, C1-C4-AIkOXy oder Fluor substituiert
ist, ist.
6. Das Verfahren nach Anspruch 5, worin das aliphatische Magnesiumhaiogenid/Arylmagnesiumhalogenid
aus einem Alkylmagnesiumbromid oder einem Cycloalkylmagnesiumbromid ausgewählt ist.
7. Das Verfahren nach Anspruch 1, worin das inerte Lösungsmittel ein
linearer oder cyclischer C4-C8-Ether ist.
8. Das Verfahren nach Anspruch 7, worin das inerte organische Lösungsmittel aus Diethylether, Di-n-butylether, Dimethoxyethan,
Tetrahydrofuran und Dioxan ausgewählt ist.
9. Das Verfahren nach Anspruch 1, worin R aus Methyl, Ethyl, Propyl und
Butyl ausgewählt ist.
10. Das Verfahren nach Anspruch 9, worin R Methyl ist.
11. Das Verfahren nach Anspruch 1, worin das Molverhältnis von t-Butylaminomagnesiumhaiogenid
zu Ester J. in dem Bereich von etwa 3,5:1 bis 5,5 zu 1 ist.
12. Das Verfahren nach Anspruch 11, worin das Molverhältnis von t-Butylaminomagnesiumhalogenid
zu Ester 1 in dem Bereich von etwa 4:1 bis 5:1 ist.
13. Eine Verbindung der Formel
CO2R
Halogenid
worin R lineares, verzweigtes oder cyclisches C1-C10-AIkYl ist, das unsubstituiert
oder mit einem oder mehreren Phenyl-Resten substituiert ist.
14. Die Verbindung nach Anspruch 13, worin das Halogenid aus Bromid und
Chlorid ausgewählt ist.
15. Die Verbindung t-Butylaminomagnesiumhalogenid.
16. Die Verbindung nach Anspruch 15, worin das Halogenid aus Bromid und
Chlorid ausgewählt ist.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US97853592A | 1992-11-19 | 1992-11-19 | |
| US08/010,734 US5468860A (en) | 1992-11-19 | 1993-01-29 | New finasteride processes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE655458T1 true DE655458T1 (de) | 1995-11-30 |
Family
ID=26681536
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE69323754T Expired - Fee Related DE69323754T2 (de) | 1992-11-19 | 1993-11-12 | Neues Verfahren zur Herstellung von Finasteriden |
| DE69317856T Expired - Lifetime DE69317856T2 (de) | 1992-11-19 | 1993-11-12 | Ein Verfahren zur Herstellung von Finasteride |
| DE0655458T Pending DE655458T1 (de) | 1992-11-19 | 1993-11-12 | Neues Verfahren zur Herstellung von Finasteriden. |
| DE0599376T Pending DE599376T1 (de) | 1992-11-19 | 1993-11-12 | Ein Verfahren zur Herstellung von Finasteride. |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE69323754T Expired - Fee Related DE69323754T2 (de) | 1992-11-19 | 1993-11-12 | Neues Verfahren zur Herstellung von Finasteriden |
| DE69317856T Expired - Lifetime DE69317856T2 (de) | 1992-11-19 | 1993-11-12 | Ein Verfahren zur Herstellung von Finasteride |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE0599376T Pending DE599376T1 (de) | 1992-11-19 | 1993-11-12 | Ein Verfahren zur Herstellung von Finasteride. |
Country Status (33)
| Country | Link |
|---|---|
| US (3) | US5468860A (de) |
| EP (3) | EP0655458B1 (de) |
| JP (2) | JPH07110875B2 (de) |
| CN (1) | CN1058018C (de) |
| AT (2) | ATE164850T1 (de) |
| AU (1) | AU658774B2 (de) |
| BG (2) | BG62362B1 (de) |
| CA (1) | CA2103107C (de) |
| CY (1) | CY2135B1 (de) |
| CZ (3) | CZ301191B6 (de) |
| DE (4) | DE69323754T2 (de) |
| DK (2) | DK0655458T3 (de) |
| DZ (1) | DZ1733A1 (de) |
| ES (2) | ES2052476T5 (de) |
| FI (4) | FI107450B (de) |
| GR (4) | GR940300045T1 (de) |
| HK (1) | HK1008338A1 (de) |
| HR (2) | HRP931410B1 (de) |
| HU (2) | HU216195B (de) |
| IL (1) | IL107574A (de) |
| IS (2) | IS1692B (de) |
| LV (2) | LV12212B (de) |
| MX (1) | MX9307222A (de) |
| MY (2) | MY110410A (de) |
| NO (3) | NO305912B1 (de) |
| PH (1) | PH31120A (de) |
| RO (2) | RO115164B1 (de) |
| RU (1) | RU2120445C1 (de) |
| SI (1) | SI9300603B (de) |
| SK (2) | SK286488B6 (de) |
| TW (1) | TW257766B (de) |
| UA (1) | UA41341C2 (de) |
| WO (1) | WO1994011387A2 (de) |
Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5468860A (en) * | 1992-11-19 | 1995-11-21 | Merck & Co., Inc. | New finasteride processes |
| IT1270660B (it) * | 1994-10-13 | 1997-05-07 | Poli Ind Chimica Spa | Procedimento microbiologico per la preparazione di 3-oxo-4-azasteroidi-17beta-carbossi sostituiti e uso dei prodotti come inibitori dell'enzima 5alfa-riduttasi |
| US5670643A (en) * | 1995-03-16 | 1997-09-23 | Glaxo Wellcome Inc. | Method for preparing finasteride |
| US5585383A (en) * | 1995-05-03 | 1996-12-17 | Merck & Co., Inc. | Process for crystallizing a 4-azasteroid 5alpha-reductase inhibitor |
| JPH11512434A (ja) * | 1995-09-15 | 1999-10-26 | メルク エンド カンパニー インコーポレーテッド | アンドロゲン過剰状態治療用の４−アザステロイド |
| GB2338234B (en) * | 1998-06-10 | 2000-05-03 | Torcan Chemical Ltd | Preparation of finasteride |
| ES2153789B1 (es) * | 1999-07-05 | 2001-10-16 | Raga Consultores S L | Procedimiento para la obtencion de 178-(n-terc-butlcarbamoil)-3-ona-4-aza-esteroides |
| EA200200524A1 (ru) * | 1999-11-01 | 2002-10-31 | Торкан Кемикал Лтд. | Получение полиморфных форм i и ii финастерида путем образования комплексов с солями металлов группы i или ii |
| CN1468254A (zh) * | 2000-09-07 | 2004-01-14 | 雷迪实验室有限公司 | 17-β-(N-叔丁基氨基甲酰基)-4-氮杂-5-α-雄甾-1-烯-3-酮的新颖多晶型物及其制备方法 |
| CZ2003679A3 (cs) * | 2000-09-07 | 2004-02-18 | Dr. Reddy´S Laboratories Ltd. | Nová polymorfní forma 17beta-(N-terc-butylkarbamoyl)-4-aza-5alfa-androst-1-en-3-on a způsob její přípravy |
| EP1322663A1 (de) * | 2000-09-07 | 2003-07-02 | Dr. Reddy's Laboratories Ltd. | Neue polymorphe form von 17-beta-(n-ter.butyl carbamoyl)-4-aza-5- g(a)-androst-1-en-3-one und ein verfahren zur ihrer herstellung |
| KR100415858B1 (ko) * | 2001-09-22 | 2004-01-24 | 한미약품 주식회사 | 17베타-(엔-3차-부틸카바모일)-3-온 스테로이드 화합물의제조방법 |
| CN100428897C (zh) * | 2002-08-16 | 2008-10-29 | 浙江寿峰堂生物工程有限公司 | 抗疲劳改善亚健康的保健食品及其制备方法 |
| ES2206065B1 (es) * | 2002-10-31 | 2005-08-16 | Ragactives, S.L. | Procedimiento para la obtencion de la forma polimorfica i de finasterida. |
| WO2004083230A1 (en) * | 2003-03-19 | 2004-09-30 | Hetero Drugs Limited | Novel crystalline forms of finasteride |
| EP1651661B1 (de) * | 2003-07-03 | 2008-08-27 | Cipla Ltd. | Verfahren zur herstellung von finasterid form i |
| US20050136015A1 (en) * | 2003-12-17 | 2005-06-23 | McKie Derrick B. | Topical use of halosalicylic acid derivatives |
| US20070167477A1 (en) * | 2006-01-13 | 2007-07-19 | Mandava Venkata Naga Brahmeswa | Processes to prepare finasteride polymorphs |
| US7531658B2 (en) * | 2006-01-20 | 2009-05-12 | Apotex Pharmachem Inc. | Process for the preparation of 17-N-substituted-carbamoyl-4-aza-androst-1-en-3-ones |
| EP1993569B1 (de) | 2006-02-03 | 2014-07-23 | OMP, Inc. | Behandlung gegen alterung mit kupfer- und zink-zusammensetzungen |
| US7897800B2 (en) | 2006-02-03 | 2011-03-01 | Jr Chem, Llc | Chemical compositions and methods of making them |
| US7687650B2 (en) | 2006-02-03 | 2010-03-30 | Jr Chem, Llc | Chemical compositions and methods of making them |
| US7867522B2 (en) | 2006-09-28 | 2011-01-11 | Jr Chem, Llc | Method of wound/burn healing using copper-zinc compositions |
| US20090076058A1 (en) * | 2007-09-17 | 2009-03-19 | Protia, Llc | Deuterium-enriched finasteride |
| US8273791B2 (en) | 2008-01-04 | 2012-09-25 | Jr Chem, Llc | Compositions, kits and regimens for the treatment of skin, especially décolletage |
| WO2009135799A2 (en) * | 2008-05-05 | 2009-11-12 | Abbott Gmbh & Co. Kg | Method for evaluating the solubility of a crystalline substance in a polymer |
| US20160184354A1 (en) | 2009-01-23 | 2016-06-30 | Jr Chem, Llc | Rosacea treatments and kits for performing them |
| US8952057B2 (en) | 2011-01-11 | 2015-02-10 | Jr Chem, Llc | Compositions for anorectal use and methods for treating anorectal disorders |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4760071A (en) * | 1984-02-27 | 1988-07-26 | Merck & Co., Inc. | 17β-N-monosubstituted carbamoyl-4-aza-5α-androst-1-en-3-ones which are active as testosterone 5α-reductase inhibitors |
| NZ211145A (en) | 1984-02-27 | 1988-10-28 | Merck & Co Inc | 4-aza-5-alpha-androst-1-en-3-ones and pharmaceutical compositions |
| DE3888378T2 (de) * | 1987-04-03 | 1994-09-29 | Merck & Co Inc | Behandlung von Prostatacarcinoma mit 17-beta-n-monosubstituierten-Carbamoyl-4-aza-5-alpha-Androst-1-en-3-onen. |
| NZ225100A (en) * | 1987-06-29 | 1991-09-25 | Merck & Co Inc | Reaction of steroids (including 4-azasteroids) with a silylating agent in the presence of a quinone to introduce a delta' double bond and silylated intermediates |
| US5084574A (en) * | 1988-04-18 | 1992-01-28 | Merck & Co., Inc. | Dehydrogenation process |
| US5237061A (en) * | 1988-10-31 | 1993-08-17 | Merck & Co., Inc. | Methods of synthesizing benign prostatic hypertropic agents and their intermediates |
| US5021575A (en) * | 1989-11-13 | 1991-06-04 | Merck & Co., Inc. | Method for introducing a 1,2 double bond into azasteroids |
| JP3282731B2 (ja) * | 1990-06-15 | 2002-05-20 | メルク エンド カムパニー インコーポレーテッド | 結晶の構造および大きさを改良する結晶化方法 |
| EP0462662A3 (en) * | 1990-06-20 | 1992-08-19 | Merck & Co. Inc. | 17beta-n-monosubstituted adamantyl/norbornanyl carbamoyl-4-aza-5alpha-androst-1-en-3-ones and androstan-3-ones |
| US5091534A (en) | 1990-08-27 | 1992-02-25 | Merck & Co., Inc. | Trialkylsilyl trifluoromethanesulfonate mediated α-methylenic carbon functionalization of 4-AZA-5α-androstan-3-one steroids |
| US5120847A (en) † | 1990-08-27 | 1992-06-09 | Merck & Co., Inc. | Process for iodinating or brominating the α-methylenic carbon of a secondary amide |
| US5061801A (en) * | 1990-09-24 | 1991-10-29 | Merck & Co., Inc. | Intermediate for making 3-oxo-4-aza-androst-1-ene 17β-ketones |
| CA2050824A1 (en) * | 1990-09-24 | 1992-03-25 | John M. Williams | Process for making 3-oxo-4-aza-androst-1-ene 17-.beta.-ketones |
| US5468860A (en) * | 1992-11-19 | 1995-11-21 | Merck & Co., Inc. | New finasteride processes |
-
1993
- 1993-01-29 US US08/010,734 patent/US5468860A/en not_active Expired - Fee Related
- 1993-11-05 CZ CZ20003686A patent/CZ301191B6/cs not_active IP Right Cessation
- 1993-11-05 SK SK1897-2000A patent/SK286488B6/sk not_active IP Right Cessation
- 1993-11-05 RU RU95112521A patent/RU2120445C1/ru active
- 1993-11-05 CZ CZ20003685A patent/CZ301160B6/cs not_active IP Right Cessation
- 1993-11-05 RO RO95-00940A patent/RO115164B1/ro unknown
- 1993-11-05 SK SK659-95A patent/SK281765B6/sk unknown
- 1993-11-05 WO PCT/US1993/010659 patent/WO1994011387A2/en active IP Right Grant
- 1993-11-05 RO RO99-00785A patent/RO115165B1/ro unknown
- 1993-11-05 IS IS4286A patent/IS1692B/is unknown
- 1993-11-05 UA UA95058438A patent/UA41341C2/uk unknown
- 1993-11-05 US US08/411,685 patent/US5652365A/en not_active Expired - Lifetime
- 1993-11-05 CZ CZ19951268A patent/CZ287842B6/cs not_active IP Right Cessation
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- 1993-11-11 TW TW082109464A patent/TW257766B/zh not_active IP Right Cessation
- 1993-11-12 ES ES93203163T patent/ES2052476T5/es not_active Expired - Lifetime
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- 1993-11-12 DK DK95200270T patent/DK0655458T3/da active
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- 1993-11-12 DE DE69323754T patent/DE69323754T2/de not_active Expired - Fee Related
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- 1993-11-12 DE DE0655458T patent/DE655458T1/de active Pending
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- 1993-11-12 DE DE0599376T patent/DE599376T1/de active Pending
- 1993-11-12 EP EP97201712A patent/EP0823436A3/de not_active Withdrawn
- 1993-11-12 EP EP93203163A patent/EP0599376B2/de not_active Expired - Lifetime
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- 1993-11-17 DZ DZ930120A patent/DZ1733A1/fr active
- 1993-11-18 HU HU9303275A patent/HU216195B/hu unknown
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1994
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1995
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1996
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1997
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1998
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1999
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2000
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2001
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2004
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