WO2005012300A1 - A novel process for the manufacture of (+)-(s)-clopidogrel bisulfate form-i - Google Patents
A novel process for the manufacture of (+)-(s)-clopidogrel bisulfate form-i Download PDFInfo
- Publication number
- WO2005012300A1 WO2005012300A1 PCT/IB2003/003104 IB0303104W WO2005012300A1 WO 2005012300 A1 WO2005012300 A1 WO 2005012300A1 IB 0303104 W IB0303104 W IB 0303104W WO 2005012300 A1 WO2005012300 A1 WO 2005012300A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- clopidogrel
- clopidogrel bisulfate
- bisulfate form
- sulfuric acid
- solvent
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P7/00—Drugs for disorders of the blood or the extracellular fluid
- A61P7/02—Antithrombotic agents; Anticoagulants; Platelet aggregation inhibitors
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P9/00—Drugs for disorders of the cardiovascular system
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P9/00—Drugs for disorders of the cardiovascular system
- A61P9/10—Drugs for disorders of the cardiovascular system for treating ischaemic or atherosclerotic diseases, e.g. antianginal drugs, coronary vasodilators, drugs for myocardial infarction, retinopathy, cerebrovascula insufficiency, renal arteriosclerosis
Definitions
- the present invention relates to a novel process for the manufacture of blood-platelet aggregation inhibiting agent.
- the present invention is directed to a process for the manufacture of Methyl-(+)-(S)- ⁇ -(2-Chlorophenyl)-6,7-dihydrot eno[3,2-c]pyridine-5(4H)- acetate bisulfate Form - 1 of Formula:
- Clopidogrel is an inhibitor of platelet aggregation. Clopidogrel' s platelet inhibiting activity makes it an effective drug for reducing the induce of ischemic strokes or heart attacks. By inhibiting platelet aggregation, Clopidogrel reduces the chance of arterial blockage, thus preventing strokes and heart attacks. Recent studies have shown that Clopidogrel is more effective in blocking platelet aggregation than Asprin. Clopidogrel is much effective than Aspirin even at much lower dosage. In addition to being more effective, Clopidogrel produces much less gastrointestinal bleeding than Asprin. European patent 281459 describes the enantiomers of tetrahydrothieno pyridine derivatives and their pharmaceutically acceptable salts.
- Clopidogrel hydrogen sulfate i.e., the dextrorotatory isomer which posses an excellent platelet WCK 03/08/04 - 2 - aggregation inhibiting activity whereas the levo-rotatory isomer is less active.
- EP 281459 makes no reference to existence of the specific polymorphic forms of clopidigrel hydrogen sulfate.
- Dextro-rotatory isomer of Clopidogrel is prepared by salt formation from the racemic compound using an optically active acid such as 10-L-camphorsulphonic acid in acetone, followed by successive re-crystallization of the salt until a product with constant rotatory power is obtained, followed by release of dextro-rotatory, isomer from its salt by a base.
- Clopidogrel hydrogen sulfate is then obtained in standard manner by the dissolution of said base in acetone cooled in ice and addition of concentrated sulfuric acid to precipitation. The precipitate thus obtained is then isolated by filtration, washed and dried to give Clopidogrel hydrogen sulfate in the form of white crystals.
- Clopidogrel bisulfate Form I and II was first time disclosed in International Publication No. WO 99/65915, though Form-I is originally disclosed in EP 281459.
- US patent 6,429,210; 6,504,030 and US patent application 2002/019829 Al disclose the manufacturing process of Clopidogrel hydrogen sulfate Form - 1 and II. These polymorphs are prepared by dissolving Clopidogrel camphor sulfate in acetone followed by addition of cone, sulfuric acid at an ambient temperature.
- the present invention relates to a novel process for the preparation of Clopidogrel bisulfate or the bisulfate of methyl-(+)-(S)- ⁇ -(2-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2,- WCK/03/08/04 - 3 - c]pyridine-5-acetate. More particularly, the invention relates to a novel process for the preparation of Clopidogrel bisulfate Form-1 having Formula:
- Form-I obtained by this process is found to be stable and does not convert to any other forms. Apart from all these technical and economical advantages of the process according to the invention, excellent yields and very good quality of the desired product, viz., Clopidogrel bisulfate Form-I is obtained.
- the process is suitable for industrial scale. The following example illustrates the invention more clearly, without limiting its scope.
- (+)-(S)-Clopidogrel-camphor-sulfonate salt is filtered under suction to get (+)-(S)-Clopidogrel-camphor-sulfonate salt and washed with acetone which yielded 5.20 gm of product.
- the (+)-(S)-Clopidogrel is characterized on the basis of specific rotation based on literature and [O.] D 20 of (+)-(S)-Clopidogrel is found + 24.70° at a concentration of 1.68 gm/100 ml methanol.
- (+)-(S)-Clopidogrel bisulfate Form-I (+)-(S)-Clopidogrel, 4.50 gm (0.0139 mole) is dissolved in ethyl acetate 50 ml and seeded with (+)-(S)-Clopidogrel bisulfate Form-I (2.5 % of the weight of base).
- sulfuric acid 1.50 gm (0015 mole) is added at room temperature. After complete addition the reaction slurry is heated at reflux for 1 hour. Then it is stirred at room temperature for 1 hour.
- the (+)-(S)-Clopidogrel bisulfate Form-I is characterized by 1H NMR, 13 C NMR, mass and CHN analyses.
- the Form-I of (+)-(S)-Clopidogrel bisulfate has been confirmed on the basis of IR, XRD and melting point etc.
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pharmacology & Pharmacy (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Heart & Thoracic Surgery (AREA)
- Cardiology (AREA)
- Diabetes (AREA)
- Hematology (AREA)
- Urology & Nephrology (AREA)
- Vascular Medicine (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003253120A AU2003253120A1 (en) | 2003-08-04 | 2003-08-04 | A novel process for the manufacture of (+)-(s)-clopidogrel bisulfate form-i |
PCT/IB2003/003104 WO2005012300A1 (en) | 2003-08-04 | 2003-08-04 | A novel process for the manufacture of (+)-(s)-clopidogrel bisulfate form-i |
JP2005507351A JP2007516934A (en) | 2003-08-04 | 2003-08-04 | Novel process for the preparation of (+)-(S) -clopidogrel bisulfate form-I |
US10/564,364 US7291735B2 (en) | 2003-08-04 | 2003-08-04 | Process for the manufacture of (+)-(s)-clopidogrel bisulfate form-1 |
ES03817742T ES2387802T3 (en) | 2003-08-04 | 2003-08-04 | Novel process for the manufacture of bisulfate of (+) - (S) -clopidogrel form I |
CA002534893A CA2534893A1 (en) | 2003-08-04 | 2003-08-04 | A novel process for the manufacture of (+)-(s)-clopidogrel bisulfate form-i |
EP03817742A EP1651646B1 (en) | 2003-08-04 | 2003-08-04 | A novel process for the manufacture of (+)-(s)-clopidogrel bisulfate form-i |
BRPI0318449-8A BR0318449A (en) | 2003-08-04 | 2003-08-04 | process for manufacturing (+) - (s) -clopidogrel bisulfate forma-i |
AT03817742T ATE557028T1 (en) | 2003-08-04 | 2003-08-04 | NEW PROCESS FOR PRODUCING (+)-(S)- CLOPIDOGRELBISULPHATE FORM-I |
US11/896,853 US7482453B2 (en) | 2003-08-04 | 2007-09-06 | Process for the manufacture of (+)-(S)-clopidogrel bisulfate form-1 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/IB2003/003104 WO2005012300A1 (en) | 2003-08-04 | 2003-08-04 | A novel process for the manufacture of (+)-(s)-clopidogrel bisulfate form-i |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/564,364 A-371-Of-International US7291735B2 (en) | 2003-08-04 | 2003-08-04 | Process for the manufacture of (+)-(s)-clopidogrel bisulfate form-1 |
US11/896,853 Division US7482453B2 (en) | 2003-08-04 | 2007-09-06 | Process for the manufacture of (+)-(S)-clopidogrel bisulfate form-1 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005012300A1 true WO2005012300A1 (en) | 2005-02-10 |
Family
ID=34113359
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2003/003104 WO2005012300A1 (en) | 2003-08-04 | 2003-08-04 | A novel process for the manufacture of (+)-(s)-clopidogrel bisulfate form-i |
Country Status (9)
Country | Link |
---|---|
US (2) | US7291735B2 (en) |
EP (1) | EP1651646B1 (en) |
JP (1) | JP2007516934A (en) |
AT (1) | ATE557028T1 (en) |
AU (1) | AU2003253120A1 (en) |
BR (1) | BR0318449A (en) |
CA (1) | CA2534893A1 (en) |
ES (1) | ES2387802T3 (en) |
WO (1) | WO2005012300A1 (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1740593A1 (en) | 2004-04-19 | 2007-01-10 | KRKA, tovarna zdravil, d.d., Novo mesto | Processes for the preparation of clopidogrel hydrogen sulfate polymorphic form i |
WO2007017886A1 (en) * | 2005-08-11 | 2007-02-15 | Arch Pharmalabs Limited | Novel process for preparation of clopidogrel bisulphate polymorphic form i |
WO2008034912A2 (en) * | 2006-09-22 | 2008-03-27 | Krka, Tovarna Zdravil, D.D., Novo Mesto | Process for the synthesis of clopidogrel and new forms of pharmaceutically acceptable salts thereof |
WO2008118030A1 (en) * | 2007-03-23 | 2008-10-02 | Tomasz Kozluk | Process for preparation of pure polymorphic form 1 of clopidogrel hydrogensulfate |
WO2008146249A1 (en) * | 2007-05-30 | 2008-12-04 | Wockhardt Research Centre | Processes for the preparation of clopidogrel |
EP2107061A1 (en) | 2008-04-02 | 2009-10-07 | Krka Tovarna Zdravil, D.D., Novo Mesto | Process for the preparation of optically enriched clopidogrel |
WO2009156279A2 (en) * | 2008-06-24 | 2009-12-30 | Zach System S.P.A. | Process for the preparation of clopidogrel hydrogen sulfate crystalline form i |
US7714133B2 (en) * | 2002-08-27 | 2010-05-11 | Zentiva, K.S. | Method for manufacturing crystalline form I of clopidogrel hydrogen sulphate |
WO2011125069A1 (en) | 2010-03-22 | 2011-10-13 | Rpg Life Sciences Limited | A process for preparation of crystalline form i of clopidogrel bisulfate |
CN102796114A (en) * | 2011-05-25 | 2012-11-28 | 浙江京新药业股份有限公司 | Method for preparing (+)-(S-)-clopidogrel hydrogen sulfate 1 crystal form |
CN103193792A (en) * | 2013-03-13 | 2013-07-10 | 广东中科药物研究有限公司 | New compound for treating ischemic cardiovascular and cerebrovascular diseases |
US8907090B2 (en) * | 2003-11-03 | 2014-12-09 | Cadila Healthcare Limited | Processes for preparing different forms of (S)-(+)-Clopidogrel bisulfate |
KR20160142578A (en) | 2015-06-03 | 2016-12-13 | 경동제약 주식회사 | Method for preparing crystalline form I of Clopidogrel hydrogen sulfate |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005012300A1 (en) * | 2003-08-04 | 2005-02-10 | Wockhardt Limited | A novel process for the manufacture of (+)-(s)-clopidogrel bisulfate form-i |
US20060223845A1 (en) * | 2005-02-24 | 2006-10-05 | Eran Turgeman | Clopidogrel base suitable for pharmaceutical formulation and preparation thereof |
US7772398B2 (en) * | 2005-03-11 | 2010-08-10 | Dr. Reddy's Laboratories, Inc. | Process for making crystalline form I of clopidogrel hydrogen sulphate |
WO2008019053A2 (en) * | 2006-08-03 | 2008-02-14 | Teva Pharmaceutical Industries Ltd. | Process for preparing clopidogrel bisulphate |
WO2011042804A2 (en) | 2009-10-08 | 2011-04-14 | Jubliant Life Sciences Limited | An improved process for the preparation of clopidogrel hydrogen sulfate form i |
WO2014118802A1 (en) | 2013-01-31 | 2014-08-07 | Pharmazell Gmbh | An improved process for the preparation of clopidogrel bisulfate form-i |
CN107337683B (en) * | 2017-08-16 | 2019-08-16 | 中荣凯特(北京)生物科技有限公司 | A kind of crystal form II of thienopyridine analog derivative disulfate and its preparation method and application |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6429210B1 (en) * | 1998-06-15 | 2002-08-06 | Sanofi-Synthelabo | Polymorphic clopidogrel hydrogenesulphate form |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CZ297472B6 (en) * | 2002-08-27 | 2006-12-13 | Zentiva, A.S. | Process for preparing crystalline form I of clopidogrel hydrogen sulfate |
WO2005012300A1 (en) * | 2003-08-04 | 2005-02-10 | Wockhardt Limited | A novel process for the manufacture of (+)-(s)-clopidogrel bisulfate form-i |
-
2003
- 2003-08-04 WO PCT/IB2003/003104 patent/WO2005012300A1/en active Application Filing
- 2003-08-04 EP EP03817742A patent/EP1651646B1/en not_active Expired - Lifetime
- 2003-08-04 ES ES03817742T patent/ES2387802T3/en not_active Expired - Lifetime
- 2003-08-04 US US10/564,364 patent/US7291735B2/en not_active Expired - Fee Related
- 2003-08-04 JP JP2005507351A patent/JP2007516934A/en not_active Abandoned
- 2003-08-04 AT AT03817742T patent/ATE557028T1/en active
- 2003-08-04 AU AU2003253120A patent/AU2003253120A1/en not_active Abandoned
- 2003-08-04 BR BRPI0318449-8A patent/BR0318449A/en not_active IP Right Cessation
- 2003-08-04 CA CA002534893A patent/CA2534893A1/en not_active Abandoned
-
2007
- 2007-09-06 US US11/896,853 patent/US7482453B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6429210B1 (en) * | 1998-06-15 | 2002-08-06 | Sanofi-Synthelabo | Polymorphic clopidogrel hydrogenesulphate form |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7714133B2 (en) * | 2002-08-27 | 2010-05-11 | Zentiva, K.S. | Method for manufacturing crystalline form I of clopidogrel hydrogen sulphate |
US8907090B2 (en) * | 2003-11-03 | 2014-12-09 | Cadila Healthcare Limited | Processes for preparing different forms of (S)-(+)-Clopidogrel bisulfate |
EP1740593A1 (en) | 2004-04-19 | 2007-01-10 | KRKA, tovarna zdravil, d.d., Novo mesto | Processes for the preparation of clopidogrel hydrogen sulfate polymorphic form i |
NO339878B1 (en) * | 2004-04-19 | 2017-02-13 | Krka Tovarna Zdravil Dd | Process for Preparation of Clopidogrel Hydrogen Sulfate Polymorph Form I |
WO2007017886A1 (en) * | 2005-08-11 | 2007-02-15 | Arch Pharmalabs Limited | Novel process for preparation of clopidogrel bisulphate polymorphic form i |
WO2008034912A2 (en) * | 2006-09-22 | 2008-03-27 | Krka, Tovarna Zdravil, D.D., Novo Mesto | Process for the synthesis of clopidogrel and new forms of pharmaceutically acceptable salts thereof |
WO2008034912A3 (en) * | 2006-09-22 | 2008-08-07 | Krka Tovarna Zdravil D D Novo | Process for the synthesis of clopidogrel and new forms of pharmaceutically acceptable salts thereof |
WO2008118030A1 (en) * | 2007-03-23 | 2008-10-02 | Tomasz Kozluk | Process for preparation of pure polymorphic form 1 of clopidogrel hydrogensulfate |
US7985859B2 (en) | 2007-05-30 | 2011-07-26 | Wockhardt Ltd. | Processes for the preparation of clopidogrel |
WO2008146249A1 (en) * | 2007-05-30 | 2008-12-04 | Wockhardt Research Centre | Processes for the preparation of clopidogrel |
EP2107061A1 (en) | 2008-04-02 | 2009-10-07 | Krka Tovarna Zdravil, D.D., Novo Mesto | Process for the preparation of optically enriched clopidogrel |
WO2009156279A2 (en) * | 2008-06-24 | 2009-12-30 | Zach System S.P.A. | Process for the preparation of clopidogrel hydrogen sulfate crystalline form i |
WO2009156279A3 (en) * | 2008-06-24 | 2011-01-13 | Zach System S.P.A. | Process for the preparation of clopidogrel hydrogen sulfate crystalline form i |
WO2011125069A1 (en) | 2010-03-22 | 2011-10-13 | Rpg Life Sciences Limited | A process for preparation of crystalline form i of clopidogrel bisulfate |
CN102796114A (en) * | 2011-05-25 | 2012-11-28 | 浙江京新药业股份有限公司 | Method for preparing (+)-(S-)-clopidogrel hydrogen sulfate 1 crystal form |
CN103193792A (en) * | 2013-03-13 | 2013-07-10 | 广东中科药物研究有限公司 | New compound for treating ischemic cardiovascular and cerebrovascular diseases |
KR20160142578A (en) | 2015-06-03 | 2016-12-13 | 경동제약 주식회사 | Method for preparing crystalline form I of Clopidogrel hydrogen sulfate |
Also Published As
Publication number | Publication date |
---|---|
AU2003253120A1 (en) | 2005-02-15 |
US20080051581A1 (en) | 2008-02-28 |
US7291735B2 (en) | 2007-11-06 |
ATE557028T1 (en) | 2012-05-15 |
BR0318449A (en) | 2006-08-01 |
EP1651646A4 (en) | 2007-03-21 |
EP1651646B1 (en) | 2012-05-09 |
ES2387802T3 (en) | 2012-10-02 |
CA2534893A1 (en) | 2005-02-10 |
EP1651646A1 (en) | 2006-05-03 |
US20060183907A1 (en) | 2006-08-17 |
US7482453B2 (en) | 2009-01-27 |
JP2007516934A (en) | 2007-06-28 |
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