WO2002050063A1 - New process - Google Patents
New process Download PDFInfo
- Publication number
- WO2002050063A1 WO2002050063A1 PCT/IB2001/002338 IB0102338W WO0250063A1 WO 2002050063 A1 WO2002050063 A1 WO 2002050063A1 IB 0102338 W IB0102338 W IB 0102338W WO 0250063 A1 WO0250063 A1 WO 0250063A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- process according
- compound
- formula
- acid
- carried out
- Prior art date
Links
- YVIKDPVKTODAEI-MRXNPFEDSA-N CC([n]1c2ccc(C=C)cc2c(C[C@@H]2N(C)CCC2)c1)=O Chemical compound CC([n]1c2ccc(C=C)cc2c(C[C@@H]2N(C)CCC2)c1)=O YVIKDPVKTODAEI-MRXNPFEDSA-N 0.000 description 1
- OIBMCOJVJQEWDG-WQEMPZKUSA-N CN(CCC1)[C@H]1[IH]/C=C1/c(cc(CCS(c2ccccc2)(=O)=O)cc2)c2NC1 Chemical compound CN(CCC1)[C@H]1[IH]/C=C1/c(cc(CCS(c2ccccc2)(=O)=O)cc2)c2NC1 OIBMCOJVJQEWDG-WQEMPZKUSA-N 0.000 description 1
- JCXOJXALBTZEFE-GFCCVEGCSA-N CN1[C@@H](Cc2c[nH]c(cc3)c2cc3Br)CCC1 Chemical compound CN1[C@@H](Cc2c[nH]c(cc3)c2cc3Br)CCC1 JCXOJXALBTZEFE-GFCCVEGCSA-N 0.000 description 1
- XYUAXZDQSDTCHO-UHFFFAOYSA-N O=S(c1ccccc1)=O Chemical compound O=S(c1ccccc1)=O XYUAXZDQSDTCHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/40—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with one nitrogen as the only ring hetero atom, e.g. sulpiride, succinimide, tolmetin, buflomedil
- A61K31/403—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with one nitrogen as the only ring hetero atom, e.g. sulpiride, succinimide, tolmetin, buflomedil condensed with carbocyclic rings, e.g. carbazole
- A61K31/404—Indoles, e.g. pindolol
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P25/00—Drugs for disorders of the nervous system
- A61P25/06—Antimigraine agents
Definitions
- the present invention is concerned with an improved process for the preparation of the anti-migraine drug, (R)-5-(2-benzenesulphonylethyl)-3-N-methylpyrrolidin-2- ylmethyl)-1 H-indole (eletriptan), available commercially as the hydrobromide salt:
- European Patent No. 0592438 describes the preparation of eletriptan by the catalytic reduction of (R)-5-(2-benzenesulphonylethenyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1 H- indole, which compound is prepared by (i) reacting N-benzyloxycarbonyl-D-proline acid chloride with 5-bromoindole in the presence of a Grignard reagent, (ii) reducing the resulting (R)-3-(N-benzyloxycarbonylpyrrolidin-2-ylcarbonyl)-5-bromo-1 H-indole to give (R)-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1 H-indole and (iii) reacting same with phenyl vinyl sulphone in the presence of a palladium catalyst, a triarylphosphine and a base.
- this dimeric impurity reduces the yield of eletriptan, but, perhaps more importantly, it requires the costly and time-consuming removal of said dimer in order to provide hydrobromide salt of sufficient purity to meet the stringent standards required for regulatory approval.
- the process of the invention comprises the preparation of eletriptan by the hydrolysis of (R)-1-acetyl-5-(2-benzenesulphonylethyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1 H- indole, which compound may conveniently be prepared by (i) N-acetylating (R)-5- bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1 H-indole, (ii) reacting the resulting (R)-1- acetyl-5-bromo-3-(N-methylpyrrolidin-2-ylmethyl)-1 H-indole with phenyl vinyl sulphone in the presence of a palladium catalyst, a triarylphosphine and a base to give (R)-1-acetyl-5-(2-benzenesulphonylethyl)-3-(N-methylpyrrolidin-2-ylmethyl)-1 H- indole, which compound may conveniently be
- a process for the preparation of a compound of formula (I) which comprises hydrolysis of a compound of formula (II), typically under basic conditions, more especially potassium carbonate in methanol/water.
- the compound of formula (II) used in the process may be obtained by catalytic reduction of a compound of formula (III), typically using hydrogen or a hydrogen source in the presence of a suitable catalyst.
- the reduction is typically carried out using hydrogen at a pressure of from 1 to 15 atmospheres or using a hydrogen source such as ammonium formate or formic acid.
- Suitable catalysts include palladium on carbon, for example, 5% w/w Pd/C, Raney nickel, platinum oxide, rhodium, or ruthenium.
- the reduction is conveniently carried out in the presence of an acid, for example, methanesulphonic acid, acetic acid, or trifluoroacetic acid.
- the compound of formula (II) so obtained is conveniently slurried with cold aqueous tetrahydrofuran before hydrolysis to the compound of formula (I).
- the invention specifically provides the aforementioned compound of formula (II) which has not hitherto been described.
- the compound of formula (III) used in the process may be obtained by treating a compound of formula (IV) with phenyl vinyl sulphone in the presence of a palladium catalyst, a triarylphosphine and a base in accordance with the process described in Example 57 of US Patent 5,607,951.
- the compound of formula (IV) used in the process may be obtained by the N-acetylation of (R)-5-bromo-3-(N- methylpyrrolidin-2-ylmethyl)-1 H-indole, also in accordance with the process described in Example 57 of aforementioned US Patent No. 5,607,951.
- Eletriptan obtained by the process of the invention may be converted to a pharmaceutically acceptable acid addition salt by treatment with an appropriate acid; said conversion may conveniently be carried out in situ without isolation of the compound of formula (I).
- a particularly preferred salt is the hydrobromide obtained by treatment with hydrobromic acid.
- dimer-free eletriptan and pharmaceutically acceptable salts thereof, particularly the hydrobromide, and pharmaceutical compositions comprising same are also provided.
- certain steps may be 'telescoped' in order to reduce handling and accelerate processing time. For example, as indicated in step (a)(ii), drying the compound of formula (II) prior to hydrolysis may be avoided by using damp material slurried in aqueous tetrahydrofuran. Likewise, as indicated in step (c), isolation of the compound of formula (I) before conversion to a salt may be avoided by forming the salt in situ.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Chemical & Material Sciences (AREA)
- Pain & Pain Management (AREA)
- Biomedical Technology (AREA)
- Neurology (AREA)
- Neurosurgery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Epidemiology (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Indole Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2003-7008081A KR20030061448A (en) | 2000-12-20 | 2001-12-06 | New process |
IL15570601A IL155706A0 (en) | 2000-12-20 | 2001-12-06 | Process for the preparation of (r)-5-(2-benzenesulfonylethyl)-3-(n-methylpyrrolidin-2-ylmethyl)-1h-indole |
PL01362716A PL362716A1 (en) | 2000-12-20 | 2001-12-06 | New process |
AU2002218440A AU2002218440A1 (en) | 2000-12-20 | 2001-12-06 | New process |
BR0116324-8A BR0116324A (en) | 2000-12-20 | 2001-12-06 | Process |
HU0302465A HUP0302465A2 (en) | 2000-12-20 | 2001-12-06 | Improved process for preparation of eletriptan and pharmaceutical composition containing it |
AT01271106T ATE308539T1 (en) | 2000-12-20 | 2001-12-06 | PROCESS FOR PRODUCING THE ANTI-MIGRAINE ACTIVE ELETRIPTAN |
DE60114668T DE60114668T2 (en) | 2000-12-20 | 2001-12-06 | Process for the preparation of the anti-migraine drug Eletriptan |
JP2002551559A JP2004516290A (en) | 2000-12-20 | 2001-12-06 | New process |
MXPA03005569A MXPA03005569A (en) | 2000-12-20 | 2001-12-06 | New process. |
EP01271106A EP1373254B1 (en) | 2000-12-20 | 2001-12-06 | Process for the preparation of the anti-migraine drug eletriptan |
CA002432138A CA2432138C (en) | 2000-12-20 | 2001-12-06 | New process for the preparation of eletriptan |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0031094.6 | 2000-12-20 | ||
GBGB0031094.6A GB0031094D0 (en) | 2000-12-20 | 2000-12-20 | New Process |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002050063A1 true WO2002050063A1 (en) | 2002-06-27 |
Family
ID=9905487
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2001/002338 WO2002050063A1 (en) | 2000-12-20 | 2001-12-06 | New process |
Country Status (20)
Country | Link |
---|---|
EP (1) | EP1373254B1 (en) |
JP (1) | JP2004516290A (en) |
KR (1) | KR20030061448A (en) |
CN (1) | CN1199969C (en) |
AR (2) | AR035406A1 (en) |
AT (1) | ATE308539T1 (en) |
AU (1) | AU2002218440A1 (en) |
BR (1) | BR0116324A (en) |
CA (1) | CA2432138C (en) |
CZ (1) | CZ20031640A3 (en) |
DE (1) | DE60114668T2 (en) |
ES (1) | ES2249386T3 (en) |
GB (1) | GB0031094D0 (en) |
HU (1) | HUP0302465A2 (en) |
IL (1) | IL155706A0 (en) |
MX (1) | MXPA03005569A (en) |
PL (1) | PL362716A1 (en) |
RU (1) | RU2256660C2 (en) |
WO (1) | WO2002050063A1 (en) |
ZA (1) | ZA200303446B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6927296B2 (en) | 2003-07-23 | 2005-08-09 | Pfizer Inc. | Process |
WO2008137134A2 (en) * | 2007-05-01 | 2008-11-13 | Teva Pharmaceuticals Usa, Inc. | Amorphous eletriptan hydrobromide and process for preparing it and other forms of eletriptan hydrobromide |
ITMI20090678A1 (en) * | 2009-04-22 | 2010-10-23 | Italiana Sint Spa | SYNTHESIS OF 3 - {[(2R) -1-METHYLPYROLIDIN-2-IL] METHYL} -5- [2- (PHENILSULFONYL) ETYL] -1H-INDOL |
WO2011024039A1 (en) * | 2009-08-25 | 2011-03-03 | Ramesh Babu Potluri | Synthesis of novel 5-(2-(phenylsulfonyl)ethyl)-1h-indole derivatives |
US8754239B2 (en) | 2010-01-19 | 2014-06-17 | Sms Pharmaceuticals Limited | Process for preparing eletriptan hydrobromide having α-form |
WO2017125351A1 (en) | 2016-01-21 | 2017-07-27 | Laboratorios Lesvi Sl | Process for preparing (( r)-3-[(-1-methylpyrrolidin-2-yl)methyl]-5-(2-phenylsulfonylethyl)-1h-indole |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012004811A1 (en) * | 2010-07-06 | 2012-01-12 | Ind-Swift Laboratories Limited | Process for the preparation of 5-substsituted indole derivative |
CN112440631B (en) * | 2020-11-02 | 2022-09-13 | 长城汽车股份有限公司 | Tire pressure adjusting device, method and system and vehicle |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992006973A1 (en) * | 1990-10-15 | 1992-04-30 | Pfizer Inc. | Indole derivatives |
-
2000
- 2000-12-20 GB GBGB0031094.6A patent/GB0031094D0/en not_active Ceased
-
2001
- 2001-12-06 HU HU0302465A patent/HUP0302465A2/en unknown
- 2001-12-06 AT AT01271106T patent/ATE308539T1/en not_active IP Right Cessation
- 2001-12-06 AU AU2002218440A patent/AU2002218440A1/en not_active Abandoned
- 2001-12-06 IL IL15570601A patent/IL155706A0/en unknown
- 2001-12-06 CA CA002432138A patent/CA2432138C/en not_active Expired - Fee Related
- 2001-12-06 CZ CZ20031640A patent/CZ20031640A3/en unknown
- 2001-12-06 KR KR10-2003-7008081A patent/KR20030061448A/en not_active Application Discontinuation
- 2001-12-06 RU RU2003118330/04A patent/RU2256660C2/en not_active IP Right Cessation
- 2001-12-06 ES ES01271106T patent/ES2249386T3/en not_active Expired - Lifetime
- 2001-12-06 JP JP2002551559A patent/JP2004516290A/en active Pending
- 2001-12-06 WO PCT/IB2001/002338 patent/WO2002050063A1/en active IP Right Grant
- 2001-12-06 BR BR0116324-8A patent/BR0116324A/en not_active IP Right Cessation
- 2001-12-06 DE DE60114668T patent/DE60114668T2/en not_active Expired - Fee Related
- 2001-12-06 CN CNB018199674A patent/CN1199969C/en not_active Expired - Fee Related
- 2001-12-06 MX MXPA03005569A patent/MXPA03005569A/en active IP Right Grant
- 2001-12-06 PL PL01362716A patent/PL362716A1/en not_active Application Discontinuation
- 2001-12-06 EP EP01271106A patent/EP1373254B1/en not_active Expired - Lifetime
- 2001-12-18 AR ARP010105858A patent/AR035406A1/en unknown
-
2003
- 2003-05-06 ZA ZA200303446A patent/ZA200303446B/en unknown
-
2004
- 2004-02-03 AR ARP040100334A patent/AR043016A2/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1992006973A1 (en) * | 1990-10-15 | 1992-04-30 | Pfizer Inc. | Indole derivatives |
Non-Patent Citations (2)
Title |
---|
KOJIMA S ET AL: "Fluorescent Properties of Model Chromophores of Tyrosine-66 Substituted Mutants of Aequorea Green Fluorescent Protein (GFP)", TETRAHEDRON LETTERS, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 39, no. 29, 16 July 1998 (1998-07-16), pages 5239 - 5242, XP004162428, ISSN: 0040-4039 * |
WILLEMS, E. ET AL.: "Porcine carotid vascular effects of eletriptan (UK-116,044): a new 5-HT1b/1D receptor agonist with anti-migraine activity", NAUNYN-SCHMIEDEBERG'S ARCH PHARMACOL, vol. 358, no. 2, 1998, pages 212-219, XP002189843 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6927296B2 (en) | 2003-07-23 | 2005-08-09 | Pfizer Inc. | Process |
US7164030B2 (en) | 2003-07-23 | 2007-01-16 | Pfizer Inc. | Process |
WO2008137134A2 (en) * | 2007-05-01 | 2008-11-13 | Teva Pharmaceuticals Usa, Inc. | Amorphous eletriptan hydrobromide and process for preparing it and other forms of eletriptan hydrobromide |
WO2008137134A3 (en) * | 2007-05-01 | 2009-02-05 | Plus Chemicals Bv | Amorphous eletriptan hydrobromide and process for preparing it and other forms of eletriptan hydrobromide |
ITMI20090678A1 (en) * | 2009-04-22 | 2010-10-23 | Italiana Sint Spa | SYNTHESIS OF 3 - {[(2R) -1-METHYLPYROLIDIN-2-IL] METHYL} -5- [2- (PHENILSULFONYL) ETYL] -1H-INDOL |
WO2010121673A1 (en) * | 2009-04-22 | 2010-10-28 | F.I.S. Fabbrica Italiana Sintetici S.P.A. | Synthesis of 3-{[(2r)-1-methylpyrrolidin-2-yl]methyl}-5-[2-(phenylsulfonyl)ethyl]-1h-indole |
US8426612B2 (en) | 2009-04-22 | 2013-04-23 | F.I.S. Fabbrica Italiana Sintetici S.P.A. | Synthesis of 3-{[(2R)-1-methylpyrrolidin-2-yl]methyl}-5[2-(phenylsulfonyl)ethyl]-1H-indole |
WO2011024039A1 (en) * | 2009-08-25 | 2011-03-03 | Ramesh Babu Potluri | Synthesis of novel 5-(2-(phenylsulfonyl)ethyl)-1h-indole derivatives |
US8754239B2 (en) | 2010-01-19 | 2014-06-17 | Sms Pharmaceuticals Limited | Process for preparing eletriptan hydrobromide having α-form |
WO2017125351A1 (en) | 2016-01-21 | 2017-07-27 | Laboratorios Lesvi Sl | Process for preparing (( r)-3-[(-1-methylpyrrolidin-2-yl)methyl]-5-(2-phenylsulfonylethyl)-1h-indole |
Also Published As
Publication number | Publication date |
---|---|
EP1373254B1 (en) | 2005-11-02 |
AU2002218440A1 (en) | 2002-07-01 |
CA2432138A1 (en) | 2002-06-27 |
GB0031094D0 (en) | 2001-01-31 |
ATE308539T1 (en) | 2005-11-15 |
BR0116324A (en) | 2003-10-14 |
CN1199969C (en) | 2005-05-04 |
EP1373254A1 (en) | 2004-01-02 |
HUP0302465A2 (en) | 2003-12-29 |
AR035406A1 (en) | 2004-05-26 |
DE60114668D1 (en) | 2005-12-08 |
CN1487932A (en) | 2004-04-07 |
CA2432138C (en) | 2007-05-08 |
AR043016A2 (en) | 2005-07-13 |
ES2249386T3 (en) | 2006-04-01 |
MXPA03005569A (en) | 2003-10-06 |
DE60114668T2 (en) | 2006-07-20 |
PL362716A1 (en) | 2004-11-02 |
JP2004516290A (en) | 2004-06-03 |
RU2256660C2 (en) | 2005-07-20 |
ZA200303446B (en) | 2004-07-05 |
IL155706A0 (en) | 2004-02-19 |
KR20030061448A (en) | 2003-07-18 |
CZ20031640A3 (en) | 2004-08-18 |
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