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WO2010084508A2 - Process for the preparation of type i, type ii and type iii crystalline prulifloxacin - Google Patents

Process for the preparation of type i, type ii and type iii crystalline prulifloxacin Download PDF

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Publication number
WO2010084508A2
WO2010084508A2 PCT/IN2009/000718 IN2009000718W WO2010084508A2 WO 2010084508 A2 WO2010084508 A2 WO 2010084508A2 IN 2009000718 W IN2009000718 W IN 2009000718W WO 2010084508 A2 WO2010084508 A2 WO 2010084508A2
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WO
WIPO (PCT)
Prior art keywords
type
prulifloxacin
acetonitrile
crystals
preparation
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.)
Ceased
Application number
PCT/IN2009/000718
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French (fr)
Other versions
WO2010084508A3 (en
Inventor
Rajiv Sakhardande
Manmohan Nimbalkar
Navin Khatri
Priti Jayesh Bhayani
Ravindra Prajapati
Azadkumar Sharma
Ashok Darekar
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Elder Pharmaceuticals Ltd
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Elder Pharmaceuticals Ltd
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Publication date
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Publication of WO2010084508A2 publication Critical patent/WO2010084508A2/en
Publication of WO2010084508A3 publication Critical patent/WO2010084508A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D513/00Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04Ortho-condensed systems

Definitions

  • the invention relates to the process for preparation of type I, type II and type III crystals of 6-fluoro-l-methyl-7-[4-[(5-methyl-2-oxo- l,3-dioxol-4-yl)methyl]-l-piperazinyl]-4-oxo-lH,4H-[l,3]Thiazeto[3,2-a]quinoline- 3-carboxylic acid.
  • 6-Fluoro-l-methyl-7-[4-[(5-methyl-2-oxo-l 5 3-dioxol-4-yl)methyl]-l-piperazinyl]-4- oxo-lH,4H-[l,3]Thiazeto[3,2-a]quinoline-3-carboxylic acid which is also known as Prulifloxacin is disclosed in US5086049 (JP 1294680 (A)).
  • the compound has an excellent antibacterial activity and is marketed as a synthetic antibacterial agent.
  • US5086049 describes the process to prepare Prulifloxacin and crude Prulifloxacin formed in the reaction that was recrystallised from chloroform - methanol (10 : 1) and the product obtained has M.P. 138°C - 140 0 C.
  • EP1626051A1 also mentioned type I, type II and type III crystals of Prulifloxacin obtained by crystallization from acetonitrile.
  • EP 1626051 describes the preparation of Type I and Type II crystals from acetonitrile by the addition of their respective seed crystals, but the means for preparation of seed crystals is not disclosed.
  • This application also discloses formation of type I 5 and type II crystal from solvents other than acetonitrile, however conditions of crystallization of type I and type II crystals are not reported.
  • Prulifloxacin is crystallized from acetonitrile with seed crystal of Type III or without addition of any seed crystal, resulted in the formation of an acetonitrile solvate of Prulifloxacin, referred to as "Compound B".
  • Pure crystal of Compound B is produced by setting the supersaturation concentration at the time of occurrence of spontaneous nucleus from acetonitrile solution of Prulifloxacin there by suppressing formation of type I and type II crystal of Prulifloxacin.
  • the Compound B is desolvated to get Type III crystals.
  • EP 1626051 teaches that Compound B needs to be prepared as an intermediate for the production of Type III crystals and Type III crystals as such are not directly obtainable by crystallization from acetonitrile, even if seeding is performed with Type III crystals.
  • the application provides several processes for the preparation of Compound B of Prulifloxacin from acetonitrile by controlling supersaturation concentration at the time of spontaneous nucleation or at the addition of Compound B seed crystals.
  • the process disclosed in EPl 626051 requires very controlled condition of crystallization and change in the condition of supersaturation concentration results into contaminated type III with type I crystal form.
  • WO2008111018 describes the process for the preparation of type I, II and III crystal form of Prulifloxacin. Preparation of type I, type II and type III crystals were carried out from acetonitrile solution by following different crystallization temperature at different cooling rate. Since type I, type II and type III crystals are isolated from the same solvent at different crystallizing temperature, at industrial level there are chances to get mixture of polymorph.
  • WO2008111018 teaches to cool the reaction mixture wherein the solvent is present. The cooling is for longer periods.
  • WO2008111018 teaches the reaction mixture to be cooled to about 25°C - 35 0 C.
  • the object of the present invention is to develop industrially feasible process to isolate pure crystalline form of Prulifloxacin.
  • Yet another object of the invention is to provide process to isolate Type I pure crystalline form of Prulifloxacin.
  • Yet another object of the invention is to provide process to isolate Type II pure crystalline form of Prulifloxacin.
  • Yet another object of the invention is to provide process to isolate Type III pure crystalline form of Prulifloxacin.
  • the invention relates to process for the preparation of pure type I, type II and type III crystals of 6-fluoro-l-methyl-7-[4-[(5-methyl-2-oxo-l,3-dioxol-4-yl)methyl]-l- piperazinyl] -4-oxo- 1 H,4H- [ 1 , 3 JThiazeto [3 ,2-a] quinoline-3 -carboxy lie acid .
  • a novel industrially feasible, simpler process for the preparation of type I crystals of Prulifloxacin which comprises, a) dissolving Prulifloxacin in acetonitrile by heating to a reflux temperature of solvent; b) distilling out substantial quantity of acetonitrile from the reaction mixture obtained in step a) which can be directly used for recycling; c) cool and filter the reaction mass obtained in step b); and d) isolating type I crystals of Prulifloxacin.
  • step a) Prulifloxacin is dissolved in acetonitrile by heating at a temperature of 75°C or more.
  • the reaction mass obtained in step b) is cooled to 35°C and solid was isolated and dried at 70 0 C - 85°C.
  • a process for the preparation of type II crystals of Prulifloxacin comprises, a) dissolving Prulifloxacin in acetonitrile by heating to a reflux temperature of solvent; b) adding water to the reaction mixture obtained in step a); c) cooling the reaction mixture obtained in step b); d) isolating the solid; and e) drying the solid to obtain type II crystals of Prulifloxacin.
  • step a) Prulifloxacin is dissolved in acetonitrile by heating at temperature of 75°C or more and water is added at 75°C - 80°C.
  • the reaction mixture obtained in step b) is cooled to 35°C - 0 0 C and the resulted solid was isolated and dried at 70 0 C - 80 0 C.
  • a process for the preparation of type III crystals of Prulifloxacin involves a) dissolving Prulifloxacin in acetonitrile by heating to a reflux temperature of solvent; b) quenching the reaction mass obtained in step a) in separately chilled acetonitrile; c) chilling the reaction mixture obtained in step b); d) isolating the solid; and e) drying the solid to obtain type III crystals of Prulifloxacin.
  • step a Prulifloxacin is dissolved in acetonitrile by heating at a temperature of 75 0 C or more.
  • acetonitrile is cooled to below 5°C and to this chilled acetonitrile, above reaction mass is added and the reaction mixture obtained from step b) is chilled to below 5°C and maintained for 2 hours. Solid isolated is dried at 75 0 C - 85°C to remove solvent.
  • Prulifloxacin used for the experiments is prepared according to the description of US5086049. Also for the preparation of type I, type II and type III solid, an y crystalline form of Prulifloxacin can be used.
  • Fig 1 represents XRPD of type I Prulifloxacin
  • Fig 2 represents XRPD of type II Prulifloxacin
  • Fig 3 represents XRPD of type III Prulifloxacin
  • Prulifloxacin 10 gm was dissolved in acetonitrile 750 ml at reflux temperature and maintained for 30 minutes with stirring. The acetonitrile was distilled out without stirring. The reaction mass was cooled to room temperature Product was isolated by filtration. The obtained product was dried at 80°C - 85°C to get type I crystals of Prulifloxacin 9.6 gm.
  • Prulifloxacin 10 gm was dissolved in acetonitrile 750 ml at reflux temperature of solvent and maintained for 30 minutes. Water 250 ml was added slowly to the reaction mixture and maintained for 15 minutes. The reaction mixture was cooled to room temperature and maintained for 1 hour. Product was isolated by filtration and suck dry. The obtained product was dried at 80°C - 85°C to get type II crystals of Prulifloxacin 5 gm.
  • Prulifloxacin 10 gm was dissolved in acetonitrile 750 ml at reflux temperature of solvent and maintained for 30 minutes.
  • acetonitrile 450 ml was charged and chilled to O 0 C - 5 0 C and quenched the above reaction mixture in the chilled acetonitrile.
  • the obtained reaction mixture is chilled to a temperature of 0°C - 5°C and maintained for 2 hours.
  • the reaction mixture was filtered and suck dried. The solid was dried under vacuum at 80°C - 85°C for 24 hours to get type III crystals of Prulifloxacin 7 gm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention relates to the process for the preparation of type I, type II and type III crystals of 6-fluoro-1-methyl-7-[4-[(5- methyl-2-oxo- 1,3 -dioxol-4-yl)methyl]- 1 -piperazinyl] -4-oxo- 1 H,4H- [1,3]Thiazeto[3,2-a]quinoline-3-carboxylic acid.

Description

Process for the preparation of Type I, Type II and Type III crystalline Prulifloxacin.
FIELD OF THE INVENTION: The invention relates to the process for preparation of type I, type II and type III crystals of 6-fluoro-l-methyl-7-[4-[(5-methyl-2-oxo- l,3-dioxol-4-yl)methyl]-l-piperazinyl]-4-oxo-lH,4H-[l,3]Thiazeto[3,2-a]quinoline- 3-carboxylic acid.
BACKGROUND OF THE INVENTION:
6-Fluoro-l-methyl-7-[4-[(5-methyl-2-oxo-l53-dioxol-4-yl)methyl]-l-piperazinyl]-4- oxo-lH,4H-[l,3]Thiazeto[3,2-a]quinoline-3-carboxylic acid which is also known as Prulifloxacin is disclosed in US5086049 (JP 1294680 (A)). The compound has an excellent antibacterial activity and is marketed as a synthetic antibacterial agent. US5086049 describes the process to prepare Prulifloxacin and crude Prulifloxacin formed in the reaction that was recrystallised from chloroform - methanol (10 : 1) and the product obtained has M.P. 138°C - 1400C.
In the prior art various solvents were studied for solubilizing Prulifloxacin, and acetonitrile was used for recrystallisation of Prulifloxacin which is resulted into type I, type II and type III crystals in descending order of melting temperature in the measurement by differential scanning calorimetry as mentioned in "Iyakuhin Kenkyu, vol. 28(1), pp. 1-11, 1987. However, the conditions of crystallization from acetonitrile for preparing type I, type II and type III crystals are not disclosed in the Iyakuhin Kenkyu, vol. 28(1), pp 1-11, 1987. Type III crystal has been placed in the market, based on the solubility, absorbability, and therapeutic effect of all the three types of crystal. EP1626051A1 also mentioned type I, type II and type III crystals of Prulifloxacin obtained by crystallization from acetonitrile. EP 1626051 describes the preparation of Type I and Type II crystals from acetonitrile by the addition of their respective seed crystals, but the means for preparation of seed crystals is not disclosed. This application also discloses formation of type I5 and type II crystal from solvents other than acetonitrile, however conditions of crystallization of type I and type II crystals are not reported.
According to EP 1626051, Prulifloxacin is crystallized from acetonitrile with seed crystal of Type III or without addition of any seed crystal, resulted in the formation of an acetonitrile solvate of Prulifloxacin, referred to as "Compound B". Pure crystal of Compound B is produced by setting the supersaturation concentration at the time of occurrence of spontaneous nucleus from acetonitrile solution of Prulifloxacin there by suppressing formation of type I and type II crystal of Prulifloxacin. The Compound B is desolvated to get Type III crystals. EP 1626051 teaches that Compound B needs to be prepared as an intermediate for the production of Type III crystals and Type III crystals as such are not directly obtainable by crystallization from acetonitrile, even if seeding is performed with Type III crystals. The application provides several processes for the preparation of Compound B of Prulifloxacin from acetonitrile by controlling supersaturation concentration at the time of spontaneous nucleation or at the addition of Compound B seed crystals. The process disclosed in EPl 626051 requires very controlled condition of crystallization and change in the condition of supersaturation concentration results into contaminated type III with type I crystal form.
WO2008111018 describes the process for the preparation of type I, II and III crystal form of Prulifloxacin. Preparation of type I, type II and type III crystals were carried out from acetonitrile solution by following different crystallization temperature at different cooling rate. Since type I, type II and type III crystals are isolated from the same solvent at different crystallizing temperature, at industrial level there are chances to get mixture of polymorph.
Hence there exists a need to improve the crystallization condition to isolate pure polymorph and to develop industrially feasible process.
To isolate Type I, WO2008111018 teaches to cool the reaction mixture wherein the solvent is present. The cooling is for longer periods.
According to WO2008111018, to isolate Type II, cooling to 0°C - 10°C in 5-20 minutes is critical using monosolvent system. Whereas, to obtain Type III crystals,
WO2008111018 teaches the reaction mixture to be cooled to about 25°C - 350C.
It is surprisingly found that it is possible to get type I crystals without cooling the mixture containing larger quantities of solvents. In fact present invention teaches to distill substantial amount of solvent, to obtain Type I crystals. It was surprisingly noticed that making use of additional solvent such as water provides Type II crystals, thereby eliminating the step of chilling to O0C - 10°C. Novelty of present invention also resides in providing Type III crystals by quenching as described in example. It was surprisingly found that when obtained reaction mixture is chilled to a temperature of below 50C and maintained for 2 hours, type III crystals are obtained which is in contrast to teachings of WO20081 11018. Novelty of the present invention also resides in the ability of the process to provide three types of crystals without making use of seeding.
OBJECTIVE OF THE INVENTION
The object of the present invention is to develop industrially feasible process to isolate pure crystalline form of Prulifloxacin.
Another object of the present invention is to provide simpler process to isolate pure crystalline form of Prulifloxacin. Yet another object of the invention is to provide a faster process to isolate pure crystalline forms of Prulifloxacin.
Yet another object of the invention is to provide process to isolate Type I pure crystalline form of Prulifloxacin.
Yet another object of the invention is to provide process to isolate Type II pure crystalline form of Prulifloxacin.
Yet another object of the invention is to provide process to isolate Type III pure crystalline form of Prulifloxacin.
SUMMARY OF THE INVENTION
The invention relates to process for the preparation of pure type I, type II and type III crystals of 6-fluoro-l-methyl-7-[4-[(5-methyl-2-oxo-l,3-dioxol-4-yl)methyl]-l- piperazinyl] -4-oxo- 1 H,4H- [ 1 , 3 JThiazeto [3 ,2-a] quinoline-3 -carboxy lie acid .
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the present invention there is provided a novel industrially feasible, simpler process for the preparation of type I crystals of Prulifloxacin which comprises, a) dissolving Prulifloxacin in acetonitrile by heating to a reflux temperature of solvent; b) distilling out substantial quantity of acetonitrile from the reaction mixture obtained in step a) which can be directly used for recycling; c) cool and filter the reaction mass obtained in step b); and d) isolating type I crystals of Prulifloxacin.
In step a), Prulifloxacin is dissolved in acetonitrile by heating at a temperature of 75°C or more. The reaction mass obtained in step b) is cooled to 35°C and solid was isolated and dried at 700C - 85°C.
In another aspect, a process for the preparation of type II crystals of Prulifloxacin is provided, which comprises, a) dissolving Prulifloxacin in acetonitrile by heating to a reflux temperature of solvent; b) adding water to the reaction mixture obtained in step a); c) cooling the reaction mixture obtained in step b); d) isolating the solid; and e) drying the solid to obtain type II crystals of Prulifloxacin.
In step a), Prulifloxacin is dissolved in acetonitrile by heating at temperature of 75°C or more and water is added at 75°C - 80°C. The reaction mixture obtained in step b) is cooled to 35°C - 00C and the resulted solid was isolated and dried at 700C - 800C.
In a further aspect, a process for the preparation of type III crystals of Prulifloxacin is discussed, which involves a) dissolving Prulifloxacin in acetonitrile by heating to a reflux temperature of solvent; b) quenching the reaction mass obtained in step a) in separately chilled acetonitrile; c) chilling the reaction mixture obtained in step b); d) isolating the solid; and e) drying the solid to obtain type III crystals of Prulifloxacin.
In step a), Prulifloxacin is dissolved in acetonitrile by heating at a temperature of 750C or more. In a separate reactor, acetonitrile is cooled to below 5°C and to this chilled acetonitrile, above reaction mass is added and the reaction mixture obtained from step b) is chilled to below 5°C and maintained for 2 hours. Solid isolated is dried at 750C - 85°C to remove solvent.
Prulifloxacin used for the experiments is prepared according to the description of US5086049. Also for the preparation of type I, type II and type III solid, an y crystalline form of Prulifloxacin can be used.
Hereunder, the present invention is explained in more detail with the following examples, However these illustrations do not limit the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS Fig 1 represents XRPD of type I Prulifloxacin Fig 2 represents XRPD of type II Prulifloxacin Fig 3 represents XRPD of type III Prulifloxacin
EXAMPLES
Example 1: Type I crystals of Prulifloxacin
Prulifloxacin 10 gm was dissolved in acetonitrile 750 ml at reflux temperature and maintained for 30 minutes with stirring. The acetonitrile was distilled out without stirring. The reaction mass was cooled to room temperature Product was isolated by filtration. The obtained product was dried at 80°C - 85°C to get type I crystals of Prulifloxacin 9.6 gm.
Example 2: Type II crystals of Prulifloxacin
Prulifloxacin 10 gm was dissolved in acetonitrile 750 ml at reflux temperature of solvent and maintained for 30 minutes. Water 250 ml was added slowly to the reaction mixture and maintained for 15 minutes. The reaction mixture was cooled to room temperature and maintained for 1 hour. Product was isolated by filtration and suck dry. The obtained product was dried at 80°C - 85°C to get type II crystals of Prulifloxacin 5 gm.
Example 3: Type III crystals of Prulifloxacin
Prulifloxacin 10 gm was dissolved in acetonitrile 750 ml at reflux temperature of solvent and maintained for 30 minutes. In another flask, acetonitrile 450 ml was charged and chilled to O0C - 50C and quenched the above reaction mixture in the chilled acetonitrile. The obtained reaction mixture is chilled to a temperature of 0°C - 5°C and maintained for 2 hours. The reaction mixture was filtered and suck dried. The solid was dried under vacuum at 80°C - 85°C for 24 hours to get type III crystals of Prulifloxacin 7 gm.

Claims

We claim,
1. A process for the preparation of type I crystals of Prulifloxacin, the process comprising: a) dissolving Prulifloxacin in acetonitrile by heating to a reflux temperature of solvent; b) distilling out a substantial amount of acetonitrile from the reaction mixture obtained in step a) to get reaction mass; c) cooling and filtering the reaction mass obtained in step b); and d) isolating type I crystals of Prulifloxacin.
2. A process to prepare type I crystal of Prulifloxacin as claimed in claim 1 , comprising distilling out acetonitrile.
3. A process for the preparation of type II crystals of Prulifloxacin, the process comprising: a) dissolving Prulifloxacin in acetonitrile by heating to a reflux temperature of solvent; b) adding water to the reaction mixture obtained in step a); c) cooling the reaction mixture obtained in step b); d) isolating the solid; and e) drying the solid to obtain type II crystals of Prulifloxacin.
4. A process to prepare type II crystals of Prulifloxacin as claimed in claim 3, from mixture of acetonitrile and water.
5. A process for the preparation of type III crystals of Prulifloxacin, the process comprising: a) dissolving Prulifloxacin in acetonitrile by heating to a reflux temperature of solvent; b) quenching the reaction mass obtained in step a) in separately chilled acetonitrile; c) chilling the reaction mixture obtained in step b); d) isolating the solid; and e) drying the solid to obtain type III crystals of Prulifloxacin.
6. A process to prepare type III crystal of Prulifloxacin as claimed in claim 5, by quenching solution of Prulifloxacin in cooled acetonitrile.
PCT/IN2009/000718 2009-01-14 2009-12-10 Process for the preparation of type i, type ii and type iii crystalline prulifloxacin Ceased WO2010084508A2 (en)

Applications Claiming Priority (2)

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IN96MU2009 2009-01-14
IN96/MUM/2009 2009-01-14

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WO2010084508A2 true WO2010084508A2 (en) 2010-07-29
WO2010084508A3 WO2010084508A3 (en) 2010-12-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012001357A1 (en) 2010-06-30 2012-01-05 Cipla Limited Crystalline form of prulifloxacin and processes for its preparation

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008111018A2 (en) * 2007-03-14 2008-09-18 Ranbaxy Laboratories Limited Process for the preparation of crystals of prulifloxacin

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012001357A1 (en) 2010-06-30 2012-01-05 Cipla Limited Crystalline form of prulifloxacin and processes for its preparation

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WO2010084508A3 (en) 2010-12-23

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