EP1086109A4 - Verfahren zur herstellung kristalliner amoxycillinsalze - Google Patents
Verfahren zur herstellung kristalliner amoxycillinsalzeInfo
- Publication number
- EP1086109A4 EP1086109A4 EP99955267A EP99955267A EP1086109A4 EP 1086109 A4 EP1086109 A4 EP 1086109A4 EP 99955267 A EP99955267 A EP 99955267A EP 99955267 A EP99955267 A EP 99955267A EP 1086109 A4 EP1086109 A4 EP 1086109A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- amoxycillin
- process according
- salt
- solution
- sodium
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D499/00—Heterocyclic compounds containing 4-thia-1-azabicyclo [3.2.0] heptane ring systems, i.e. compounds containing a ring system of the formula:, e.g. penicillins, penems; Such ring systems being further condensed, e.g. 2,3-condensed with an oxygen-, nitrogen- or sulfur-containing hetero ring
- C07D499/04—Preparation
- C07D499/14—Preparation of salts
- C07D499/16—Preparation of salts of alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D499/00—Heterocyclic compounds containing 4-thia-1-azabicyclo [3.2.0] heptane ring systems, i.e. compounds containing a ring system of the formula:, e.g. penicillins, penems; Such ring systems being further condensed, e.g. 2,3-condensed with an oxygen-, nitrogen- or sulfur-containing hetero ring
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
Definitions
- This invention relates to a process for the preparation of crystalline salts of the beta lactam antibiotic amoxycillin viz. 6-[[amino (4-hydroxyphenyl)acetyl]-amino]-3,3- dimethyl-7-oxo-4-thia-l-azabicyclo [3.2.0] heptane-2-carboxylic acid.
- this invention relates to a process for the preparation of crystalline sodium amoxycillin.
- Crystalline sodium amoxycillin is a known substance and processes for its preparation are disclosed in the state of the art.
- EP 0131147 A discloses a process in which amoxycillin trihydrate is converted into a crystalline solvate of sodium amoxycillin from which the solvating solvent is removed.
- amoxycillin trihydrate is suspended in methyl acetate, then a solution of a mixture of triethylamine and sodium 2-ethylhexanoate is added to this suspension.
- amoxycillin trihydrate is dissolved in a methyl acetate / isopropanol / triethylamine mixture, then this solution is added to a solution of sodium 2-ethylhexanoate in a methyl acetate / methanol mixture.
- a crystalline solvate of sodium amoxycillin is believed to crystallize out from the reaction mixture, from which the solvating solvent is removed.
- amoxycillin trihydrate is added to an ethanol / triethylamine mixture to form a solution which is then reacted with sodium 2-ethylhexanoate in ethanolic solution, and a crystalline product is obtained.
- amoxycillin trihydrate is suspended in a mixture of an aprotic solvent, such as methylene chloride, and a lower alcohol, the amoxycillin is solubilized using a low molecular weight amine, and to this mixture is added the sodium salt of diethyloxalacetic acid. Sodium amoxycillin is then precipitated by addition of more of the aprotic solvent.
- a process for the preparation of a crystalline alkali metal salt of amoxycillin in which; a suspension of an amine salt of amoxycillin is formed in a first organic solvent, the suspension is admixed with a second organic solvent and the amine salt is caused to enter solution in the so-formed mixture of first and second organic solvents, the amine salt is reacted with a salifying compound of the alkali metal, the so-formed alkali metal salt of amoxycillin is isolated from the solution as a crystalline product.
- the process of the invention it is believed that the formation of the suspension of the amine salt in the first solvent, and rapid dissolution of the salt when the second organic solvent l-5is admixed, leads to decreased breakdown of the amoxycillin, and consequently increased yield and purity of the crystalline product.
- the reagents are formed into solution, which facilitates sterilising filtration and consequent use of the product as an injectible pharmaceutical product.
- the process of the present invention may equally effectively be used without a sterile filtration step to prepare crystalline sodium amoxycillin which may be administered orally.
- the crystalline alkali metal salt of amoxycillin prepared by the process of this invention is crystalline sodium amoxycillin.
- the amine salt of amoxycillin is a salt of a tri- or di- (Cl-51-5)alkyl amine, such as triethylamine, diethylamine or diisopropylamine, especially the triethylamine, salt of amoxycillin.
- a mixture of amine salts may be used such as a mixture of the salts of amoxycillin with triethylamine and diisopropylamine.
- Other suitable amine salts include the salt with dicyclohexylamine.
- a preferred first organic solvent is a (Cl-51-5)alkyl (Cl-51-5)alkanoate ester, a preferred such ester being a (Cl-51-5)alkyl acetate ester, particularly methyl acetate.
- the first organic solvent may comprise a single solvent or a mixture of solvents, for example a mixture of said esters or said esters and other co-solvents.
- the suspension is formed by first forming a suspension of amoxycillin, preferably in the form of amoxycillin trihydrate, in the first organic solvent then admixing the amine with this suspension so that the amine reacts with the amoxycillin to form the amine salt.
- This reaction is preferably carried out at below ambient temperature, for example below 10°C, especially at 0-5°C.
- the amoxycillin trihydrate may be suspended in a volume of methyl acetate at a ratio weight of amoxycillin trihydrate : volume of methyl acetate ca. 1 : 1 - 1 :2.5, for example typically 1 : 1.7 - 1 : 2, and this suspension may be admixed with the triethylamine in a stoichiometric excess to the amoxycillin, for example at a molar ratio amoxycillin : triethylamine 1 : 1 - 1 :2, for example typically 1:1.3 - 1:1.5.
- a suitable second organic solvent with which the suspension of the amine salt may be admixed is a (Cl-51-5)alcohol, such as methyl alcohol, which is preferred, or ethyl alcohol, propyl alcohol e.g. isopropyl alcohol, or butyl alcohol e.g. iso-butyl alcohol.
- the second organic solvent may comprise a single solvent or a mixture of solvents, for example a mixture of said alcohols or said alcohols and other co-solvents.
- the admixing of the second solvent and the suspension of the amine salt in the first solvent causes the salt to enter solution, and the volume of the second solvent e.g. the alcohol used may be determined experimentally as the minimum volume of the second solvent necessary to achieve this.
- the first solvent is the above-described ester and the second solvent is the above-described alcohol a volume ratio ester : alcohol of ca. 1: 0.3 - 0.6 will be found suitable, e.g. about 1 : 0.4-0.5 of methyl acetate : methyl alcohol. If such a volume ratio of methyl alcohol is admixed with the above-described suspension of the triethylamine salt of amoxycillin then the salt generally dissolves immediately upon stirring.
- the so-formed solution of the amine salt of amoxycillin may for example be filtered and/or treated by other standard purification steps e.g. treatment with dicalite or other materials which selectively absorb impurities. If the solution is filtered the filter medium may subsequently be washed with more of the second solvent e.g. the alcohol, e.g. corresponding to an amount 0.5 - 1.0 of the amount already in admixture with the solution of the salt.
- the second solvent e.g. the alcohol
- a suitable salifying compound is a pharmaceutically acceptable salifying compound of a suitable alkali metal, for example the sodium salt of an organic compound, for example an alcoholate such as of a (Cl-51-5)alcohol e.g. the methoxide and/or ethoxide, or a salt of an organic acid e.g. a (C 1-121-5) carboxylic acid such as an alkyl substituted- alkanoate for example a 2-ethylhexanoate.
- a suitable salifying compound for example the sodium salt of an organic compound, for example an alcoholate such as of a (Cl-51-5)alcohol e.g. the methoxide and/or ethoxide, or a salt of an organic acid e.g. a (C 1-121-5) carboxylic acid such as an alkyl substituted- alkanoate for example a 2-ethylhexanoate.
- a suitable salifying compound for example the sodium salt of an organic compound, for
- the reaction of the amine salt is suitably carried out by admixing the solution of the amine salt with a solution of the salifying compound.
- the salifying compound is in solution in a solvent mixture which comprises the abovementioned first and second organic solvents, e.g. the abovementioned (Cl-51-5)alkyl (Cl-51-5)alkanoate ester and (Cl-51-5)alcohol, for example a methyl acetate : methanol mixture comprising predominantly the ester, for example a 9-12 : 1 v:v, e.g. 10-1 1 : 1 v:v methyl acetate : methanol mixture.
- a stoichiometric excess of the salifying compound relative to the amoxycillin is used, e.g. a 1.5 - 2.5 : 1 molar ratio of sodium 2-ethyl hexanoate : amoxycillin.
- a solution of sodium 2-ethylhexanoate in the abovementioned solvent mixture which is of concentration around 1.8 - 2.5 M may be used. This solution may be filtered and/or subjected to other appropriate purification steps before the reaction with the amoxycillin.
- the reaction between the salifying compound and the amoxycillin is carried out at below ambient temperature, e.g. below 10°C, especially at 0-5°C.
- the solution of the amine salt is added to the solution of the salifying compound, although the reverse mode of addition, i.e. addition of the solution of the salifying compound to the solution of the amine salt, or concurrent admixing, may be used.
- the mixing of the two solutions is carried out as fast as possible, with rapid stirring.
- Spontaneous crystallization of the reaction product may occur, but it is preferred to induce crystallization by the addition of seed crystals, e.g. of crystalline sodium amoxycillin or some crystallographically equivalent material e.g. a solvate of crystalline sodium amoxycillin, to the reaction mixture immediately after the mixing of the solutions.
- seed crystals e.g. of crystalline sodium amoxycillin or some crystallographically equivalent material e.g. a solvate of crystalline sodium amoxycillin
- seed crystals e.g. of crystalline sodium amoxycillin or some crystallographically equivalent material e.g. a solvate of crystalline sodium amoxycillin
- some crystallographically equivalent material e.g. a solvate of crystalline sodium amoxycillin
- first organic solvent e.g. the (Cl-51-5)alkyl (Cl-51-5)alkanoate ester, e.g. methyl acetate
- This admixing of the first organic solvent may be carried out relatively slowly, e.g. over a period of ca. 30-40 minutes. After the admixing of this further amount of the first solvent the mixture may be stirred for a time, e.g. ca. 1 hour preferably below ambient temperature, e.g. below 10°C, especially at 0-5°C.
- the crystalline product may be separated off from the reaction medium using standard procedures, e.g. filtered off, and washed with a suitable wash liquid, preferably the first organic solvent.
- a suitable wash liquid preferably the first organic solvent.
- the crystalline product obtained in this way is believed to be a crystalline solvate of sodium amoxycillin, e.g. the methyl acetate solvate from which the solvating solvent may be removed by a drying process, e.g. the process disclosed in EP 0131147 A, the contents of which are incorporated herein by reference.
- This drying process may be in vacuum preferably at an elevated temperature such as 50-65°C, for example 60-65°C to remove residual reaction medium solvents, wash liquids and solvating solvents, to yield the crystalline alkali metal salt of amoxycillin.
- Crystalline sodium amoxycillin prepared by the process of this invention may be used as a pharmaceutical antibiotic product e.g. in injectible form. For this purpose it may be provided contained in sealed sterile vials. Alternatively the sodium amoxycillin prepared by the process of this invention may be used in formulations for oral administration e.g. in tablet, granule, syrup etc formulations and for oral administration sterile formulation is not necessarily required.
- the product crystalline alkali metal salt of amoxycillin is administered in combination with a pharmaceutically acceptable beta-lactamase inhibitor such as a salt of clavulanic acid, particularly potassium clavulanate.
- Example 1 Laboratory Scale.
- Amoxycillin trihydrate 250g was slurried in methyl acetate (450ml). Triethylamine (120 ml) was added to the slurry creating a thick suspension. Methanol (200ml) was added, causing the amoxycillin triethylamine salt to dissolve instantly. The solution was stirred for 5 minutes before dicalite ( 1 Og) was added and the mixture was allowed to stir for a further 5 minutes. The solution was then filtered through Whatman No. 1 filter paper followed by a wash with methanol (120ml) and transferred to the crystallization vessel containing sodium 2-ethyl hexanoate from 1.1 above.
- the crystalline product from 1.3 was dried under vacuum at 50-55°C for 36 hours, or alternatively at 65°C for the shorter period of 16 hours. Product quality was found to be unaffected by the drying temperature. The product was confirmed to be crystalline sodium amoxycillin by chemical analysis, infrared spectroscopy and X-ray powder diffractometry.
- the product obtained had an amoxycillin content of 91.0%, with a total content of impurities of 2.13 - 2.16%.
- Example 2 Scale up.
- Methyl acetate (124L) was added to sodium 2-ethyl hexanoate (64kg), and methanol (12L) was added with stirring until the sodium 2-ethyl hexanoate dissolved. The solution was filtered and transferred to a crystallization vessel, washing in with methyl acetate (84L).
- Methyl acetate (124L) was added to amoxycillin trihydrate (87.1kg) and the resulting suspension was cooled to 0-5°C.
- Triethylamine (48.1L) was added to the slurry and the slurry was stirred for 5 minutes.
- Methanol (80L) was added causing the amoxycillin triethylamine salt to dissolve and the solution was stirred for 5 minutes.
- Dicalite (2kg) was added and the mixture was stirred for a further 5 minutes. The solution was then filtered and the cake was washed through with methanol (48L).
- the crystalline product from 2.3 was blow dried with nitrogen, and then dried in vacuum at 60-65°C.
- the product obtained had an amoxycillin content of 89.7 - 93.6%, with a total content of impurities of 1.72 - 1.42% over three batches.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Communicable Diseases (AREA)
- Oncology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Pharmacology & Pharmacy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US8755498P | 1998-06-01 | 1998-06-01 | |
US87554P | 1998-06-01 | ||
PCT/US1999/011991 WO1999062910A1 (en) | 1998-06-01 | 1999-06-01 | Process for preparing crystalline salts of amoxycillin |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1086109A1 EP1086109A1 (de) | 2001-03-28 |
EP1086109A4 true EP1086109A4 (de) | 2001-12-19 |
Family
ID=22205864
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99955267A Withdrawn EP1086109A4 (de) | 1998-06-01 | 1999-06-01 | Verfahren zur herstellung kristalliner amoxycillinsalze |
Country Status (15)
Country | Link |
---|---|
EP (1) | EP1086109A4 (de) |
JP (1) | JP2002517398A (de) |
KR (1) | KR20010043942A (de) |
CN (1) | CN1182138C (de) |
AU (1) | AU760934B2 (de) |
BR (1) | BR9910804A (de) |
CA (1) | CA2333943A1 (de) |
HU (1) | HUP0102008A3 (de) |
IL (1) | IL139736A (de) |
NO (1) | NO20006073D0 (de) |
NZ (1) | NZ508179A (de) |
PL (1) | PL344348A1 (de) |
TR (1) | TR200003517T2 (de) |
WO (1) | WO1999062910A1 (de) |
ZA (1) | ZA200006946B (de) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6878386B1 (en) | 1999-04-13 | 2005-04-12 | Beecham Pharmaceuticals (Pte) Limited | Method of treating a bacterial infection comprising amoxycillin and potassium clavulanate |
US6294199B1 (en) | 1999-04-13 | 2001-09-25 | Beecham Pharmaceuticals (Pte) Limited | Method of treating a bacterial infection comprising administering amoxycillin |
WO2006072577A1 (en) * | 2005-01-07 | 2006-07-13 | Sandoz Ag | Process for preparing granulates comprising amoxicillin |
CN101633663B (zh) * | 2009-08-28 | 2011-12-21 | 沈阳顺旺动物药业有限公司 | 一种青霉素类钠、钾盐的合成方法 |
WO2011158133A1 (en) * | 2010-06-16 | 2011-12-22 | Vardhman Chemtech Limited | Improved process for preparing amoxicillin sodium |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0596262A1 (de) * | 1992-10-05 | 1994-05-11 | ISTITUTO BIOCHIMICO ITALIANO GIOVANNI LORENZINI S.p.A. | Verfahren zur Herstellung von sterilen beta-Lactam-Antibiotika |
WO1997015579A1 (en) * | 1995-10-26 | 1997-05-01 | Biochemie Gesellschaft Mbh | Production of a crystalline salt of amoxicillin |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES8606871A1 (es) * | 1985-10-21 | 1986-06-01 | Antibioticos Sa | Un procedimiento de preparacion de amoxicilina sodica |
-
1999
- 1999-06-01 CA CA002333943A patent/CA2333943A1/en not_active Abandoned
- 1999-06-01 IL IL13973699A patent/IL139736A/en not_active IP Right Cessation
- 1999-06-01 JP JP2000552121A patent/JP2002517398A/ja not_active Withdrawn
- 1999-06-01 BR BR9910804-6A patent/BR9910804A/pt not_active IP Right Cessation
- 1999-06-01 TR TR2000/03517T patent/TR200003517T2/xx unknown
- 1999-06-01 WO PCT/US1999/011991 patent/WO1999062910A1/en not_active Application Discontinuation
- 1999-06-01 AU AU43216/99A patent/AU760934B2/en not_active Ceased
- 1999-06-01 NZ NZ508179A patent/NZ508179A/xx unknown
- 1999-06-01 CN CNB998069272A patent/CN1182138C/zh not_active Expired - Fee Related
- 1999-06-01 KR KR1020007013513A patent/KR20010043942A/ko not_active Application Discontinuation
- 1999-06-01 HU HU0102008A patent/HUP0102008A3/hu unknown
- 1999-06-01 PL PL99344348A patent/PL344348A1/xx not_active Application Discontinuation
- 1999-06-01 EP EP99955267A patent/EP1086109A4/de not_active Withdrawn
-
2000
- 2000-11-27 ZA ZA200006946A patent/ZA200006946B/en unknown
- 2000-11-30 NO NO20006073A patent/NO20006073D0/no not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0596262A1 (de) * | 1992-10-05 | 1994-05-11 | ISTITUTO BIOCHIMICO ITALIANO GIOVANNI LORENZINI S.p.A. | Verfahren zur Herstellung von sterilen beta-Lactam-Antibiotika |
WO1997015579A1 (en) * | 1995-10-26 | 1997-05-01 | Biochemie Gesellschaft Mbh | Production of a crystalline salt of amoxicillin |
Non-Patent Citations (1)
Title |
---|
See also references of WO9962910A1 * |
Also Published As
Publication number | Publication date |
---|---|
ZA200006946B (en) | 2002-01-28 |
HUP0102008A3 (en) | 2002-07-29 |
PL344348A1 (en) | 2001-11-05 |
CN1304412A (zh) | 2001-07-18 |
TR200003517T2 (tr) | 2001-06-21 |
HUP0102008A2 (hu) | 2001-12-28 |
AU4321699A (en) | 1999-12-20 |
CN1182138C (zh) | 2004-12-29 |
NZ508179A (en) | 2002-10-25 |
CA2333943A1 (en) | 1999-12-09 |
WO1999062910A1 (en) | 1999-12-09 |
BR9910804A (pt) | 2001-02-13 |
NO20006073L (no) | 2000-11-30 |
IL139736A0 (en) | 2002-02-10 |
EP1086109A1 (de) | 2001-03-28 |
JP2002517398A (ja) | 2002-06-18 |
IL139736A (en) | 2004-02-19 |
NO20006073D0 (no) | 2000-11-30 |
KR20010043942A (ko) | 2001-05-25 |
AU760934B2 (en) | 2003-05-22 |
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