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HK1156209B - Stable benzimidazole formulation - Google Patents

Stable benzimidazole formulation Download PDF

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Publication number
HK1156209B
HK1156209B HK11109701.8A HK11109701A HK1156209B HK 1156209 B HK1156209 B HK 1156209B HK 11109701 A HK11109701 A HK 11109701A HK 1156209 B HK1156209 B HK 1156209B
Authority
HK
Hong Kong
Prior art keywords
substrate
core
solution
omeprazole
coating
Prior art date
Application number
HK11109701.8A
Other languages
German (de)
French (fr)
Chinese (zh)
Other versions
HK1156209A1 (en
Inventor
Valerie Azoulay
Avi Avramoff
Adel Penhasi
Maxim Gomberg
Original Assignee
Dexcel Pharma Technologies Ltd
Priority date (The priority date 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 date listed.)
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Publication date
Application filed by Dexcel Pharma Technologies Ltd filed Critical Dexcel Pharma Technologies Ltd
Priority claimed from PCT/IL2009/000467 external-priority patent/WO2009136398A2/en
Publication of HK1156209A1 publication Critical patent/HK1156209A1/en
Publication of HK1156209B publication Critical patent/HK1156209B/en

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Abstract

A benzimidazole formulation which lacks an intermediate layer and yet which is stable both during storage and during the passage through the stomach, and which has low levels of residual volatile excipients, including but not limited to residual alkalinizing agents and/or residual solvents.

Description

FIELD OF THE INVENTION
The present invention relates to a novel stable formulation for an acid labile benzimidazole, and methods of preparation and administration thereof, and in particular, for a stable formulation of a benzimidazole which is suitable for oral administration, and has low levels of residual volatile excipients such as solvents.
BACKGROUND OF THE INVENTION
Omeprazole, Pantoprazole, Lansoprazole and other derivatives of benzimidazole, which are active proton pump inhibitors and used conventionally for decreasing gastric secretion are known to be susceptible to degradation and transformation in acid media. Omeprazole, 5-methoxy-2(((4-methoxy-3,5-dimethyl-2-pyridinyl)methyl)sulfinyl)-1H-benzimidazole, is disclosed and described in European Patent No. 5129 and European Patent No. 124495 , as well as in numerous other patents and published patent applications.
The susceptibility of these active proton pump inhibitor substances to degradation and transformation in acid media increases the difficulty of preparing a pharmaceutical form designed for oral administration. If the active substance comes into contact with the stomach content, which is a highly acidic medium, these chemical substances become degraded. Thus, these benzimidazole derivatives should be protected both during storage and during their passage through the acidic environment of the stomach.
The stability of Omeprazole has been extensively studied (see for example A. Pilbrant and C. Cederberg, Scan. J. Gastroenterol., 20: 113-120, 1985). Omeprazole degrades with a half-life of less than 10 minutes in an environment with pH values below 4.0. At pH 6.5, the half life of Omeprazole is 18 hours and at pH 11 about 300 days. Therefore, the environment of Omeprazole should be kept at a sufficiently high pH value in order to maintain the stability of the compound, in a formulation which is suitable as a product for oral administration, for example by locating Omeprazole within a core which also contains alkaline constituents. This leads to an alkaline reaction aimed at improving stability of the active substance during manufacture thereof and during storage of the pharmaceutical formulation.
In addition, such a formulation must protect Omeprazole from the acidic environment of the stomach, since if Omeprazole is given orally without any protective coating, it will degrade in the acid environment of the stomach. European Patent No. 237,200 discloses one solution, which is to directly coat the solid core containing Omeprazole, or another benzimidazole derivative, with an enteric coating layer.
However, this apparent solution to the instability of Omeprazole caused further complications, in that the alkaline core containing Omeprazole was found to react with the enteric coating, thereby causing the enteric coating to degrade. A solution to these further complications is disclosed in United Kingdom Patent Application No. 2,189,698 , in which Omeprazole is contained within a solid active core, which is coated first with a subcoating layer and then with an enteric coating layer. The enteric coating layer protects the Omeprazole during the passage through the stomach, while the subcoating layer protects the enteric coating layer from reacting negatively with the alkaline core containing Omeprazole.
The background art describes other attempts to provide formulations which are suitable for oral administration of acid-labile substances. For example, PCT Application No. WO 97/12581 discloses a composition adapted for oral administration containing Omeprazole which specifically does not include alkaline-reacting compounds. Instead, the composition features a core composed of a nuclei and Omeprazole compressed together, an intermediate layer and an enteric layer.
European Patent Application No. 519,144 discloses a formulation for Omeprazole, which features a neutral (sugar) core. Omeprazole is sprayed onto the sugar core, after which an intermediate coating layer and an enteric coating layer are sprayed onto the core.
PCT Application No. WO 98/00114 discloses a modification to other background art formulations for Omeprazole, in which the intermediate subcoating layer is partially neutralized with an alkaline compound. However, this modified formulation still features the subcoating layer, which is a disadvantage in that it complicates the manufacturing process and increases the expense and difficulty of manufacture. Thus, the formulation disclosed in PCT Application No. WO 98/00114 , like those disclosed in European Patent Application No. 519,144 and other background art references, has the disadvantage of requiring the intermediate layer.
PCT Application No. WO 83/00435 discloses a solid dosage form, such as a capsule or tablet, containing a pharmacologically active agent coated with an anionic polymer, which is insoluble in gastric juice and in intestinal juice below pH 7. The preferred anionic polymer is a partly methyl esterified methacrylic acid polymer in which the ratio of free carboxylic groups to ester groups is about 1:2. In contrast to the present invention, Omeprazole is not disclosed as one of the active agents.
French Application No. 2,692,146 discloses stable compositions of microgranules of gastro-protected Omeprazole. The composition features a center of Omeprazole diluted in mannitol. This center is coated with an intermediate layer featuring mannitol. An enteric coating is then added over this intermediate layer. PCT Application No. WO 97/12581 discloses a formulation in which an intermediate layer between the core and an enteric coating contains silicium dioxide.
PCT Application No. WO 96/37195 discloses a formulation which lacks a subcoating layer, but which features a core containing titanium dioxide. Both the core containing Omeprazole and the enteric coating layer placed on top of the core include titanium dioxide as an ingredient. Unfortunately, titanium dioxide is only able to mask the discoloration caused by the reaction between Omeprazole and the enteric coating layer, but cannot prevent such an undesirable reaction. Thus, the disclosed formulation does not prevent the undesirable reaction between the benzimidazole derivative and the enteric coating, which is known in the art.
German Patent Application No. 196 26 045 A1 discloses a method for stabilizing Omeprazole by coating small tablets or pellets, containing large amounts of mannitol, with a subcoating of Eudragit L. The subcoating of Eudragit L is neutralized, after which a final enteric coat of non-neutralized Eudragit L is applied.
A formulation of a benzimidazole derivative, such as Omeprazole, which lacks an intermediate coating layer and yet which is stable both during storage and during the passage through the stomach, is described in U.S. Patent Application No. 10/018,992 . This formulation involves neutralization of the enteric coating with an alkaline compound, such as ammonium hydroxide. The formulation is simple to manufacture and exposes the sensitive benzimidazole derivative to fewer production steps, thereby decreasing degradation of the active compound during production.
However, neutralization of enteric coatings with an alkalinizing agent usually results in a certain amount of the alkalinizing agent remaining in the final product. Furthermore, benzimidazole formulations are frequently prepared using volatile organic solvents, a residual amount of which is also found in the final product. Since there is no therapeutic benefit from residual alkalinizing agents and residual solvents, and these may, in fact, have a harmful effect, it is desirable to keep the levels of such residual solvents as low as possible for toxicity/safety reasons.
WO 2004/089333 discloses methods for preparing coated oral pharmaceutical formulations containing benzimidazole compounds, which involve adjusting the pH of the coating solution to a pH of between 4.5 to 5.5 using ammonia solution and subsequently coating the solution onto a core material, containing the active substance.
WO 2000/12064 relates to methods for preparing pharmaceutical compositions comprising omeprazole, wherein the pH of an organic based solvent coating solution is adjusted to 5.0 by means of sodium hydroxide.
US 2004/028737 discloses a method for preparing an enteric coated stable pharmaceutical composition containing an acid labile active compound, which comprises the preparation of an inner coating layer having an essentially neutral pH and an outer coating layer having an acidic pH.
WO1999/27917 discloses methods for preparing peroral medicaments containing benzimidazoles, by coating a core containing the active ingredient with a gastric juice resistant coating, which had been neutralized prior to coating by means of sodium carbonate.
US 2002/054913 relates to benzimidazole containing drugs for oral administration which had been prepared by applying two layers on the active core, the inner one being partially neutralized and the outer one exhibiting an lower pH to provide resistance.
WO2000/78284 discloses methods for preparing stable compositions containing benzimidazole derivatives, which comprise coating a core containing the active compound with a coating, which had been neutralized with sodium hydroxide.
SUMMARY OF THE INVENTION
The background art does not teach or suggest a benzimidazole formulation, particularly for Omeprazole, which lacks an intermediate layer and yet which is stable both during storage and during the passage through the stomach, and which has low levels of residual alkalinizing agents and residual solvents.
The present invention overcomes these drawbacks of the background art by providing a benzimidazole formulation which lacks an intermediate layer and yet which is stable both during storage and during the passage through the stomach, and which has low levels of residual volatile excipients, including but not limited to residual alkalinizing agents and/or residual solvents.
According to some embodiments of the present invention, there is provided a stable composition for a benzimidazole derivative, the composition comprising a substrate comprising the benzimidazole derivative and a single coating layer consisting of hydroxypropyl methylcellulose acetate succinate (HPMCAS) treated by monoethanol amine and ammonium hydroxide as alkalizing agents prior to applying over the substrate. The composition comprises less than 500 parts per million of residual volatile alkalizing agents relative to the composition weight, and a pH of the coating layer is in the range of from about 4.5 to about 6.5 as measured in 30 ml of distilled water at 20-25°C.
Optionally and preferably, the pH is in the range of from about 5 to about 6; more preferably the pH is about 5.
Optionally, the enteric polymer is dissolved in an organic solvent prior to application. Optionally and preferably, such a composition comprises less than about 1000 parts per million of residual organic solvent.
Non-limiting examples of organic solvents include acetone, ethanol, isopropanol or a mixture thereof.
Optionally and preferably, the substrate is an active core for containing the benzimidazole derivative, such as, for example, a pellet, a bead or a tablet.
Optionally and preferably, the active core is a tablet formed by compression.
According to some embodiments of the present invention, the substrate features a neutral core; and an active coating containing the benzimidazole derivative, wherein the active coating is layered over the neutral core; such that the composition is in a form of a pellet.
Optionally and preferably, the substrate features a core containing the benzimidazole derivative with a suitable binding agent, the core being prepared by spheronisation and pelletization; such that the composition is in a form of a pellet.
The benzimidazole is optionally one or more of Omeprazole, Pantoprazole, Lansoprazole, Leminoprazole, Perprazole, Rabeprazole, or pharmaceutically acceptable salts thereof, or combinations thereof.
Optionally, the substrate further comprises a filler, such as, for example, one or more of microcrystalline cellulose, sodium carboxymethycellulose, ethylcellulose, cellulose acetate, starch, lactose, glucose, fructose, sucrose, dicalcium phosphate, sorbitol, mannitol, mantitol, lactitol, xylitol, isomalt, erythritol, and hydrogenated starch hydrolysates, or a mixture thereof.
Optionally, the substrate further comprises a disintegrant, such as, for example, one or more of low-substituted carboxymethyl cellulose sodium, cross-linked polyvinyl pyrrolidone, sodium starch glycolate, cross-linked sodium carboxymethyl cellulose, pregelatinized starch, microcrystalline starch, water insoluble starch, calcium carboxymethyl cellulose, and low substituted hydroxypropyl cellulose magnesium aluminum silicate, or a mixture thereof.
Optionally, the substrate further comprises a lubricant, such as, for example, one or more of sodium stearyl fumarate, polyethylene glycol, silica colloidal anhydrous and magnesium stearate, or a mixture thereof.
Optionally, the substrate further comprises an alkalinizing agent, such as, for example, one or more of sodium stearate, meglumine, disodium phosphate, and ammonia, or a mixture thereof.
Optionally, the coating layer further comprises a plasticizer, such as, for example, one or more of a citric acid ester and a phthalic acid ester.
Optionally, the coating layer further comprises a surfactant, such as, for example, one or more of polysorbate 80 and sodium lauryl sulfate.
Optionally, the coating layer further comprises a glidant, such as, for example one or more of talc and titanium dioxide.
Optionally, the coating layer further comprises at least one of a coloring agent and a polishing agent.
According to the invention there is provided a method for preparing a stable composition for a benzimidazole derivative, the method comprising neutralizing hydroxypropyl methylcellulose acetate succinate (HPMCAS) with ammonium hydroxide and monoethanol amine; and layering the neutralized enteric polymer over a substrate comprising the benzimidazole derivative to form a coating layer, the composition comprising the substrate and the coating layer, such that the composition comprises less than 500 parts per million of residual volatile alkalizing agent relative to composition weight.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is herein described, by way of example only, with reference to the accompanying drawings. With specific reference now to the drawings in detail, it is stressed that the particulars shown are by way of example and for purposes of illustrative discussion of the preferred embodiments of the present invention only, and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of the invention. In this regard, no attempt is made to show structural details of the invention in more detail than is necessary for a fundamental understanding of the invention, the description taken with the drawings making apparent to those skilled in the art how the several forms of the invention may be embodied in practice.
In the drawings:
  • Figures 1-6 relate to the suitability of test method for determination of residual monoethanol amine.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The formulation of the present invention contains a benzimidazole derivative, such as Omeprazole, and is able to maintain the stability of this active ingredient without a separating layer between the active compound and an enteric coating layer. Instead, the enteric coating layer is prepared as an aqueous dispersion or in organic solvent and neutralized with ammonium hydroxide and monoethanol amine, before being applied as a solution directly to the benzimidazole derivative substrate.
The aqueous dispersion has a pH in the range of at from 7 to 9.
After being applied to the substrate, the aqueous dispersion dries to form a coating layer, preferably having a pH in the range of from about 4.5 to about 6.5, and more preferably from about 5 to about 6, as measured in 30 ml of distilled water at 22°C.
The resulting formulation comprises less than about 500 parts per million of residual volatile alkalizing agent relative to the total weight of the composition.
Preferably, the composition comprises less than about 1000 parts per million of residual organic solvent and more preferably less than about 500 ppm.
The resultant formulation maintains the stability of the benzimidazole derivative during storage and at the same time protects the product during passage through the acidic environment of the stomach. The problem of interaction between the enteric coat and the alkaline core is thus completely eliminated as the enteric coat at this stage does not release the free protons that are responsible for its acidic properties. At the same time, the formulation has low levels of residual volatile alkalinizing agent and residual organic solvent in the final product.
The preparation of the benzimidazole-containing compositions of the present invention is described first with reference to the following general description and then with reference to the following non-limiting examples of the preparation and application of the compositions of the present invention.
The formulation of the present invention includes a substrate which features the benzimidazole derivative. A coating suspension, which has a pH value of from 7 to 9, is prepared with the enteric coating material hydroxypropyl methylcellulose acetate succinate (HPMCAS). The pH value in the desired range is obtained by adding ammonium hydroxide and monoethanol amine to an enteric coating material
This enteric coating solution is then layered directly over the substrate to form the composition of the present invention.
The term "substrate" refers to substantially any structure which features the benzimidazole derivative, such as Omeprazole. For example, this structure could be an active core containing the benzimidazole derivative. The active core may comprise, for example, a pellet, a bead, or a tablet. This active core could be prepared in a number of different ways which are known in the art. For example, the active core could be formed by compressing the benzimidazole derivative with an alkaline substance. As another example, the active core could be prepared by mixing the benzimidazole derivative with an alkaline substance, spheronizing the mixture and then forming cores through pelletisation. As yet another example, the active core is optionally and preferably prepared by embedding the active ingredient in a poloxamer and compressing the embedded material into tablets. The active core is also optionally formed by granulating the active ingredient with an alkaline substance and compressing the granulation into tablets.
Alternatively and optionally, the structure could include a neutral core, such as a sugar bead which does not contain the benzimidazole derivative, over which the benzimidazole derivative is coated. The coating includes Omeprazole or other benzimidazole derivative with a suitable adhesive polymer. The pellet may optionally be prepared by spheronization and pelletization of the benzimidazole derivative and a suitable binding agent.
The benzimidazole derivative of the present invention may comprise, for example, Omeprazole, Pantoprazole, Lansoprazole, Leminoprazole, Perprazole, or Rabeprazole, or pharmaceutically acceptable salts thereof. Preferably, the benzimidazole derivative is omeprazole.
Optionally, the substrate may further comprise a filler. Examples of suitable fillers include microcrystalline cellulose, sodium carboxymethycellulose, ethylcellulose, cellulose acetate, starch, lactose, glucose, fructose, sucrose, dicalcium phosphate, sorbitol, manitol, mantitol, lactitol, xylitol, isomalt, erythritol, and hydrogenated starch hydrolysates, or a mixture thereof.
Further optionally, the substrate may comprise a disintegrant, such as, for example, low-substituted carboxymethyl cellulose sodium, cross-linked polyvinyl pyrrolidone, sodium starch glycolate, cross-linked sodium carboxymethyl cellulose, pregelatinized starch, microcrystalline starch, water insoluble starch, calcium carboxymethyl cellulose, and low substituted hydroxypropyl cellulose magnesium aluminum silicate, or a mixture thereof.
Also optionally, the substrate may further comprise a lubricant, such as, for example, sodium stearyl fumarate, polyethylene glycol, silica colloidal anhydrous and magnesium stearate, or a mixture thereof.
The substrate may optionally further comprises an alkalinizing agent, such as, for example, sodium stearate, meglumine, disodium phosphate, magnesium carbonate, and ammonia, or a mixture thereof.
As used herein, the term "neutralized enteric coating material" refers to the enteric coating material hydroxypropyl methylcellulose acetate succinate (HPMCAS) which has been at least partially neutralized by reaction with the alkalizing agents, monoethanol amine and ammonium hydroxide.
Preferably, the enteric coating material is at least about 60 % neutralized, more preferably the enteric coating material is at least about 80 % neutralized, and most preferably the enteric coating material is at least about 95 % neutralized.
The enteric coating is optionally prepared in an organic solvent, such as, for example, acetone, ethanol or isopropanol, or a combination thereof; such as a mixture of ethanol and water (30/70 or 40/60); or a mixture of isopropyl alcohol and ethanol.
The enteric coating optionally contains at least one of a plasticizer (such, as for example, a citric acid ester or a phthalic acid ester), a surfactant (such as, for example, polysorbate 80 or sodium lauryl sulfate), a glidant (such as, for example, talc or titanium dioxide), a coloring agent and a polishing agent.
The method for applying the enteric coating material to the substrate can vary. Substantially any coating method can be used, such as pan coating or fluidized bed coating, with the solution of the enteric coat chosen.
A preferred embodiment of the formulation of the present invention is presented in Example 1 below. Residual akalinizing agent in the coating was analyzed as described in Examples 2 and 3, respectively.
The following specific examples illustrate various aspects of the compositions of the present invention, and are not intended to be limiting in any way. Specific reference is made to Omeprazole for the purposes of description only and without intending to be limiting.
EXAMPLES
reference is made to Omeprazole for the purposes of description only and without intending to be limiting.
EXAMPLES Example 1: Delayed release tablets, 20 mg OTC formulation
Omeprazole USP Active 20.00 6.51
Lactose monohydrate NF Filler 203.00 66.12
Sodium starch glycolate NF disintegrant 10.00 3.25
Sodium stearate NF alkalinizing agent 10.00 3.25
Sodium stearyl fumarate NF lubricant 7.00 2.28
Hypromellose acetate succinate NF enteric coating polymer 32.00 10.42
Triethyl citrate NF plasticizer 4.50 1.47
Sodium lauryl sulfate NF wetting agent 0.50 0.16
Talc USP Glidant 8.14 2.65
Strong ammonium solution NF alkalinizing agent NA* -
Monoethanolamine NF alkalinizing agent 1.00 0.33
Sepisperse AP 3527 coloring agent 10.80 3.52
Carnauba wax NF polishing agent 0.06 0.02
Purified water Solvent NA* -
Total weight 307.00 Ca 100
* strong ammonium solution is used as a volatile alkalizing agent which is evaporated during the coating process.
Preparation of the substrate: Omeprazole was thoroughly mixed with lactose, sodium starch glycolate, sodium stearate and sodium stearyl fumarate. The mixture was then compressed into tablets weighing 250mg each. The tablets were then transferred into a conventional coating pan and coated with the enteric coating, prepared as described below.
Preparation of enteric coating
Coating A: triethyl citrate was dissolved in water, sodium lauryl sulfate was then added to this solution, HPMCAS and talc were dispersed in this solution, such that the concentration of HPMCAS was about 7% weight per volume. Monoethanolamine was added to this dispersion. Ammonia in a 25% solution was added to adjust the pH value in a range of from about 7 to about pH 9. The pigment was then added to the enteric coating dispersion.
Coating B: Triethyl citrate was dissolved in a mixture of isopropyl alcohol and alcohol, sodium lauryl sulfate was then added to this solution, HPMCAS and talc were dispersed in this solution, such that the concentration of HPMCAS was about 6% weight per volume. Ammonia in a 25% solution was added to adjust the pH value in a range of from about 7 to about pH 9. The pigment was then added to the enteric coating dispersion. The tablet cores were then transferred into a conventional coating pan and coated with the enteric coating layer.
Coating C: Triethyl citrate was dissolved in water to form an aqueous solution; sodium lauryl sulfate was then added to this aqueous solution. HPMCAS, colloidal silicon dioxide and talc were dispersed in this solution, such that the concentration of HPMCAS was about 7% weight per volume. Ammonia in a 25% solution was added to adjust the pH value of the coating dispersion in a range of from about 7 to about pH 9.
Coating D: Triethyl citrate was dissolved in water to form an aqueous solution; sodium lauryl sulfate was then added to this aqueous solution. HPMCAS, talc, and monoethanolamine were dispersed in this solution,. Ammonia in a 25% solution was added to adjust the pH value of the coating dispersion in a range of from about 7 to about pH 9.
Example 2: Omeprazole delayed release tablets 20 mg - Determination of ammonia Samples were stored at room temperature prior to analysis.
The samples were analyzed according to Standard Methods for Examination of Water and Waste Water, Ed. 19, 1995, Method 4500-NH3 F (phenate method). The samples were prepared in triplicate by adding 30 ml HPLC grade water to one tablet, shaking overnight on an inverting shaker, followed by centrifugation at 4000 rpm for 15 minutes. This solution was filtered through 2 layers of glass fiber cartridge (GFC) filters and analyzed according to the above mentioned method. Quantitation was performed using a calibration curve prepared from solutions of NH4Cl in water in the concentration range of 0.05 µg/mL to 1.0 µg/mL NH3. The uncoated tablets served as a control sample for the analysis of the coated tablets.
Results are presented in Table 1.
3789 BO415 (coated) 0.011; 0.07; 0.011 Mean 0.010
3980 BO425 (coated) 0.09; 0.010; 0.010 Mean 0.010
3981 BO515 (coated) 0.010; 0.012; 0.011 Mean 0.011
Example 3: Omeprazole delayed release tablet 20 mg - Determination of residual monoethanolamine
Samples were stored at room temperature prior to analysis.
Materials
Dansyl chloride Across 1158500
Sodium hydrogen carbonate Merck 106329
Acetone J.T. Baker 9002
Acetonitrile J.T. Baker 9017
Sodium hydroxide J.T. Baker 3722
Water HPLC grade Milli-Q in-house
Monoethanolamine Analyst sample 5015
Hydrochloric acid Riedel de Haen 30721
Equipment
Test tubes PP 50 ml
Laboratory glassware Class A
GFC filter paper 12.5 cm Whatman 1822-125
Shaker Heidolf
Centrifuge capable of maintaining 4000 rpm
HPLC instrument and conditions
Apparatus: Agilent 1100 with variable wavelength detector and autosampler and Chemstation Rev A 10.01 software
Column: Symmetry C 18 4.6 x 150 mm, 3.5 µ
Injection volume: 10 µL
Flow rate: 1.0 mL/min
Detection: 254 nm
Column temperature: ambient
Run time: 10 minutes
Retention time of MEA derivative: -5.3 minutes
Solutions
Hydrochloric acid 4 N was prepared by mixing 83.3 mL of concentrated hydrochloric acid (specific gravity 1.19, 37%) with 200 mL water in a 250 mL volumetric flask. The volume was made up with water.
Dilute hydrochloric acid was prepared by adding 1.2 mL hydrochloric acid (specific gravity 1.19, 37%) to a 1 L volumetric flask containing about 500 mL water, diluting to volume with water and mixing well.
Mobile phase was prepared by mixing 600 mL of water with 400 mL acetonitrile, mixing well and sonicating to degas.
0.2% dansyl chloride was prepared by weighing accurately about 100 mg dansyl chloride in a 50 mL volumetric flask and diluting with acetone.
0.1 M sodium hydrogen carbonate was prepared by weighing about 840 mg of sodium hydrogen carbonate into a 100 mL volumetric flask, diluting with water to give a pH of 9.0.
Monoethenolamine standard stock solution (1000 µg/mL) was prepared in duplicate by weighing accurately about 100 mg of monoethanolamine into a 100 ml volumetric flask, dissolving and diluting with water.
Monoethanolamine intermediate standard stock solution (100 µg/mL) was prepared by adding 5.0 mL standard stock solution to a 50 mL volumetric flask with dilute hydrochloric acid.
Monoethanolamine working standard solution (10 µg/mL) was prepared from intermediate standard stock solution by adding 5.0 mL to a 50 mL volumetric flask with dilute hydrochloric acid.
Sample preparation
Samples were prepared in duplicate. One tablet was placed per 50 mL conical test tube and 50 mL of water added. Test tubes were placed on an inverting shaker at speed 6 for 2-3 hours, until disintegration of the tablets, then acidified by adding 200 µL of 4 N HCl. Test tubes were centrifuged for 15 minutes at 4000 rpm and filtered through Whatman GFC.
Derivatization reaction
The procedure was performed on water as control and on all standards and samples, directly in autosampler vials.
100 µL of water, standard or sample solution was mixed with 200 µL 0.2% dansyl chloride solution. 400 µL 0.1 M sodium hydrogen carbonate and 400 µL acetone were added. The vials were closed, mixed and heated for 20 minutes in a water bath at 60°C. The contents of the vials were cooled to room temperature and injected into the HPLC system.
Results are presented in Table 2.
3789 BO415 0.77 (%RSD=6.0)
3980 BO425 0.730; 0.681 Mean 0.71
3981 BO515 0.822; 0.755 Mean 0.79
5273 BO615 0.908; 0.780 Mean 0.84
Example 4: Suitability of test Method for determination of residual monoethanolamine
In order to evaluate the suitability of the method as described above, the method was evaluated for specificity, linearity, precision (system and method) and recovery.
In order to demonstrate the specificity, the following samples and solutions were analyzed: a sample blank (water); a standard containing 10 µg/mL monoethanolamine that had undergone the derivatization procedure; omeprazole tablets, prepared without the use of monoethanolamine, prepared according to the test method; and water.
Specificity
As shown in Figures 1 to 6, no interfering peaks at the retention time of monoethanolamine were recorded in the chromatograms of the blank sample, water, or the tablet without monoethanolamine.
Linearity
The linearity of the method was demonstrated in the range of from 1 to 50 µg/mL monoethanolamine, corresponding to 0.05 to 2.5 mg/tablet. Results are presented in Table 3.
0/96 7.4978E±00 43.7
1.92 1.5817E±01 10.9
4.81 4.4112E±01 -2.5
9.62 9.2365E±01 -6.0
19.24 2.0443±02 -0.4
48.10 5.2640±02 0.3
correlation 0.99982
square correlation 0.99963
slope 1.1074E+01
intercept -7.8104E+00 -7.6
Precision
The precision of the method was evaluated by replicate injections of a standard containing a nominal 10 µg/mL monoethanolamine derivatized according to the test method (system precision) and by preparing a sample of omeprazole tablets in 6 independent replicates according to the test method (method precision).
The system precision results as presented in Table 4 show that good precision was obtained for the peak areas as well as for the retention times.
1 5.291 9.0628E+01
2 5.286 8.9055E+01
3 5.283 9.1252E+01
4 5.283 8.8879E+01
5 5.262 8.9296E+01
6 5.225 9.0930E+01
Mean 5.272 9.0007E+01
% RSD 0.5 1.2
Method precision was performed using 6 preparations of omeprazole tablets (analyst sample 3789). Results were calculated against a standard containing 9.62 µg/mL monothenaolamine with an average peak area of 9.5519E+01 mAU*s, using the following formula:
area smp
= monoethanolamine peak area in sample chromatogram
area st
= average peak area of standard "10 µg/mL"
cst
= standard concentration in µg/mL
50
= sample extraction volume (mL)
1000
= conversion factor of µg to mg
A representative chromatogram is presented in Figure 5.
Method precision data and results are presented in Table 5.
3789-1 coated BO4 15 1.4518E+0.2 14.6 0.731
3789-2 1.6711E+0.2 16.8 0.842
3789-3 1.4151E+0.2 14.3 0.713
3789-4 1.5385E+0.2 15.5 0.775
3789-5 1.5710E+0.2 15.8 0.791
3789-6 1.5804E+0.2 15.9 0.796
MEAN 0.774
% RSD 6.0
Recovery
The recovery of the method was demonstrated by spiking control (no monoethanolamine) and monoethanolamine-containing omeprazole tablets with three levels of monoethanolamine.
Omeprazole tablets containing monoethanolamine (sample 3789, batch BO415) were spiked at the 0.1% w/w level in triplicate. Omeprazole control tablets (no MEA) were spiked at three levels with 0.15, 0.3 and 0.9 mg/tablet, corresponding to 0.05, 0.1 and 0.3% w/w. The test was performed by transferring the tablets to 50 mL test tubes, adding suitable volumes of a solution of 1000 µg/mL MEA, followed by 50 ml of water and preparation according to the method described above.
Results as presented in Tables 6 and 7 show good recovery results, within generally accepted limits for residue analysis. Recovery results were calculated against a standard containing 9.62 µg/mL MEA with an average peak area of 9.5519E+01 mAU*s. The recovery results in the tablets containing MEA were calculated as follows:
A representative chromatogram of omeprazole tablets (analyst sample 3789 Batch BO415) spiked with MEA is presented in Figure 6.
5274-1 omeprazole 0.0000E+00 0.0 0.000
5274-2 20 mg 0.0000E+00 0.0 0.000
5274-3 uncoated 0.0000E+00 0.0 0.000
100605
Mean 0.000
5274-1 omeprazole 2.4417E+0.1 0.144 2.46 0.123 85.5
5274-2 20 mg 2.4339E+01 2.45 0.123 85.2
5274-3 uncoated 2.4966E+01 2.51 0.126 87.4
100605
Mean 0.124 86.0
% RSD 1.4 1.4
5274-1+0.1% omeprazole 4.9693E+01 0.289 5.00 0.252 87.2
5274-2+0.1% 20 mg 5.1115E+01 5.15 0.259 89.7
5274-3+0.1% uncoated 5.1356E+01 5.17 0.260 90.1
100605
Mean 0.257 89.0
% RSD 1.8 1.8
5274-1+0.3% Omeprazole 1.845E+02 0.962 18.59 0.948 98.5
5274-2+0.3% 20 mg 1.8919E+02 19.05 0.972 101.0
5274-3+0.3% uncoated 1.8982E+02 19.12 0.975 101.4
100605
Mean 0.965 100.3
% RSD 1.5 1.5
3789-1 coated 1.4518E+02 14.6 0.731
3789-2 BO415 1.6711E+02 16.8 0.842
3789-3 1.4151E+02 14.3 0.713
Mean 0.762
% RSD 9.2
3789-1+0.1% coated 2.1507E+0.2 0.289 21.721.723.8 1.083 107.6
3789-2+0.1% B0415 2.1576E+0.2 1.086 107.9
3789-3+0.1% 2.3641E+0.2 1.1190 118.2
Mean 1.120 111.2
%RSD 5.5 5.5
Standard and sample solution stability
During the method development, stock solution stability was demonstrated for 48 hours at room temperature. In addition, it was found that the MEA derivative is stable in autosampler vials at room temperature for at least 48 hours, because the response of the MEA derivative did not change upon reinjection.
Example 5:_Omeprazole delayed release tablets 20 mg - Determination of final pH of enteric coating
Enteric coated omeprazole tablets were prepared according to the composition of Example 1 (Batch # B0425). The enteric coating was prepared in aqueous dispersion, and the pH value of the coating dispersion was adjusted to the range from about 7 to about pH 9 by a combination of monoethanolamine and concentrated ammonia solution. The ammonia solution evaporated during the coating process.
The pH of the coating layer following evaporation of the ammonia solution was measured in the following test solutions:
  1. 1. Purified water (pH 5.9 at 22 °C), obtained from MILI Q system; and
  2. 2. 1% buffer solution of Intestinal Fluid NF (pH 6.9 at 22 °C) using potassium dihydrogenphosphate (lot # B36148 purchased from Baker), and sodium hydroxide (lot # B452998549 from Merck), with no pancreatin added.
For each test solution, three coated tablets were split and the core was removed by washing using purified water. The resulting film coats were then transferred into a vial containing 30 ml test solution, and stirred for 2 hours with a magnetic stirrer at 1000 rpm. The pH of the medium was determined.
It was found that in purified water, the coating films partially disintegrated and partially dissolved. The pH value of the medium was found to be 5.4.
In intestinal fluid, the coating films were fully disintegrated and fully dissolved (except for talc and the coloring powder of Sepisperse). The pH value of the medium was found to be 5.3. Hence, it is shown that the polymer retains its acidic properties and thus provides an acidic reaction.
Since the pH of the coating solution was initially basic, it can be concluded that the change in pH occurs due to evaporation of ammonia solution, causing the polymer, hydroxypropyl methylcellulose acetate succinate (HPMCAS) to revert to its acid form, having enteric properties. The acidic form of HPMCAS can be soluble in water only through ionization of all free acidic groups in an aqueous medium with pH values above 5.5. This is in fact the reason that the polymer is characterized as an enteric polymer. While the native pH value of pure HPMCAS aqueous dispersion is about 4.5, the pH value of about 5.3 found using the composition of the present invention may be due to the presence of residual monoethanolamine, which is used a second alkalizing agent for neutralization of HPMCAS.
The present study shows that when the entering coating polymer is placed in purified water as test medium, a partial dissolution of the polymer first takes place, which continues for as long as the pH of the medium remains basic. Once the pH of the medium reaches an acidic value of about 5.4, dissolution of the polymer stops and the polymer disintegrates. In diluted neutral buffer solution-1% simulated intestinal fluid, on the other hand, an acidic pH was achieved only after full polymer dissolution.
The temporarily neutralized HPMCAS coating prepared using a high concentration of ammonia during the coating process provides an enteric film coat surrounding the omeprazole-containing cores which can withstand pH values of up to about 5. This can provide the active material with an appropriate protection while passing through the stomach even if the pH values of gastric fluid are elevated.

Claims (10)

  1. A method for preparing a stable composition comprising a benzimidazole derivative selected from the group consisting of Omeprazole, Pantoprazole, Lansoprazole, Leminoprazole, Perprazole, Rabeprazole, and pharmaceutically acceptable salts thereof, the method comprising:
    applying a solution or dispersion comprising a neutralized hydroxypropyl methylcellulose acetate succinate (HPMCAS) polymer obtained by neutralizing the HPMCAS with ammonium hydroxide and monoethanol amine;
    wherein the pH of the solution or dispersion is 7 - 9,
    to a substrate comprising the benzimidazole derivative to form a single coating layer over said substrate without an intermediate layer between said substrate and said enteric coating,
    wherein a solution or dispersion prepared from the coating layer of the stable composition has a pH in the range of from about 4.5 to about 6.5 as measured in 30 ml of distilled water at 20-25°C, and
    wherein said stable composition comprises less than about 500 parts per million of residual ammonium hydroxide relative to the total weight of the composition.
  2. The method of claim 1, wherein the solution or dispersion comprising the neutralized HPMCAS polymer further comprises an organic solvent, wherein said organic solvent is optionally selected from the group consisting of acetone, ethanol, isopropanol and a mixture thereof.
  3. The method of any of claims 1 to 2, wherein said substrate is an active core for containing the benzimidazole derivative, said active core being optionally selected from the group consisting of a pellet, a bead and a tablet.
  4. The method of claim 3, wherein said active core is a tablet formed by compression.
  5. The method of claim 1, wherein said substrate is in a form of a pellet featuring:
    (i) a neutral core; and
    (ii) an active coating containing the benzimidazole derivative, said active coating being layered over said neutral core.
  6. The method of claim 1, wherein said substrate is in a form of a pellet featuring a core containing the benzimidazole derivative, said core being prepared by spheronisation and pelletization of the core with a suitable binding agent.
  7. The method of any of claims 1 to 6, wherein said substrate further comprises an alkalizing agent, wherein said alkalizing agent is optionally selected from the group consisting of sodium stearate, meglumine, disodium phosphate, and ammonia, or a mixture thereof.
  8. The method of any of claims 1 to 7, wherein said substrate further comprises at least one of a filler, a disintegrant, and a lubricant.
  9. The method of any of claims 1 to 8, wherein the solution or dispersion comprising the neutralized HPMCAS polymer further comprises at least one of a plasticizer, a surfactant and a glidant.
  10. A composition obtainable by a method according to any of the preceding claims.
HK11109701.8A 2008-05-06 2009-05-05 Stable benzimidazole formulation HK1156209B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US7155708P 2008-05-06 2008-05-06
US61/071557 2008-05-06
PCT/IL2009/000467 WO2009136398A2 (en) 2008-05-06 2009-05-05 Stable benzimidazole formulation

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Publication Number Publication Date
HK1156209A1 HK1156209A1 (en) 2012-06-08
HK1156209B true HK1156209B (en) 2015-12-18

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