Magnesium omeprazole

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...

Reexamination Certificate

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C546S273700

Reexamination Certificate

active

06713495

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to an improved form of magnesium omeprazole, a process for making same, and pharmaceutical compositions same.
BACKGROUND OF THE INVENTION
The compound known under the generic name omeprazole is described in European patent 0005129.
Omeprazole is useful for inhibiting gastric acid secretion and has gastric mucosa protective activity in mammals and man. Omeprazole may be used for prevention and treatment of gastric acid related disorders and gastrointestinal inflammatory diseases in mammals and man, including for example gastritis, gastric ulcer and duodenal ulcer.
The term “omeprazole” as used in this specification designates the neutral form of the compound, that is the form without a salt-forming cation present.
Certain salts of omeprazole are described in European patent 0124495.
In EP 0124495, example 5 specifically discloses the synthesis of magnesium omeprazole dihydrate, and example 6 specifically discloses the synthesis of magnesium omeprazole anhydrate. Manufacturing of the described magnesium omeprazole salts presents significant difficulties.
The process of manufacture and isolation of the dihydrate according to example 5 is relatively complex. It requires making the sodium salt, adding a solution of magnesium chloride to obtain a precipitate, removing water by centrifuging the precipitate, washing the precipitate with deionized water until no Cl

is detectable, drying in air, grinding, and the drying in vacuum at 40° C. for 24 h. Moreover, because the resulting magnesium omeprazole dihydrate is crystalline, the rate of dissolution in intestinal fluid is relatively slow, unless the material is milled to a relatively fine particle size.
The process of making the anhydrate according to example 6 is simpler. Magnesium is reacted with methanol to give a solution of magnesium methoxide in methanol. The solution is added to a solution of omeprazole in methanol, the quantity of omeprazole being one mole for each two moles of magnesium. The methanol is then evaporated to give a crystalline solid, which is magnesium omeprazole anhydrate. However, the anhydrate as made by this process is also not without a problem. As the magnesium omeprazole precipitates from the solution upon evaporation of the methanol, residual methanol is entrapped in the solid particles and cannot easily be removed by evaporation. Methanol is toxic and high levels are generally considered unacceptable in pharmaceutical chemicals.
Canadian patent 2166794 describes what is said to be an improved form of magnesium omeprazole dihydrate, which has a higher degree of crystallinity than that of example 5 of EP 0124495. This form has a methanol content of less than 0.1%. However, like the product of example 6 of EP 0124495, it is a crystalline dihydrate, and the process of manufacture is relatively complex. According to Canadian patent 2166794, the degree of crystallinity of a sample made according to example 6 of EP 0124495 was 67%, whereas the degree of crystallinity of the improved form is at least 70%.
Canadian patent application No. 2254572 discloses improved processes for the production of magnesium omeprazole crystalline dihydrate. The disclosure reviews the prior art, and in particular, in relation to the anhydrate of example 6 of EP 0124495, states as follows: “This procedure cannot be practised on a large scale because of the need to evaporate to dryness. It has been found that unacceptable and potentially dangerous amounts of methanol become trapped in this solid, making it pharmaceutically unacceptable.” The processes of Canadian patent 2254572 are again relatively complex.
Improved processes for the production of magnesium omeprazole crystalline dihydrate are also described in PCT Publication No. WO 97/4114. The degree of crystallinity of the product of example 1 is said to be 80%. Again, the processes disclosed are relatively complex.
In summary, the only magnesium omeprazole according to the prior art that has an acceptably low level of methanol is magnesium omeprazole crystalline dihydrate, which has a degree of crystallinity of 67% or higher and is produced only by relatively complex processes.
In light of the foregoing, the object of the present invention is to produce magnesium omeprazole that has acceptably low levels of methanol, but is substantially amorphous (non-crystalline), and can be produced by a simple process.
BRIEF SUMMARY OF THE INVENTION
Magnesium omeprazole of the present invention is made by reacting magnesium in a lower alcohol to form magnesium alkoxide, adding omeprazole in a quantity of about two moles per mole of magnesium, and flash-evaporating the alcohol, so as to form a solid precipitate without allowing the growth of crystals or particles that entrap the alcohol at unacceptable levels. The resulting material is substantially amorphous (non-crystalline).
DETAILED DESCRIPTION OF THE INVENTION
In the process of manufacture of magnesium omeprazole according to the present invention, magnesium is reacted in a lower alcohol, preferably methanol, to form a solution of magnesium alkoxide in the alcohol.
The atomic weight of magnesium is 24.3 and the molecular weight of omeprazole is 345.4. Since magnesium is divalent, the amount of magnesium required to convert 345.4 grams of omeprazole to magnesium omeprazole is 12.15 grams.
Hence 35.2 grams of magnesium is needed to convert 1 kilo of omeprazole to magnesium omeprazole.
The process of converting 1 kilo of omeprazole to magnesium omeprazole thus begin with reacting 35.2 grams of magnesium in a lower alcohol, preferably methanol. The minimum amount of methanol needed to fully react and dissolve 35.2 grams of magnesium is about 1000 grams.
When the magnesium is immersed in the alcohol, the reaction will be evident from the generation of hydrogen bubbles, and the reaction will be complete when all the magnesium has been consumed and the effervescence has ceased. All of the magnesium will then be present as magnesium alkoxide in the alcohol (i.e. magnesium methoxide in methanol, if methanol is used as the alcohol).
The omeprazole can then added directly to the magnesium alkoxide solution. Attentively, the omeprazole may first be dissolved in an alcohol or another organic solvent that is miscible with the alcohol used to make the magnesium alkoxide, and the resultant solution may then be added to the magnesium alkoxide solution.
Where methanol is used as the sole solvent, a total of only about 1.5 kilos is needed for converting 1 kilo of omeprazole to magnesium omeprazole in solution by the methanol.
Hence, using quantities based on 1 kilo of omeprazole, the simplest and best procedure is to react 35.2 grams of magnesium in about 1.5 kilos of methanol, wait until the magnesium has been fully reacted, and then add the 1 kilo of omeprazole to the solution and stir to dissolve. The resulting solution will be a solution of magnesium omeprazole equivalent to 1 kilo of omeprazole in methanol.
In order to obtain solid magnesium omeprazole that is substantially free of organic solvent (i.e. substantially free of methanol, if methanol is used), it is then necessary to eliminate the solvent.
It has been found that this can be done by “flash-evaporating” the solvent. Flash-evaporating will be understood to mean evaporating in such a way as to avoid the precipitation of crystals or large particles which entrap the alcohol.
One method of flash-evaporating the solvent is to mix the solution into a solid excipient such as, for example, microcrystalline cellulose so that a damp mass is formed. The mass can then be dried in a conventional oven, a fluid bed drier, or under vacuum to remove the solvent. Because the solution has been dispersed throughout the solid excipient, as the solvent evaporates, the omeprazole magnesium is deposited as a thin layer over the surface of the particles of the solid excipient and does not precipitate as crystals or large granules, so that there is little or no entrapment of solvent.
The preferred way of flash-evaporating the solvent is by spray-drying the

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