CN100384839C - Prepn process of [(substituted pyridyl) methyl] sulfenyl-1H-benzimidazole compound and its antimer zinc salt - Google Patents
Prepn process of [(substituted pyridyl) methyl] sulfenyl-1H-benzimidazole compound and its antimer zinc salt Download PDFInfo
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- CN100384839C CN100384839C CNB2006100239569A CN200610023956A CN100384839C CN 100384839 C CN100384839 C CN 100384839C CN B2006100239569 A CNB2006100239569 A CN B2006100239569A CN 200610023956 A CN200610023956 A CN 200610023956A CN 100384839 C CN100384839 C CN 100384839C
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Abstract
The present invention relates to a preparation method for the zinc salt of [(substituted pyridyl) methyl] sulfenyl-1H-benzimidazole compound which can be used as a proton pump inhibitor. Under the condition of an organic solvent with or without a quenching agent, [(substituted pyridyl) methyl] sulfenyl-1H-benzimidazole compound or an (S)-antimer and an organic zinc agent react for obtaining the zinc salt. The method of the present invention is simple and is suitable for industrial production.
Description
Technical field
The present invention relates to [(pyridyl of replacement) methyl] sulfinyl-1
HThe preparation method of the zinc salt of-benzimidazoles compound.The invention still further relates to [(pyridyl of replacement) methyl] sulfinyl-1
HThe preparation method of the zinc salt of (the S)-enantiomorph of-benzimidazoles compound and comprise [(pyridyl of replacement) methyl] sulfinyl-1
HThe pharmaceutical composition of the zinc salt of the zinc salt of-benzimidazoles compound and (S)-enantiomorph.
Background technology
Has [(pyridyl of the replacement) methyl] sulfinyl-1 shown in structural formula (1)
H-benzimidazoles compound, as omeprazole (I), pantoprazole (II), rabeprazole (III) and lansoprazole (IV), with their the corresponding magnesium salts of (S)-enantiomorph, be the medicine that a class can be used as proton pump inhibitor, particularly omeprazole wherein presses down the acid effect by force, curative ratio height, healing time weak point, can eliminate the intractable ulcer crisis, and safe and reliable, become the important drugs of gastric and duodenal ulcer and reflux esophagitis.And the single enantiomer of omeprazole, (S)-and omeprazole has the better medicament kinetic property, to the inhibition effect and the security of acid, and bioavailability is also higher, and it is littler to suppress degree of variation in Different Individual.The structural formula of above-claimed cpd is as follows:
I R
1=-OCH
3R
2=-CH
3R
3=-OCH
3R
4=-CH
3Omeprazole
II R
1=-OCF
2H; R
2=R
3=-OCH
3R
4=-H pantoprazole
III R
1=-H; R2=-CH
3R3=-OCH
2CH
2CH
2OCH
3The R4=-H rabeprazole
IV R
1=-H; R2=-CH
3R3=-OCH
2CF
3The R4=-H lansoprazole.
With the omeprazole is example, the existing relevant report of the preparation method of this compounds salt.United States Patent (USP) 5714504 has been described the basic salt of (S)-omeprazole, as sodium salt, magnesium salts, lithium salts, sylvite, calcium salt and trialkyl amine salt.Wherein, the preparation method of (S)-omeprazole sodium salt and magnesium salts has only been described except having reported the synthetic of the free alkali of (S)-omeprazole.World patent WO 98/54171 and WO 00/44744 have reported the preparation method of (S)-omeprazole sylvite.World patent WO 2004/099182 has reported the preparation method of (S)-omeprazole zinc salt, with the alkaline aqueous solution of the free alkali of (S)-omeprazole or (S)-and the aqueous solution and the mineral acid or the reaction of organic acid zinc salt of omeprazole an alkali metal salt, obtain the precipitation of (S)-omeprazole zinc salt.Chinese patent CN1683369A has reported the preparation method with world patent WO 2004/099182 identical (S)-omeprazole zinc salt.
Summary of the invention
The purpose of this invention is to provide a kind of might be as medicinal [(pyridyl of replacement) methyl] sulfinyl-1
HThe preparation method of the zinc salt of-benzimidazoles compound and their (S)-enantiomorph.These compounds can relate to currently reported any as in omeprazole (I), pantoprazole (II), rabeprazole (III) and lansoprazole (IV) and their compounds such as the corresponding zinc salt of (S)-enantiomorph that can be used as in the proton pump inhibitor class medicine at least.
Method of the present invention be a kind of be reaction medium with the organic solvent, simple and easily under the reaction conditions, by [(pyridyl of replacement) methyl] sulfinyl-1
HThe free alkali of-benzimidazoles compound and their free alkali of (S)-enantiomorph and organic zinc reagent prepared in reaction [(pyridyl of replacement) methyl] sulfinyl-1
HThe method of the zinc salt of-benzimidazoles compound and their (S)-enantiomorph.
[(pyridyl of replacement) methyl] sulfinyl-1 that the present invention describes
HThe zinc salt of-benzimidazoles compound and their (S)-enantiomorph refers to any comprising [(pyridyl of replacement) methyl] sulfinyl-1
HThe negatively charged ion and the zinc cation of-benzimidazoles compound and their (S)-enantiomorph.For example: solid form or solution form, crystal state or unformed state.Can be anhydrous form and/or solvent-free form and/or hydrated form and/or contain solvent version.
[(pyridyl of replacement) methyl] sulfinyl-1 that the present invention describes
H(the S)-enantiomorph of-benzimidazoles compound refers to [(pyridyl of replacement) methyl] sulfinyl-1 of (the R)-enantiomer-pure that does not wherein contain free state fully
H-benzimidazoles compound, for example: the ee value is 60%, perhaps the ee value is 80%.Under given conditions, (S)-to refer to the ee value minimum be 95% to enantiomorph, perhaps at least 98%, perhaps at least 99.0%, perhaps at least 99.5%.
[(pyridyl of replacement) methyl] sulfinyl-1 that the present invention describes
HThe zinc salt of-benzimidazoles compound and their (S)-enantiomorph comprises stoichiometry and non-stoichiometric [(pyridyl of replacement) methyl] sulfinyl-1
HThe negatively charged ion and the zinc cation of-benzimidazoles compound and their (S)-enantiomorph.[(pyridyl of replacement) methyl] sulfinyl-1
H-benzimidazoles compound and their (S)-enantiomorph and molar ratio zinc are unqualified to be 1: 1.[(pyridyl of replacement) methyl] sulfinyl-1 in specific specific examples
HThe zinc salt of-benzimidazoles compound and their (S)-enantiomorph, [(pyridyl of replacement) methyl] sulfinyl-1
HThe negatively charged ion of (the S)-enantiomorph of-benzimidazoles compound and they and the molar ratio of zinc cation are 2: 1, though in the forming process of zinc salt [(pyridyl of replacement) methyl] sulfinyl-1
H-benzimidazoles compound and their (S)-enantiomorph or organic zinc reagent are excessive.
[(pyridyl of replacement) methyl] sulfinyl-1 that the present invention describes
HThe zinc salt of-benzimidazoles compound and their (S)-enantiomorph has following structure:
R wherein
1, R
2, R
3And R
4Be hydrogen, C independently
1～20Alkyl, C
1～20Alkoxyl group or ester group, halogen, phenyl, trifluoromethyl or nitro.
[(pyridyl of replacement) methyl] sulfinyl-1 that the present invention describes
HThe zinc salt of-benzimidazoles compound and their (S)-enantiomorph is recommended to exist with the unformed shape form.Compare with crystal habit, powder more tiny in the unformed shape might obtain better solvability.
Preparation [(pyridyl of the replacement) methyl] sulfinyl-1 that the present invention describes
HThe method of the zinc salt of-benzimidazoles compound and their (S)-enantiomorph comprises following steps:
In organic solvent and under the room temperature, [(pyridyl of replacement) methyl] sulfinyl-1
H-benzimidazoles compound or their (S)-enantiomorph and organic zinc reagent reaction 0.5～3 hour add or do not add quencher cancellation reaction and obtain [(pyridyl of replacement) methyl] sulfinyl-1
HThe zinc salt of-benzimidazoles compound and their (S)-enantiomorph.
Also can obtain [(pyridyl of replacement) methyl] sulfinyl-1 after the reaction by separation
HThe zinc salt of-benzimidazoles compound and their (S)-enantiomorph.
Described [(pyridyl of replacement) methyl] sulfinyl-1
H-benzimidazoles compound has following structure:
Wherein, R
1, R
2, R
3Or R
4Be hydrogen, C independently
1～20Alkyl, C
1～220Alkoxyl group or ester group, halogen, phenyl, trifluoromethyl or nitro;
Described organic zinc reagent has following structure: R
5-Zn-R
6, R wherein
5And R
6Independently for C is arranged
1～ 6Alkyl, C
1～6Thiazolinyl, C
1～6Alkynyl or aryl; That preferential use is R among the present invention
5And R
6Be the alkyl zinc reagent of ethyl, i.e. zinc ethyl.
Described quencher is protic solvent or their mixtures such as water, alcohol.The preferential quencher that uses is a water among the present invention.
Described [(pyridyl of replacement) methyl] sulfinyl-1
HThe mol ratio of-benzimidazoles compound or their (S)-enantiomorph, organic zinc reagent and quencher is 1: 0.5～2: 0～1000; When adopting quencher, use more quencher to not influence of reaction.Adopt quencher to also help and separate unreacted organic zinc reagent.Recommend described [(pyridyl of replacement) methyl] sulfinyl-1
HThe mol ratio of-benzimidazoles compound or their (S)-enantiomorph, organic zinc reagent and quencher is 1: 0.8～1.5: 10～500.
The organic solvent that the present invention describes can be methylene dichloride, chloroform, tetracol phenixin, hexane, benzene, toluene, chlorobenzene, oil of mirbane, dimethylbenzene, ether, tertbutyl ether, tetrahydrofuran (THF) and dioxane or their mixture.The preferential organic solvent that uses is a tetrahydrofuran (THF) among the present invention.Described protic solvent can be the alcohols that comprises as methyl alcohol, ethanol, propyl alcohol or butanols etc.
The method of employing the present invention description can be used the method separation and purification of filtration or centrifugation etc. after the reaction, and then washs and drying.The preferential separation method that uses is to filter among the present invention.
[(pyridyl of replacement) methyl] used in the present invention sulfinyl-1
H(the S)-enantiomorph of-benzimidazoles compound can be by synthetic acquisitions such as known method in the document such as United States Patent (USP)s 5714504.
[(pyridyl of replacement) methyl] sulfinyl-1
HThe zinc salt of-benzimidazoles compound and their (S)-enantiomorph is effectively as gastric acid secretion inhibitor, can be used as anti-ulcerative drug.On general significance more, it can be used for treating among Mammals and the particularly mankind and the hydrochloric acid in gastric juice diseases associated, and these diseases comprise for example reflux esophagitis, gastritis, duodenitis, stomach ulcer and duodenal ulcer.In addition, what it can be used for treating other needs the inhibiting gastrointestinal illness of hydrochloric acid in gastric juice, for example take nonsteroidal anti-inflammatory agent (NSAID) patient, suffer from non-ucler dyspepsia patient, suffer from the patient of gastroesophageal reflux disease and the patient who suffers from gastrinoma.[(pyridyl of replacement) methyl] sulfinyl-1
HThe zinc salt of-benzimidazoles compound and their (S)-enantiomorph also can be used for providing special care to patient, acute patient, art preceding and postoperative prevention hydrochloric acid in gastric juice suction and the treatment stress ulcer that goes up gastrointestinal hemorrhage.In addition, [(pyridyl of replacement) methyl] sulfinyl-1
HThe zinc salt of (the S)-enantiomorph of-benzimidazoles compound and they can be used for treating psoriasis and treatment spiral mattress (Helicobacter) infects and diseases associated with it.[(pyridyl of replacement) methyl] sulfinyl-1
HThe zinc salt of-benzimidazoles compound and their (S)-enantiomorph also can be used for treating the mammiferous inflammation that comprises the mankind.
What any suitable route of administration all can be used for offering patient's effective dose for example can use oral preparation etc. by the present invention.Formulation comprises capsule, tablet, dispersion or suspension etc.
In addition, the inventive method obtains comprises [(pyridyl of replacement) methyl] sulfinyl-1
HThe zinc salt of-benzimidazoles compound and their (S)-enantiomorph is as active constituent and pharmaceutically acceptable carrier, thinner or vehicle and randomly other treats the pharmaceutical composition of component.
Method of the present invention is a kind of easy synthetic method, is a kind of method of suitable suitability for industrialized production.
Embodiment
Below the embodiment by the embodiment form is described in further detail foregoing of the present invention again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment, all technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
The preparation of embodiment 1 omeprazole zinc salt
Omeprazole 5 grams (14.5 mmole) are dissolved in 50 milliliters of tetrahydrofuran (THF)s, slowly add zinc ethyl 0.98 gram (8 mmole), stir after 1～2 hour, slowly add 50 ml waters, continue fully to stir 30 minutes, separate out white solid, suction filtration, methanol wash, 40-45 degree centigrade of drying is 12 hours in the air, obtain 5.05 gram omeprazole zinc salts, productive rate 95%.Zinc content (mass/mass): 10.01%.
The preparation of embodiment 2 (S)-omeprazole zinc salt
With (S)-omeprazole 5 gram (14.5 mmoles, 99%ee) be dissolved in 50 milliliters of tetrahydrofuran (THF)s, slowly add zinc ethyl 0.98 gram (8 mmole), stir after 2 hours, slowly add 50 ml waters, continue fully to stir 30 minutes, separate out white solid, suction filtration, methanol wash, 40-45 degree centigrade of drying is 12 hours in the air, obtains 5.05 gram (S)-omeprazole zinc salts, productive rate 95%.Zinc content (mass/mass): 9.28%.HPLC purity=99%, chirality HPLC purity=99.5%.
The preparation of embodiment 3 pantoprazole zinc salts
Pantoprazole 5 grams (13 mmole) are dissolved in 50 milliliters of methylene dichloride, slowly add zinc ethyl 0.89 gram (7.2 mmole), stir after 2 hours, slowly add the mixture of 50 ml waters and 20 ml methanol, continue fully to stir 30 minutes, separate out white solid, suction filtration, methanol wash, 40-45 degree centigrade of drying is 12 hours in the air, obtain 4.95 gram pantoprazole zinc salts, productive rate 92%.Zinc content (mass/mass): 8.36%.
The preparation of embodiment 4 (S)-pantoprazole zinc salt
With (S)-pantoprazole 5 gram (13 mmoles, 92%ee) be dissolved in 50 milliliters of chloroforms, slowly add zinc ethyl 0.89 gram (7.2 moles), stir after 2 hours, slowly add 50 ml waters and 20 milliliters of alcoholic acid mixtures, continue fully to stir 30 minutes, separate out white solid, suction filtration, methanol wash, 40-45 degree centigrade of drying is 12 hours in the air, obtains 5.12 gram pantoprazole zinc salts, productive rate 95%.Zinc content (mass/mass): 8.03%.HPLC purity=99%, chirality HPLC purity=92%.
The preparation of embodiment 5 rabeprazole zinc salts
Rabeprazole 5 grams (14 mmole) are dissolved in 50 milliliters of toluene, slowly add zinc ethyl 0.95 gram (7.7 mmole), stir after 2 hours, slowly add 50 ml methanol, continue fully to stir 30 minutes, separate out white solid, suction filtration, methanol wash, 40-45 degree centigrade of drying is 12 hours in the air, obtain 5.00 gram rabeprazole zinc salts, productive rate 91%.Zinc content (mass/mass): 9.87%.
The preparation of embodiment 6 (S)-rabeprazole zinc salt
With (S)-rabeprazole 5 gram (14 mmoles, 85%ee) in 50 milliliters of tetrahydrofuran (THF)s, slowly add zinc ethyl 0.95 gram (7.7 moles), stir after 2 hours, slowly add 50 milliliters of ethanol, continue fully to stir 30 minutes, separate out white solid, suction filtration, methanol wash, 40-45 degree centigrade of drying is 12 hours in the air, obtains 4.91 gram rabeprazole zinc salts, productive rate 89%.Zinc content (mass/mass): 9.17%.HPLC purity=99%, chirality HPLC purity=85%.
The preparation of embodiment 7 lansoprazole zinc salts
Lansoprazole 5 grams (13.5 mmole) are dissolved in 50 milliliters of tetracol phenixin, slowly add zinc ethyl 0.91 gram (7.4 mmole), stir after 2 hours, slowly add 50 ml waters, continue fully to stir 30 minutes, separate out white solid, suction filtration, methanol wash, 40-45 degree centigrade of drying is 12 hours in the air, obtain 5.23 gram lansoprazole zinc salts, productive rate 97%.Zinc content (mass/mass): 10.13%.
The preparation of embodiment 8 (S)-lansoprazole zinc salt
With lansoprazole 5 gram (13.5 mmoles, 86%ee) be dissolved in 50 milliliters of dioxane, slowly add zinc ethyl 0.91 gram (7.4 mmole), stir after 2 hours, slowly add 50 ml waters, continue fully to stir 30 minutes, separate out white solid, suction filtration, methanol wash, 40-45 degree centigrade of drying is 12 hours in the air, obtains 5.11 gram lansoprazole zinc salts, productive rate 95%.Zinc content (mass/mass): 9.39%.HPLC purity=99%, chirality HPLC purity=86%.
Embodiment 92-[[(4-methoxyl group-3,5-dimethyl-2-pyridyl) methyl]-sulfinyl]-preparation of 1H-benzoglyoxaline zinc salt
With 2-[[(4-methoxyl group-3; 5-dimethyl-2-pyridyl) methyl]-sulfinyl]-1H-benzoglyoxaline 5 gram (16 mmole) is dissolved in 50 milliliters of tetrahydrofuran (THF)s and the 10 milliliters of hexanes; slowly add zinc ethyl 1.09 grams (8.8 mmole); stir after 2 hours; slowly add 50 ml waters; continue fully to stir 30 minutes; separate out white solid; suction filtration; methanol wash, 40-45 degree centigrade of drying is 12 hours in the air, obtains 5.17 gram 2-[[(4-methoxyl groups-3; 5-dimethyl-2-pyridyl) methyl]-sulfinyl]-1H-benzoglyoxaline zinc salt, productive rate 93%.Zinc content (mass/mass): 11.21%.
Embodiment 10 (S)-2-[[(4-methoxyl group-3,5-dimethyl-2-pyridyl) methyl]-sulfinyl]-preparation of 1H-benzoglyoxaline zinc salt
With (S)-2-[[(4-methoxyl group-3; 5-dimethyl-2-pyridyl) methyl]-sulfinyl]-1H-benzoglyoxaline 5 gram (16 mmoles; 92%ee) be dissolved in 50 milliliters of tetrahydrofuran (THF)s; slowly add zinc ethyl 0.91 gram (7.4 mmole); stir after 2 hours; slowly add 50 ml waters; continue fully to stir 30 minutes; separate out white solid, suction filtration, methanol wash; 40-45 degree centigrade of drying is 12 hours in the air; obtain 5.02 gram (S)-2-[[(4-methoxyl groups-3,5-dimethyl-2-pyridyl) methyl]-sulfinyl]-1H-benzoglyoxaline zinc salt, productive rate 90%.Zinc content (mass/mass): 9.39%.HPLC purity=99%, chirality HPLC purity=92%.
Embodiment 115-methoxyl group-2-2[[[3-methyl-4-(2,2, the 2-trifluoro ethoxy)-2-pyridyl] methyl] sulfinyl]-preparation of 1H-benzoglyoxaline zinc salt
With 5-methoxyl group-2-2[[[3-methyl-4-(2,2, the 2-trifluoro ethoxy)-2-pyridyl] methyl] sulfinyl]-1H-benzoglyoxaline 5 gram (12.5 mmole) is dissolved in 50 milliliters of tetrahydrofuran (THF)s; slowly add zinc ethyl 0.85 gram (6.9 mmole); stir after 2 hours, slowly add 50 ml waters, continue fully to stir 30 minutes; separate out white solid; suction filtration, methanol wash, 40-45 degree centigrade of drying is 12 hours in the air; obtain 4.80 gram lansoprazole zinc salts, productive rate 89%.Zinc content (mass/mass): 8.31%.
Embodiment 12 (S)-5-methoxyl group-2-2[[[3-methyl-4-(2,2, the 2-trifluoro ethoxy)-2-pyridyl] methyl] sulfinyl]-preparation of 1H-benzoglyoxaline zinc salt
With (S)-5-methoxyl group-2-2[[[3-methyl-4-(2; 2; the 2-trifluoro ethoxy)-and the 2-pyridyl] methyl] sulfinyl]-1H-benzoglyoxaline 5 gram (12.5 mmoles; 92%ee) be dissolved in 50 milliliters of tetrahydrofuran (THF)s; slowly add zinc ethyl 0.85 gram (6.9 mmole); stir after 2 hours, slowly add 50 ml waters, continue fully to stir 30 minutes; separate out white solid; suction filtration, methanol wash, 40-45 degree centigrade of drying is 12 hours in the air; obtain 4.86 gram (S)-5-methoxyl group-2-2[[[3-methyl-4-(2; 2, the 2-trifluoro ethoxy)-the 2-pyridyl] methyl] sulfinyl]-1H-benzoglyoxaline zinc salt, productive rate 90%.Zinc content (mass/mass): 8.47%.HPLC purity=99%, chirality HPLC purity=92%.
Claims (8)
1. the preparation method of the zinc salt of one kind [(pyridyl of replacement) methyl] sulfinyl-1 H-benzimidazole compounds or its (S)-enantiomorph is characterized in that comprising following steps:
In organic solvent and under the room temperature, [(pyridyl of replacement) methyl] sulfinyl-1 H-benzimidazole compounds or their (S)-enantiomorph and organic zinc reagent reaction 0.5～3 hour add or do not add the zinc salt that quencher cancellation reaction obtains [(pyridyl of replacement) methyl] sulfinyl-1 H-benzimidazole compounds and their (S)-enantiomorph;
The mol ratio of described [(pyridyl of replacement) methyl] sulfinyl-1 H-benzimidazole compounds or their (S)-enantiomorph, organic zinc reagent and quencher is 1: 0.5～2: 0～1000;
Described [(pyridyl of replacement) methyl] sulfinyl-1 H-benzimidazole compounds has following structure:
Wherein, R
1, R
2, R
3Or R
4Be hydrogen, C independently
1～20Alkyl, C
1～20Alkoxyl group or ester group, halogen, phenyl, trifluoromethyl or nitro;
Described organic zinc reagent has following structure: R
5-Zn-R
6, R wherein
5And R
6Independently for C is arranged
1～6Alkyl;
Described quencher is protic solvent or their mixture.
2. the method for claim 1 is characterized in that the zinc salt of described [(pyridyl of replacement) methyl] sulfinyl-1 H-benzimidazole compounds and their (S)-enantiomorph is to exist with the unformed shape form.
3. the method for claim 1 is characterized in that described organic solvent is methylene dichloride, chloroform, tetracol phenixin, hexane, benzene, toluene, chlorobenzene, oil of mirbane, dimethylbenzene, ether, tertbutyl ether, tetrahydrofuran (THF), dioxane or their mixture.
4. method as claimed in claim 3 is characterized in that described organic solvent is a tetrahydrofuran (THF).
5. the method for claim 1 is characterized in that described organic zinc reagent is a zinc ethyl.
6. the method for claim 1 is characterized in that described protic solvent is water, methyl alcohol, ethanol, propyl alcohol or butanols.
7. method as claimed in claim 6 is characterized in that described quencher is a water.
8. the method for claim 1 is characterized in that the reaction back by filtration or centrifugation, and then washs and drying.
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|---|---|---|---|
| CNB2006100239569A CN100384839C (en) | 2006-02-17 | 2006-02-17 | Prepn process of [(substituted pyridyl) methyl] sulfenyl-1H-benzimidazole compound and its antimer zinc salt |
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|---|---|---|---|
| CNB2006100239569A CN100384839C (en) | 2006-02-17 | 2006-02-17 | Prepn process of [(substituted pyridyl) methyl] sulfenyl-1H-benzimidazole compound and its antimer zinc salt |
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| CN100384839C true CN100384839C (en) | 2008-04-30 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998054171A1 (en) * | 1997-05-30 | 1998-12-03 | Astra Aktiebolag | Novel form of s-omeprazole |
| WO2000044744A1 (en) * | 1999-01-28 | 2000-08-03 | Astrazeneca Ab | Potassium salt of ($i(s))-omeprazole |
| CN1683369A (en) * | 2005-03-15 | 2005-10-19 | 天津市轩宏医药技术有限公司 | S-omeprazole zinc salt and its preparing method and use |
-
2006
- 2006-02-17 CN CNB2006100239569A patent/CN100384839C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998054171A1 (en) * | 1997-05-30 | 1998-12-03 | Astra Aktiebolag | Novel form of s-omeprazole |
| WO2000044744A1 (en) * | 1999-01-28 | 2000-08-03 | Astrazeneca Ab | Potassium salt of ($i(s))-omeprazole |
| CN1683369A (en) * | 2005-03-15 | 2005-10-19 | 天津市轩宏医药技术有限公司 | S-omeprazole zinc salt and its preparing method and use |
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| CN1810804A (en) | 2006-08-02 |
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