CN101735283A - 一种氨基葡萄糖盐酸盐与氨基葡萄糖硫酸钾/钠盐的共结晶技术 - Google Patents
一种氨基葡萄糖盐酸盐与氨基葡萄糖硫酸钾/钠盐的共结晶技术 Download PDFInfo
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- CN101735283A CN101735283A CN200810194623A CN200810194623A CN101735283A CN 101735283 A CN101735283 A CN 101735283A CN 200810194623 A CN200810194623 A CN 200810194623A CN 200810194623 A CN200810194623 A CN 200810194623A CN 101735283 A CN101735283 A CN 101735283A
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- glucosamine
- potassium
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- sodium salt
- glucosamine hydrochloride
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- CBOJBBMQJBVCMW-BTVCFUMJSA-N (2r,3r,4s,5r)-2-amino-3,4,5,6-tetrahydroxyhexanal;hydrochloride Chemical compound Cl.O=C[C@H](N)[C@@H](O)[C@H](O)[C@H](O)CO CBOJBBMQJBVCMW-BTVCFUMJSA-N 0.000 title claims abstract description 23
- 229960001911 glucosamine hydrochloride Drugs 0.000 title claims abstract description 23
- 238000002288 cocrystallisation Methods 0.000 title claims abstract description 18
- 239000011591 potassium Substances 0.000 title claims abstract description 16
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229960002442 glucosamine Drugs 0.000 title claims abstract description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title abstract description 10
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 title abstract description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 title abstract description 4
- 235000011152 sodium sulphate Nutrition 0.000 title abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title abstract 3
- 229910052939 potassium sulfate Inorganic materials 0.000 title abstract 3
- 235000011151 potassium sulphates Nutrition 0.000 title abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- MTDHILKWIRSIHB-UHFFFAOYSA-N (5-azaniumyl-3,4,6-trihydroxyoxan-2-yl)methyl sulfate Chemical compound NC1C(O)OC(COS(O)(=O)=O)C(O)C1O MTDHILKWIRSIHB-UHFFFAOYSA-N 0.000 claims description 14
- 229960002849 glucosamine sulfate Drugs 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 159000000000 sodium salts Chemical class 0.000 claims description 9
- 159000000001 potassium salts Chemical class 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 5
- -1 glucosamine hydrochlorides Chemical class 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 1
- 230000008719 thickening Effects 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000010413 mother solution Substances 0.000 abstract 1
- 150000003109 potassium Chemical class 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 208000006558 Dental Calculus Diseases 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 102000011759 adducin Human genes 0.000 description 2
- 108010076723 adducin Proteins 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 201000003068 rheumatic fever Diseases 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CVCQAQVBOPNTFI-AAONGDSNSA-N (3r,4r,5s,6r)-3-amino-6-(hydroxymethyl)oxane-2,4,5-triol;sulfuric acid Chemical compound OS(O)(=O)=O.N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O.N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O CVCQAQVBOPNTFI-AAONGDSNSA-N 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 208000010392 Bone Fractures Diseases 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- MKQWTWSXVILIKJ-LXGUWJNJSA-N Chlorozotocin Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](C=O)NC(=O)N(N=O)CCCl MKQWTWSXVILIKJ-LXGUWJNJSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
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- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008414 cartilage metabolism Effects 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 229940099148 glucosamine sulfate potassium chloride Drugs 0.000 description 1
- 208000019622 heart disease Diseases 0.000 description 1
- 239000000568 immunological adjuvant Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000011275 oncology therapy Methods 0.000 description 1
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- 239000005017 polysaccharide Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
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- 206010039073 rheumatoid arthritis Diseases 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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Abstract
一种氨基葡萄糖盐酸盐与氨基葡萄糖硫酸钾/钠盐的共结晶技术，其特征是：以(2∶0.95～2∶1的摩尔比)加入氨基葡萄糖盐酸盐、硫酸钾/钠盐，每两摩尔氨基葡萄糖盐酸盐加1500-3000ml纯水，加热至50～70℃，保温搅拌0.5～2h；冷却至20～40℃，过滤，控制在50～70℃真空浓缩至出现大量结晶，停止加热浓缩，加入1000～2000ml 95％乙醇，静止4～24h，离心去除母液，结晶干燥即得产品。该技术具有操作简便、成本低、钾/钠盐反应完全等优点。
Description
技术领域
本发明涉及一种共结晶技术，确切地说公开了一种氨基葡萄糖盐酸盐与氨基葡萄糖硫酸钾盐/氨基葡萄糖硫酸钠盐的共结晶技术。
技术背景
氨基葡萄糖盐酸盐(Glucosamine Hydrochloride)，可由甲壳素经盐酸水解生成。它应用广泛，是抗癌药物氯脲霉素合成的主要原料，是最新的第三代功能性保健食品添加剂。它可作为抗细菌感染、免疫佐剂，是人体抗流感病毒的活化剂。它能促进软骨细胞蛋白多糖的合成，提高关节滑液粘性，改善关节软骨代谢，有效治疗风湿关节炎。
氨基葡萄糖硫酸钾盐(Glucosamine sulfate potassium chloride)由氨基葡萄糖盐酸盐与硫酸钾盐反应生成。它对风湿性关节炎、心脏病、肺炎及骨折均有辅助治疗作用，也是抗生素等多种药物制剂的辅料，还是制造隐形眼镜及双歧杆菌培养基的重要成分之一。
氨基葡萄糖硫酸钠盐(Glucosamine sulfate sodium chloride)由氨基葡萄糖盐酸盐与硫酸钠盐反应生成。它作为抗风湿性关节炎的原料药，近年发现有吸收自由基，抗氧化，抗衰老，减肥，调节内分泌，调节植物生长等多种有益的生理作用。故被广泛用于食品添加剂和保健食品的生产中。
目前工业生产氨基葡萄糖硫酸钾/钠盐的工艺流程为：以虾蟹壳或柠檬酸渣为原料，经过酸水解、浓缩、脱色、共结晶、洗涤和干燥等，最终获得氨基葡萄糖硫酸钾/钠盐。
传统的共结晶技术主要有3种：氨基葡萄糖硫酸盐与NaCl/KCl反应，乙醇等有机溶剂萃取；氨基葡萄糖盐酸盐水溶液与Na2SO4/K2SO4反应，乙醇等有机溶剂萃取；氨基葡萄糖水溶液与硫酸、金属氯化物反应，乙醇等有机溶剂萃取。传统共结晶工艺复杂、成本高、钾/钠盐不能完全反应等问题。本发明公开了一种氨基葡萄糖盐酸盐与氨基葡萄糖硫酸钾/钠盐的共结晶技术，该技术具有操作简便、成本低、钾/钠盐反应完全等优点。
发明内容
本发明公开的一种氨基葡萄糖盐酸盐与氨基葡萄糖硫酸钾/钠盐的共结晶技术，其特征是：以优化氨基葡萄糖盐酸盐与氨基葡萄糖硫酸钾/钠盐的共结晶工艺，使钾/钠盐反应完全。
氨基葡萄糖硫酸钠盐共结晶反应式为：
2C6H13NO5·HCl+Na2SO1＝(C6H14NO5)2SO4·2NaCl
431.2+142.0＝573.2
氨基葡萄糖硫酸钾盐共结晶反应式为：
2C6H13NO5·HCl+K2SO4＝(C6H14NO5)2SO4·2KCl
431.2+174.3＝605.5
得率(％)＝共结晶产晶(g)/按照氨基葡萄糖盐酸盐计算的理论产量(g)×100％
其方法步骤为：
以(2∶0.95～2∶1的摩尔比)加入氨基葡萄糖盐酸盐、硫酸钾/钠盐，每两摩尔氨基葡萄糖盐酸盐加1500-3000ml纯水，加热至50～70℃，保温搅拌0.5～2h；冷却至20～40℃，过滤，控制在50～70℃真空浓缩至出现大量结晶，停止加热浓缩，加入1000～2000ml 95％乙醇，静止4～24h，离心去除母液，结晶干燥即得产品。
附图说明
参见附图，是本发明的化学反应方程式。
实施方式
下面结合实施例进一步说明本发明的技术特征，但本发明并不受这些实施例的限制。
实施例1：
称取431.2g(2mol)氨基葡萄糖盐酸盐，加入142.0g(1mol)无水硫酸钠，加2000ml纯水，加热至60～65℃，保持温度在此范围内搅拌1h；然后冷却到30～35℃，0.22μm聚丙烯滤膜过滤；在50～70℃下，减压浓缩至出现大量结晶，停止加热浓缩，加入95％乙醇1000ml，静置12h，离心，结晶干燥，得562.7g，得率为98.2％。
所得氨基葡萄糖硫酸钠盐含量99.6％，旋光度+53.1°，pH 4.4，灰份24.2％，水分0.2％。
实施例2：
称取431.2g(2mol)氨基葡萄糖盐酸盐，加入170.8g(0.98mol)硫酸钾，加2000ml纯水，加热至60～65℃，保持温度在此范围内搅拌1h；然后冷却到30～35℃，0.22μm聚丙烯滤膜过滤；在50～70℃下，减压浓缩至出现大量结晶，停上加热浓缩，加入95％乙醇1000ml，静置12h，离心，结晶干燥，得591.0g，得率为97.6％。
所得氨基葡萄糖硫酸钾盐含量99.3％，旋光度+51.3°，pH 4.3，灰份28.5％，水分0.2％。
Claims (3)
1.一种氨基葡萄糖盐酸盐与氨基葡萄糖硫酸钾/钠盐的共结晶技术，其特征是：优化氨基葡萄糖盐酸盐和硫酸钾/钠盐的化学反应条件；优化共结晶条件，包括配料比、溶解温度、浓缩温度等。
2.根据权利要求1所述的氨基葡萄糖盐酸盐与氨基葡萄糖硫酸钾/钠盐的共结晶技术，其特征是：上述方法的步骤为：
以(2∶0.95～2∶1的摩尔比)加入氨基葡萄糖盐酸盐、硫酸钾/钠盐，每两摩尔氨基葡萄糖盐酸盐加1500～3000ml纯水；加热至50～70℃，保温搅拌0.5～2h；冷却至20～40℃，过滤；控制在50～70℃真空浓缩至出现大量结晶，停止加热浓缩；加入1000～2000ml 95％乙醇，静置4～24h；离心去除母液，结晶干燥即得产品。
3.根据权利要求1、2所述的氨基葡萄糖盐酸盐与氨基葡萄糖硫酸钾/钠盐的共结晶技术，其特征是：氨基葡萄糖盐酸盐反应完全，产品收率高达98％左右。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110305176A (zh) * | 2019-06-28 | 2019-10-08 | 山东润德生物科技有限公司 | 一种提高氨基葡萄糖盐酸盐热稳定性的制备方法 |
| CN110818751A (zh) * | 2019-12-02 | 2020-02-21 | 山东润德生物科技有限公司 | 一种硫酸氨基葡萄糖氯化钠复盐的制备方法 |
| CN114853826A (zh) * | 2022-05-12 | 2022-08-05 | 山西辅仁恒峰药业有限公司 | 一种硫酸氨基葡萄糖氯化钠复盐制备方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CH690719A5 (it) * | 1996-08-19 | 2000-12-29 | Rotta Res B V Amsterdam Swiss | Procedimento per la preparazione di sali misti della glucosamina. |
| US5843923A (en) * | 1998-05-22 | 1998-12-01 | Jame Fine Chemicals, Inc. | Glucosamine sulfate potassium chloride and process of preparation thereof |
| WO2002043653A2 (en) * | 2000-12-01 | 2002-06-06 | Nicholas Piramal India Limited | Crystalline glucosamine sulphate metal salts |
| CN1142172C (zh) * | 2001-09-14 | 2004-03-17 | 湖北普爱生物工程有限公司 | 氨基葡萄糖硫酸盐的制备方法 |
| CN101012251A (zh) * | 2007-01-11 | 2007-08-08 | 庄建华 | 一种硫酸氨基葡萄糖复合盐的制备方法 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110305176A (zh) * | 2019-06-28 | 2019-10-08 | 山东润德生物科技有限公司 | 一种提高氨基葡萄糖盐酸盐热稳定性的制备方法 |
| CN110818751A (zh) * | 2019-12-02 | 2020-02-21 | 山东润德生物科技有限公司 | 一种硫酸氨基葡萄糖氯化钠复盐的制备方法 |
| CN110818751B (zh) * | 2019-12-02 | 2020-11-10 | 山东润德生物科技有限公司 | 一种硫酸氨基葡萄糖氯化钠复盐的制备方法 |
| CN114853826A (zh) * | 2022-05-12 | 2022-08-05 | 山西辅仁恒峰药业有限公司 | 一种硫酸氨基葡萄糖氯化钠复盐制备方法 |
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