CN1044475C - Preparing matrine and matrine oxide from sophora alopecuroide and its producing technology - Google Patents
Preparing matrine and matrine oxide from sophora alopecuroide and its producing technology Download PDFInfo
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- CN1044475C CN1044475C CN96109730A CN96109730A CN1044475C CN 1044475 C CN1044475 C CN 1044475C CN 96109730 A CN96109730 A CN 96109730A CN 96109730 A CN96109730 A CN 96109730A CN 1044475 C CN1044475 C CN 1044475C
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Abstract
The present invention relates to matrine and oxymatrine prepared from sophora herb and a production technology thereof. The present invention is characterized in that stems and leaves or seeds of sophora herb are made into coarse matrine by the steps of pulverization, leaching, solvent extraction, transconformation, sedimentation, catalytic hydrogenation and aqueous phase organic extraction. A matrine product is obtained by recrystallizing and drying the coarse matrine. The matrine is made into an oxymatrine product by the steps of oxidation by using hydrogen peroxide, dewatering, distillation by pressure reduction, filtration, crystallization, washing and drying. The matrine and the oxymatrine are raw materials for producing medicines, and can be used for preparing therapeutic medicines for treating gynecopathy, hepatitis B and hyperleucocytosis.
Description
The present invention relates to have the matrine technology of pharmaceutical value a kind of the preparation from Herba Sophorae alopecuroidis.
Herba Sophorae alopecuroidis Sophora alopecuroides L. is a kind of per nnial herb that cattle and sheep do not eat on China's desert steppe, belongs to the Sophora leguminous plants, and the output of China accounts for 62% of world wide production, in China North China, northwest growth is arranged all.Its root, stem, leaf, seed contain more than 20 kind of alkaloid, especially to be called in the sophora alopecuroide alkaloid higher for its seed, wherein great majority are identical with the contained alkaloid of herbal medicine kuh-seng SophoraflavescensAit, and kuh-seng is a kind of the most ancient, one of the most frequently used Chinese medicine, it is widely used in clinical, prove not only have anticancer, press down cancer, suppress and kill various microbial processs, and immunity system, neural system, cardiovascular systems are had pharmacological action widely.Therefore since the thirties just to Herba Sophorae alopecuroidis, kuh-seng is studied, various alkaloids have therefrom been found, only did structural research at that time, and do not carry out applicating and exploitation, in recent years, the world of medicine pays much attention to the applied research of Herba Sophorae alopecuroidis both at home and abroad, active development wherein has the alkaloid of pharmaceutical use, at present verified pharmaceutical use arranged matrine matrine arranged, kuh-seng alkene alkali Sophocapine, sophorine Sophoridine, sophoramine Sophoramine, Oxymatyine N-oxymatrine, Cytisine N-methylcyticine, and from Herba Sophorae alopecuroidis, extract alkaloid, majority is in the in the majority of laboratory study at present, because the problem of process aspect at present can't scale production.Therefore, still can not provide and meet bitter alkali and the Oxymatyine of giving birth to of the medicine of producing medicine.
Purpose of the present invention is just in order to solve the problem of above-mentioned existence, and through doing painstaking research for many years, provide a kind of possessing skills to go up the advanced person, the technology that reasonably prepares matrine economically from Herba Sophorae alopecuroidis, thereby obtain the matrine that meets pharmaceutical production of the high yield of high purity, for medicinal career has been started a new road again.
The objective of the invention is to realize by following technical proposal:
A kind of matrine from the Herba Sophorae alopecuroidis preparation, it is characterized in that containing in this product molecular formula is C
15H
24N
2O, structural formula is
The matrine component content more than 98%, surplus is the white needles or the granular crystal of water.
Production technique of the present invention is to be that form with salt exists according to the biology total alkali that contains in the Herba Sophorae alopecuroidis plant, when leach sophora alopecuroide or stem and the Ye Shi that pulverizes with diluted alkaline, can be converted into the alkaloid of unbound state, carry out enrichment by organic solvent extraction, and then make the transition with acid, make alkaloid go into aqueous phase from the organic phase transfer, and exist with the form of salt, when precipitating with alkali, because various alkaloid chemical property differences, wherein kuh-seng alkene alkali and small part matrine precipitation is separated out, and most of matrine of aqueous phase, sophorine and other alkaloid are stayed in the mother liquor of precipitation of ammonium, because kuh-seng alkene alkali structurally has a two key, but this pair key hydrogenation is opened, therefore, behind kuh-seng alkene alkali hydrogenation, just change into matrine, and the most of matrine in the mother liquor of precipitation of ammonium, sophorine and other alkaloid optionally extract with organic extractant, making matrine be extracted the back separates again with other alkaloid with sophorine and extracts, the matrine of organic extractant phase is removed organic phase through underpressure distillation, reclaim again and reuse, obtain the matrine of solid matrine and hydrogenation conversion, merge the back and carry out recrystallization with sherwood oil, can obtain the matrine product through vacuum-drying, also can be with preparing matrine with production technique in the step, water after transition is reconciled pH value directly extract matrine, sophorine can reach same effect.
Concrete preparation method is as described below:
A kind ofly prepare the technology of matrine, it is characterized in that it is made up of following operation from Herba Sophorae alopecuroidis:
A) seed of selection fine Herba Sophorae alopecuroidis or stem and leaf are that material is pulverized, and its granularity is the 10-80 order, and in the container of packing into, the alkaline solution that adds 1-10% concentration leaches, and the alkaline solution consumption is the 20-30% of weight of material, extraction time 24-48 hour;
B) (a) being leached the material that finishes packs in the enamel reaction still of chuck heating, the compound or the haloalkane organic solvent that add weight of material 1-5 benzene doubly simultaneously, and stirring heating 70-120 ℃, the pump around circuit of carrying out more than at least seven sections is extracted alkaloid, each 2-6 hour pump around circuit time, lifeless matter alkali in material extracts and finishes, and its material slag tail is abandoned.Each organic solvent extraction liquid changes in the container, with 5-10% concentration consumption is that 1/2 acid solution of organic solvent extraction liquid makes the transition, transition, the back was precipitated with 30% alkali lye adjusting PH=7-9, will precipitate through centrifugation to obtain matrine and kuh-seng alkene alkali mixture and aqueous solution mother liquor again;
C) matrine of (b) and kuh-seng alkene alkali mixture are packed in the reactor,, add the metallic nickel catalyzer with less water or dissolve with ethanol, catalyst levels and kuh-seng alkene alkali weight ratio are 1: 5-15, seal still then,, feed 0.2-1.0Kg/cm with rare gas element argon gas or nitrogen excluding air
2The hydrogen of pressure till thin-layer chromatography does not have kuh-seng alkene alkali, stops hydrogenation in reactant, reaction finishes.Through centrifugation, underpressure distillation concentrates, and is solvent-free in reactant, obtains rough matrine then, reuses behind the catalyst regeneration that separation obtains;
(d) again the aqueous solution mother liquor of (b) is regulated PH=7-11 with alkali lye after, compound or haloalkane with benzene carry out extracting more than at least seven sections matrine, consumption is 0.5-1.0 a times of mother liquor, the water tail is abandoned, extracted organic phase is through vacuum distillation recovered solvent, and solid is rough matrine and (c) the rough matrine merging of item, carries out recrystallization with 5-10 sherwood oil doubly again, obtain refining matrine crystal, last vacuum-drying obtains final matrine product.
Wherein one step of leach liquor back transition is regulated PH=7-11 with alkali lye, compound or haloalkane with benzene carry out extracting more than at least seven sections matrine, the water tail is abandoned, extracted organic phase is through vacuum distillation recovered solvent, and solid is the mixture of rough kuh-seng alkene alkali, matrine, and mixture is packed into and dissolved with small amount of ethanol in the reactor, add the metallic nickel catalyzer with above-mentioned method, carry out hydrogenation reaction, till no kuh-seng alkene alkali, reaction finishes.Through centrifugation, underpressure distillation is concentrated into solvent-free then, obtains rough matrine, and rough matrine obtains final matrine product through recrystallization, washing, vacuum-drying, and promptly a step neutralisation prepares matrine technology.
The metallic nickel catalyzer is that single nickel salt, nickelous nitrate, nickelous chloride and four kinds of any one nickel salt waters of nickelous acetate or dissolve with ethanol add the water of 1M POTASSIUM BOROHYDRIDE or sodium borohydride or the product that the ethanolic soln reaction obtains.The catalyzer that obtains is separated in the reaction back can add less water, adds the water or the ethanolic soln reaction regeneration of 1M POTASSIUM BOROHYDRIDE or sodium borohydride again, reuses; The compound of benzene be three kinds of benzene,toluene,xylenes wherein any one, haloalkane be two kinds of ethylene dichloride, trichloromethane wherein any one; Leaching alkali lye be four kinds in sodium hydroxide, potassium hydroxide, ammonium hydroxide, yellow soda ash wherein any one; The acid that diluted acid makes the transition is sulfuric acid or hydrochloric acid.
Matrine of the present invention adopts thin layer chromatography to measure.
Concrete grammar is: get hydrogenation reaction testing sample and matrine standard model and be made into 0.5% solution respectively with dehydrated alcohol, get the 10 microlitres different positions o'clock on 1% carboxymethyl cellulose, 200 order silica gel G chromatoplates respectively, with the inclination ascending method with benzene: acetone: diethylamine=mixture launched in 5: 2: 0.2, with rare Dragendorff's reagent colour developing, kuh-seng alkene alkali colour developing spot must not be arranged after the reduction.
The sophora alopecuroide that the present invention adopts contains biology total alkali 2.2-2.7%, and wherein matrine is 0.6-0.8%, kuh-seng alkene alkali 0.6-0.8%, and sophorine 0.7-0.9%, other alkaloid is below 0.1%.Stem and leaf contain biology total alkali 0.5-1.2%, and wherein matrine is 0.1-0.3%, kuh-seng alkene alkali 0.1-0.3%, and sophorine 0.2-0.4%, other alkaloid is below 0.05%.
Adopt production technique of the present invention, kuh-seng alkene alkali transforms the transformation efficiency 70-80% of matrine, and total alkaloids reclaims the rate of recovery 80-85% of matrine.
Owing to take technique scheme to make the technology of the present invention compared with the prior art have following advantage and effect.
A) the product matrine of the present invention preparation meets the medicinal raw material of producing medicine fully, and purity height, good, the inclusion-free of quality are used to prepare the medicine of multiple diseases such as the leukopenia for the treatment of gynecopathy, hepatitis B, a variety of causes and causing, diarrhoea;
B) technology of the present invention, owing to adopt the advanced catalysis agent to carry out low-voltage hydrogenation, technical process is simplified, and reduces facility investment, improves the rate of recovery, has improved benefit.
C) make full use of the Herba Sophorae alopecuroidis natural resources, the people have broken away from poverty for Desert Area, have improved standard of living; can also accelerate simultaneously the vegetation protection of Desert Area and sand ground, check winds and fix drifting sand, improve environment; nourishing moisture, improve environment, is the eternal lasting matter of fundamental importance that benefits future generations boundless beneficence.
D) product nontoxic, have no side effect, produce the three wastes and meet national environmental standard.
Description of drawings:
Fig. 1 is preparation matrine process flow sheet;
Fig. 2 prepares the matrine technical process for adopting a step neutralisation.
Embodiment further specifies the technology of the present invention below in conjunction with accompanying drawing:
Embodiment 1,
Prepare matrine by technical process shown in the accompanying drawing 1, select for use North China to produce sophora alopecuroide 1000Kg, contain matrine 0.8%, kuh-seng alkene alkali 0.8%, sophorine 0.9%, other alkaloid 0.1%, be crushed to and add 1% potassium hydroxide alkali lye 200Kg in the container of packing into behind 10 orders and leached 48 hours, the sophora alopecuroide material that then leaching is finished is packed into and is added the dimethylbenzene organic solvent simultaneously in the enamel reaction still of chuck heating, and its consumption is 1000Kg, be heated with stirring to 80-90 ℃, begin to carry out the solvent refluxing circulation and extract alkaloid, each return time 2 hours is through 10 reflux cycle, lifeless matter alkali afterreaction finishes in the material, and sophora alopecuroide slag tail is abandoned.Gained solvent extraction liquid makes the transition with 10% hydrochloric acid, the dilute hydrochloric acid consumption is 500Kg, transition, the back transferred pH value=7 to precipitate with 30% concentration liquid caustic soda, emit precipitation, precipitation obtains matrine and kuh-seng alkene alkali mixture 9.8Kg and aqueous solution mother liquor 500Kg through centrifugation, mixture is packed in the still again, dissolves with small amount of ethanol, add metallic nickel catalyzer 0.5Kg, catalyzer is taken from by the product of 1Kg single nickel salt water 10Kg dissolving back with the POTASSIUM BOROHYDRIDE reactant aqueous solution of 1M.Seal still then, logical nitrogen exhausted air feeds 0.2Kg/cm
2The hydrogen of pressure till thin-layer chromatography is measured no kuh-seng alkene alkali, stops hydrogenation in reactant, reaction finishes.Carry out centrifugation again, underpressure distillation concentrates, make in the reactant solvent-free, obtain rough matrine 9.8Kg, reuse behind the isolating catalyst regeneration, obtained aqueous solution mother liquor 500Kg transfers pH value=7 with 30% sodium hydroxide, stirring extraction water tail after seven sections extractions with xylene solvent 200Kg abandons, extracted organic phase is through vacuum distillation recovered solvent, solid is that rough matrine 5.1Kg and aforesaid rough matrine merge 14.9Kg altogether, carries out recrystallization with the 75Kg sherwood oil again, the refining matrine crystal that obtains, last vacuum-drying, be matrine product 11.98Kg of the present invention, matrine content is 98.6%, water 1.4%, kuh-seng alkene alkali transformation efficiency 90%, the rate of recovery 84.5% of recovery matrine from biology total alkali.
Embodiment 2,
Extract matrine by technical process shown in Figure 2, select for use the northwest to produce sophora alopecuroide 1000Kg, contain matrine 0.65%, kuh-seng alkene alkali 0.7%, sophorine 0.75%, other alkaloid 0.1% is pulverized 40 orders, add 5% sodium hydroxide solution 250Kg and leach after 36 hours, the sophora alopecuroide material that then leaching is finished is packed in the enamel still of chuck heating, adds ethylene dichloride solvent 1500Kg simultaneously, be heated with stirring to temperature 110-120 ℃, begin to carry out solvent refluxing circulation and extract alkaloid, each 4 hours time is through after 8 reflux cycle, make lifeless matter alkali reaction end in the material, sophora alopecuroide slag tail is abandoned.Gained solvent extraction liquid makes the transition with 10% sulphuric acid soln 500Kg, transition, pH value=8 were transferred with 30% concentration liquid caustic soda potassium hydroxide in the back, use ethylene dichloride 250Kg, carry out cycling extraction 8 times, the water tail is abandoned, organic phase is through underpressure distillation, solvent recycled is used, the rough matrine of the solid that obtains, kuh-seng alkene alkali mixture, again this material is packed into and use water dissolution in the still, the nickel salt that adding nickel catalyzator 0.7Kg takes from by nickelous nitrate is the product of the POTASSIUM BOROHYDRIDE ethanolic soln reaction of 1.4Kg adapted water 12Kg dissolving back and 1M, seals still then.Use the argon gas excluding air, feed 0.6Kg/cm
2The hydrogen of pressure does not have kuh-seng alkene alkali until reactant, stops hydrogenation reaction and finishes.Carry out centrifugation, underpressure distillation concentrates, and is solvent-free to the reactant, obtains rough matrine, returns use behind the isolating catalyst regeneration, and rough matrine 13Kg with 130Kg sherwood oil recrystallization, obtains matrine 11.5Kg of the present invention after the vacuum-drying.Matrine content 98.7%, moisture 1.3%, kuh-seng alkene alkali turnover ratio 85%, the rate of recovery 80% of matrine from total alkaloids.
Embodiment 3:
Prepare matrine by technical process shown in the accompanying drawing 1, stem and the leaf of selecting for use the northwest to produce Herba Sophorae alopecuroidis are raw material 1000Kg, contain matrine 0.2%, kuh-seng alkene alkali 0.15%, sophorine 0.3%, other alkaloid 0.05% is crushed in the container of packing into behind 80 orders, adding 10% ammonium hydroxide alkali lye 300Kg leached 24 hours, stem that leaching is finished and leaf material are packed into and are added the trichloromethane organic solvent simultaneously in the enamel reaction still of chuck heating then, its consumption is 2000Kg, begin to be heated with stirring to 70-80 ℃, carry out the solvent refluxing circulation and extract alkaloid, each return time 6 hours.Through 7 sections reflux cycle, lifeless matter alkali afterreaction finishes in the material.Stem and leaf slag tail are abandoned, gained solvent extraction liquid makes the transition with 5% sulfuric acid, the dilute sulphuric acid consumption is 500Kg, transition, the back transferred pH value=9 to precipitate with 30% concentration liquid caustic soda, emit precipitation, precipitation obtains matrine and sophorine mixture 2.1Kg and aqueous solution mother liquor 500Kg through centrifugation, again mixed biologic alkali is packed in the still, dissolve with small amount of ethanol, add metallic nickel catalyzer 0.1Kg, catalyzer take from by behind the 0.5Kg nickelous acetate water 6Kg dissolve with ethanol with the product of the ethanol solution of sodium borohydride reaction of 1M.Seal still then, logical nitrogen exhausted air feeds 1.0Kg/cm
2The hydrogen of pressure till thin-layer chromatography is measured no kuh-seng alkene alkali, stops hydrogenation in reactant, reaction finishes.Carry out centrifugation again, underpressure distillation concentrates, and makes in the reactant solvent-freely, obtains rough matrine 2.1Kg, reuses behind the isolating catalyst regeneration.Obtained aqueous solution mother liquor 500Kg transfers pH value=11 with 30% sodium hydroxide, 300Kg stirs extraction with the trichloromethane solvent, the water tail is abandoned after eight sections extractions, and extracted organic phase is through vacuum distillation recovered solvent, and solid is that rough matrine 1.2Kg and aforesaid rough matrine merge 3.3Kg altogether.Carry out recrystallization with the 33Kg sherwood oil again, obtain refining matrine crystal, last vacuum-drying, be matrine product 2.64Kg of the present invention, matrine content is 98%, water 2%, kuh-seng alkene alkali transformation efficiency 70%, the rate of recovery 85% of recovery matrine from biology total alkali.
Claims (6)
1, a kind ofly prepare the technology of matrine, it is characterized in that it is made up of following operation from Herba Sophorae alopecuroidis:
A) seed of selection fine Herba Sophorae alopecuroidis or stem and leaf are that material is pulverized, and its granularity is the 10-80 order, and in the container of packing into, the alkaline solution that adds 1-10% concentration leaches, and the alkaline solution consumption is the 20-30% of weight of material, extraction time 24-48 hour;
B) (a) being leached the material that finishes packs in the enamel reaction still of chuck heating, the compound or the haloalkane that add weight of material 1-5 benzene doubly simultaneously, and stirring heating 70-120 ℃, the pump around circuit of carrying out more than at least seven sections is extracted alkaloid, each 2-6 hour pump around circuit time, lifeless matter alkali in material, extract and finish, its material slag tail is abandoned, each organic solvent extraction liquid changes in the container, with 5-10% concentration consumption is that 1/2 acid solution of organic solvent extraction liquid makes the transition, and the back was regulated PH=7-9 with 30% alkali lye and precipitated transition, will precipitate the process centrifugation again and obtain matrine and kuh-seng alkene alkali mixture and aqueous solution mother liquor;
C) matrine of (b) and kuh-seng alkene alkali mixture are packed in the reactor,, add the metallic nickel catalyzer with less water or dissolve with ethanol, catalyst levels and kuh-seng alkene alkali weight ratio are 1: 5-15, seal still then,, feed 0.2-1.0Kg/cm with rare gas element argon gas or nitrogen excluding air
2The hydrogen of pressure till no kuh-seng alkene alkali behind the thin-layer chromatography, stops hydrogenation in reactant, reaction finishes.Through centrifugation, underpressure distillation concentrates, and is solvent-free in reactant, obtains rough matrine then, reuses behind the catalyst regeneration that separation obtains;
(d) again the aqueous solution mother liquor of (b) is regulated PH=7-11 with alkali lye after, compound or haloalkane with benzene carry out extracting more than at least seven sections matrine, consumption is 0.5-1.0 a times of mother liquor, the water tail is abandoned, extracted organic phase is through vacuum distillation recovered solvent, and solid is rough matrine and (c) the rough matrine merging of item, carries out recrystallization with 5-10 sherwood oil doubly again, obtain refining matrine crystal, last vacuum-drying obtains final matrine product.
2, technology according to claim 1, afterwards a step is regulated PH=7-11 with alkali lye to it is characterized in that making the transition described leach liquor, compound or haloalkane with benzene carry out extracting more than at least seven sections matrine, kuh-seng alkene buck phase tail is abandoned, extracted organic phase is through vacuum distillation recovered solvent, solid is rough kuh-seng alkene alkali, the mixture of matrine, mixture is packed in the reactor with less water or dissolve with ethanol, add the metallic nickel catalyzer with above-mentioned method, carry out hydrogenation reaction, till no kuh-seng alkene alkali, reaction finishes, and then through centrifugation, underpressure distillation is concentrated into solvent-free, obtain rough matrine, rough matrine is through recrystallization, washing, vacuum-drying obtains final matrine product.
3, production technique according to claim 1 and 2 is characterized in that the metallic nickel catalyzer is that single nickel salt, nickelous nitrate, nickelous chloride and four kinds of any one nickel salt waters of nickelous acetate or dissolve with ethanol add the water of 1M POTASSIUM BOROHYDRIDE or sodium borohydride or the product that the ethanolic soln reaction obtains.The catalyzer that obtains is separated in the reaction back can add less water, adds the water or the ethanolic soln reaction regeneration of 1M POTASSIUM BOROHYDRIDE or sodium borohydride again, reuses.
4, production technique according to claim 1 and 2 it is characterized in that the compound of benzene be three kinds of benzene,toluene,xylenes wherein any one, haloalkane be two kinds of ethylene dichloride, trichloromethane wherein any one.
5, production technique according to claim 1 and 2, it is characterized in that leaching alkali lye and be four kinds in sodium hydroxide, potassium hydroxide, ammonium hydroxide, yellow soda ash wherein any one.
6, production technique according to claim 1 and 2 is characterized in that the acid that diluted acid makes the transition is sulfuric acid or hydrochloric acid.
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|---|---|---|---|
| CN96109730A CN1044475C (en) | 1996-09-10 | 1996-09-10 | Preparing matrine and matrine oxide from sophora alopecuroide and its producing technology |
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|---|---|---|---|
| CN96109730A CN1044475C (en) | 1996-09-10 | 1996-09-10 | Preparing matrine and matrine oxide from sophora alopecuroide and its producing technology |
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| CNB991091876A Division CN1148370C (en) | 1999-06-22 | 1999-06-22 | Process for preparing oxymatrine from sophora alopecuroide |
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| CN1149584A CN1149584A (en) | 1997-05-14 |
| CN1044475C true CN1044475C (en) | 1999-08-04 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1119347C (en) * | 2000-06-19 | 2003-08-27 | 宁夏药物研究所（有限公司） | Preparation of matrine from foxtail-like sophora seed |
| CN1325496C (en) * | 2000-11-18 | 2007-07-11 | 宁夏药物研究所（有限公司） | Preparation process of sophora alopecuroides series alkaloid salts substances |
| CN1325495C (en) * | 2000-11-18 | 2007-07-11 | 宁夏药物研究所（有限公司） | Preparation process of sophoridine |
| CN1111533C (en) * | 2000-11-18 | 2003-06-18 | 宁夏药物研究所 | The preparation technology of Oxymatyine |
| CN101130541B (en) * | 2007-09-11 | 2010-09-29 | 重庆大学 | Method for extracting and separating matrine and oxymatrine from trialkyl phosphine oxide inverse micellar solution |
| CN102633798A (en) * | 2012-04-26 | 2012-08-15 | 宁夏紫荆花制药有限公司 | Method for preparing high-purity matrine from sophora alopecuroides |
| CN102786523A (en) * | 2012-07-19 | 2012-11-21 | 宁夏紫荆花制药有限公司 | Technology for preparing sophocarpine from Sophora alopecuroides L |
| CN102850352A (en) * | 2012-07-26 | 2013-01-02 | 宁夏紫荆花制药有限公司 | Preparation method high-purity high-yield oxysophocarpine |
| CN102875552B (en) * | 2012-10-12 | 2014-10-08 | 塔里木大学 | Composite solvent for efficiently extracting alkaloids |
| CN112047946A (en) * | 2020-09-08 | 2020-12-08 | 北方民族大学 | A method for preparing matrine from oxymatrine by transfer hydrogenation |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073681A (en) * | 1991-12-23 | 1993-06-30 | 傅维芳 | The freezing vacuum extraction method of matrine |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073681A (en) * | 1991-12-23 | 1993-06-30 | 傅维芳 | The freezing vacuum extraction method of matrine |
Non-Patent Citations (3)
| Title |
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| 中草药成分化学，第一版 1980.1.1 北京医学院，北京中医学院主编 * |
| 中草药成分化学，第一版 1980.1.1 北京医学院，北京中医学院主编;内蒙古大学学报，自然科学版，VOL.25(6) 1994.1.1 ZHANG,WEN ET AL * |
| 内蒙古大学学报，自然科学版，VOL.25(6) 1994.1.1 ZHANG,WEN ET AL * |
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Owner name: NEI MENGGU ZHONGKANG BIOLOGY TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: KUSHEN BIOCHEMICAL GROUP CO LTD, INNER MONGOLIAN AUTONOMOUS REGION Effective date: 20030124 |
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Effective date of registration: 20030124 Address after: 010051 Inner Mongolia Hohhot Kang biological technology Co., Ltd., 546 East Sea Road, Xincheng District, the Inner Mongolia Autonomous Region Patentee after: Zhongkang Biotechnology Co., Ltd. Address before: 010020 No. 41 health Street, Hohhot, the Inner Mongolia Autonomous Region Patentee before: Kuh-seng Biochemical Group Co., Ltd., Nei Monggol |
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