CN1793143A - Process for producing high purity matrine oxide - Google Patents
Process for producing high purity matrine oxide Download PDFInfo
- Publication number
- CN1793143A CN1793143A CN 200510048244 CN200510048244A CN1793143A CN 1793143 A CN1793143 A CN 1793143A CN 200510048244 CN200510048244 CN 200510048244 CN 200510048244 A CN200510048244 A CN 200510048244A CN 1793143 A CN1793143 A CN 1793143A
- Authority
- CN
- China
- Prior art keywords
- high purity
- producing high
- oxide
- solvent
- purity matrine
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
The invention relates to a method to make high purity oxymatrine that includes the following steps: mixing kuhseng or fenugreek raw material with acid solution , taking sonic oscillation, filtering, adjusting pH value to below 3, degreasing by non-polar solvent; adjusting the pH value to over 11, extracting by organic solvent, adding crystal solvent to dissolve, decoloring, crystallizing, solving by alcohol or methanol adding catalyst to take hydrogenation reaction, hydrogen peroxide oxidation to gain raw oxymatrine, adding to crystal solvent to take recrystallizing to gain oxymatrine. The invention simplifies separating process, decreases cost and realizes high purity oxymatrine distillation.
Description
Technical field
The present invention relates to a kind of method of producing high purity matrine oxide.
Technical background
Kuh-seng and Herba Sophorae alopecuroidis all are rich in Radix Sophorae Flavescentis alkaloid class and bioflavonoid active ingredient, present research mainly concentrates on the Radix Sophorae Flavescentis alkaloid aspect, Radix Sophorae Flavescentis alkaloid is to be the similar alkaloid of a class chemical structure of representative with the matrine, 23 kinds of alkaloids have now been isolated, comprise matrine, Oxymatyine, sophocarpine, Sophocarpidin, sophoranol, sophorine, Anagyrine, Ba Puye alkali, sophoranole etc., sophocarpidine has multiple physiologically active, for hepatitis, viral myocarditis, tumours etc. all have restraining effect, also have broad application prospects in field of biological pesticide.Bureau of Drugs Supervision of country has proposed higher standard for medicinal matrine, Oxymatyine, all requires purity greater than 98.0%, and this purification technique for the matrine series product is a challenge.
Patent of invention " bitter beans comprehensive use " is (CN85108322A) by the bitter beans detoxification of acid treatment, again with acid solution with alkaloid back extraction successively, but various alkaloidal physicochemical property are very approaching, rely on the adjusting of pH value to be difficult to obtain high purity product merely; Patent of invention " utilizes transfer hydrogenation to be prepared the method for matrine by sophocarpine " (ZL00118510.1) by hydrazine hydrate and sophocarpine prepared in reaction matrine in the presence of oxygen, but separating of high purity sophocarpine own and matrine purified with regard to existing problems, because the existence of Oxymatyine and sophocarpine, gained matrine product purity is inevitable limited; Patent of invention " preparation technology of ALOPERINE " (CN00136814.1) (CN1368502A) directly extracts by sophora alapecuroides liquid with " preparation technology of sophora alapecuroides ", obtain the ALOPERINE crude product, recrystallization obtains purity greater than 98% ALOPERINE, this process can not realize the separation of matrine, Oxymatyine, sophocarpine, Sophocarpidin, sophoranol etc., so 98% purity should be the content of biology total alkali, rather than the product of single chemical composition; Patent of invention " adopts the CO2 supercritical extraction technique to prepare the method for aqueous matrine solution and matrine pulvis " and (CN02103757.4) obtains content less than the former powder of 50% matrine by supercritical extraction, but Ge Fahuan (Chinese medicinal materials, 2003,426) etc. 26 (6): the people's studies show that under the condition without entrainment agent, supercritical co almost can not extract for matrine, it is also undesirable to add ethanol entrainment agent effect of extracting, need or introduce nonionogenic tenside by the ammoniacal liquor alkalization and just can obtain higher yield, but ammoniacal liquor has stronger corrosive nature to overcritical device, and tensio-active agent be separating fully of product one than complicated problems.
By tubular fibre membrane ultrafiltration (Zhengzhou Engineering College's journal, 2003,56), Zeo-karb (Xibei Forest College's journal 24 (4):, 113), micro-filtration-Amberlyst process (ACAD J GCP, 2,003 2004,11 (1):, 334), resin purification-column chromatography (extracts the production method of matrine from Herba Sophorae alopecuroidis 19 (4):, CN1583743A) the alkaloidal report of separating matrine-like is a lot, but all has the running cost height, the problem that production lot is little.
Alkaloid is mainly based on matrine, Oxymatyine, Sophocarpidin in kuh-seng and the Herba Sophorae alopecuroidis, and after testing, three's content accounts for more than 95% of sophocarpidine.The separation of high purity sophocarpidine series product at present is mainly by column chromatography, and there is the problem little in batches, that cost is high in industrial production.The breach of dealing with problems just is shortening and selective oxidation, realizes that by reaction conversion between the different alkaloids is to simplify sepn process.Most of alkaloids and various organic acids be present in the plant materials with the form of salt, if directly use solvent extraction, effect is not satisfactory, so need to pass through certain processing before extraction, makes it to break away from plant materials, is dissolved in the extraction solvent.Patent of invention " technology for preparing matrine from Herba Sophorae alopecuroidis " (ZL96109730.2) is directly extracted Herba Sophorae alopecuroidis by alkali lye, pass through extractions such as benzene,toluene,xylene, ethylene dichloride, trichloromethane again, the nickel shortening, centrifugal, distillation, recrystallization obtains matrine.Though the author has introduced the notion of hydrogenation, but it is not fine to adopt alkali lye directly to extract alkaloidal effect in the production technique, technological process adopts 70-120 ℃ of high temperature simultaneously, destroyed the intravital flavonoid component of plant, make the Oxymatyine generation deoxidation in the plant material simultaneously, be converted into matrine.Patent of invention " a kind of kurarinone and preparation technology thereof " (CN1277202A) with pure matrine by hydrogen peroxide oxidation, concentrate, industrial alcohol dissolving, evaporate to dryness, anhydrous alcohol solution, evaporate to dryness and acetone backflow, suction filtration etc. obtain white kurarinone, though introducing oxidizing process, but pure matrine also is not easy to obtain, and, the process engineering complexity, running cost is higher.Patent of invention " technology for preparing Oxymatyine from Herba Sophorae alopecuroidis " is (CN1148370) by technologies such as extraction, organic solvent extraction, sour water back extraction, alkaline chemical precipitation, shortening, crystallization, hydrogen peroxide oxidation, crystallizing and dryings, obtain Oxymatyine, but Radix Sophorae Flavescentis alkaloid class material all has bigger solubleness in water, alkaline chemical precipitation in the technology, precipitation often is difficult to obtain, even obtain, the yield of Radix Sophorae Flavescentis alkaloid is not high yet; The sour water back extraction also is difficult to the extraction of the alkaloid in the organic solvent fully, and utilizes the toluene recrystallization, and except yield was low, removing the bigger toluene of toxicity fully also was a problem.Patent of invention " a kind of preparation method of axcnic high pure oxymatrine " (CN1687063A) is extracted Radix Sophorae Flavescentis alkaloid with alkaline solution, supercritical co directly extracts from alkaline solution and obtains sophocarpidine then, hydrogenation, oxidation, crystallization, obtain product, but facts have proved that supercritical co is very limited to the solubleness of Radix Sophorae Flavescentis alkaloid, and Radix Sophorae Flavescentis alkaloid all has bigger solubleness in the aqueous solution, so the product yield that this method obtains is low, and introducing supercritical technology, technology cost height, output is restricted.
Summary of the invention
The method that the purpose of this invention is to provide a kind of low cost production high purity matrine oxide.
The present invention is to be that raw material is at first used the acid extraction Radix Sophorae Flavescentis alkaloid under the sonic oscillation effect with kuh-seng or Herba Sophorae alopecuroidis, filters the treated biological general flavone that obtains of filter residue; Filtrate adds acid for adjusting pH≤3, and degreasing adds alkali then and regulates pH 〉=11, organic solvent extraction, and the organic phase evaporation, decolouring, crystallization obtains the kuh-seng biology total alkali; The kuh-seng biology total alkali is by shortening, hydrogen peroxide oxidation, and recrystallization obtains purity greater than 98.0% Oxymatyine.
Intravital Radix Sophorae Flavescentis alkaloid of plant and various organic acid so need to alkalize or acidifying before extracting, make it to be converted into free alkali or salt in conjunction with forming salt, utilize concentration difference to be diffused into extracting solution; Radix Sophorae Flavescentis alkaloid can generate salt with acid and be soluble in the sour water, and kuh-seng or Herba Sophorae alopecuroidis Flavonoid substances solubleness in acidity or neutral water is very little, so, utilize sour water Radix Sophorae Flavescentis alkaloid can be extracted, and Flavonoid substances is retained in the plant materials.Supersound extract extracted fully in the short period at normal temperatures, not only saves time, and handled easily, and can protect the Flavonoid substances of unstable chemcial property not to be damaged; The total alkaloids that crystallizes out is found through liquid-phase chromatographic analysis: oxymatrine concentration is up to 40%, and Sophocarpidin reaches 20%, and matrine is 20～35%.The ethanolic soln that is rich in matrine, Oxymatyine, Sophocarpidin is through shortening, hydrogen peroxide oxidation, realize the conversion of Sophocarpidin and matrine to Oxymatyine, the Oxymatyine crude product that reaction obtains after finishing is higher than 90% through the liquid-phase chromatographic analysis oxymatrine concentration, can obtain content greater than 98% Oxymatyine through two step recrystallizations again.
Concrete operations step of the present invention is as follows:
(1) granularity 10～120 purpose kuh-sengs or Herba Sophorae alopecuroidis raw material and pH value are that 3～5 sour water mixes with 1: 3～10 part by weight, at 10～50 ℃,, filter with 19～200KHz frequency sonic oscillation, 20～60min, filter residue repeats to extract 1～3 time, filters the filtrate that obtains and merges;
(2) filtrate that (1) is obtained adds acid for adjusting pH≤3, uses the non-polar solvent degreasing;
(3) aqueous solution after (2) degreasing is added alkali and regulate pH 〉=11, being taken to water with organic solvent extracting does not have alkaloid, and the organic phase evaporate to dryness adds the recrystallisation solvent dissolving, decolouring, crystallization;
(4) crystallization that (3) are obtained adds catalyzer with ethanol or dissolve with methanol, and at 0.1～0.3MPa, 25～80 ℃, hydrogenation reaction 2～3 hours is filtered, and filtrate concentrates; Concentrated solution in 5～30% aqueous hydrogen peroxide solution 10～50 ℃ of oxidations, complete to oxidation, add the excessive hydrogen peroxide of reductive agent reduction, the solution evaporate to dryness obtains the Oxymatyine crude product;
(5) the bitter oxidation ginseng alkali crude product that (4) is obtained joins and carries out the two-step approach crystallization in the recrystallisation solvent, obtains Oxymatyine.
In (1) step, the sour water of described extraction Radix Sophorae Flavescentis alkaloid is hydrochloric acid, nitric acid, acetic acid or the vitriolic aqueous solution as mentioned above.
In described (2) step, the acid that is added is hydrochloric acid, nitric acid, acetic acid or sulfuric acid.
In described (2) step, the non-polar solvent that degreasing is used is rudimentary ether, lower member ester, halohydrocarbon, aliphatic hydrocarbon or arene material.
In described (2) step: degreasing is with the preferred ether of non-polar solvent, ethyl acetate, sherwood oil, chloroform or toluene.
In described (3) step: used alkali is potassium hydroxide, sodium hydroxide, calcium hydroxide, yellow soda ash or sodium bicarbonate etc.
In described (3) step: extraction is halohydrocarbon, lower member ester or arene material with organic solvent, preferred chloroform, ethyl acetate and toluene.
In described (3) step: discoloring agent is gac or aluminum oxide; Recrystallisation solvent is ketone, ether, alcohol or Ester, preferred acetone, ether, ethanol, methyl alcohol or ethyl acetate.
In described (4) step, hydrogenation catalyst used therein is meant loading type Pt, Pd, Ni or Raney Ni; Support of the catalyst is silica gel, gac or aluminum oxide.
In described (4) step: used reductive agent is Sulfothiorine, S-WAT, sodium sulphite or low price molysite.
In described (5) step, adopt the two-step crystallization method, the first step crystallization solvent for use is lower ketones, rudimentary ether, rudimentary Ester etc., the second step crystallization solvent for use is ethanol, methyl alcohol etc.
In described (5) step: the preferred acetone of described recrystallization the first step recrystallisation solvent, ether, the second step recrystallisation solvent preferred alcohol, methyl alcohol.
The inventive method mainly contains following characteristics:
1, ultrasonic extract at room temperature not only can shorten extraction time, does not destroy the structure of biological general flavone class material, in obtaining the process of Radix Sophorae Flavescentis alkaloid, obtains biological general flavone simultaneously.
2, on basis not, realized the purification of high purity matrine oxide, reached the kurarinone quality standard of national Bureau of Drugs Supervision, be easy to suitability for industrialized production, reduced production cost simultaneously by column chromatography for separation.
3, in the sepn process of matrine series product, introduce the notion of shortening, selective oxidation, realized the conversion of Sophocarpidin and matrine, simplified separating technology, improved yield, shortened the production cycle to Oxymatyine.
4, Oxymatyine purity is more than or equal to 98.0%
Embodiment
Embodiment 1:
(1) 10～40 purpose Lightyellow Sophora Root 100g adds the aqueous hydrochloric acid 300ml of pH=3, and 50 ℃ of supersound extraction 30min filter, and filter residue repeats to extract twice, merging filtrate.
(2) it is 0.5 that the filtrate that (1) is obtained adds the salt acid for adjusting pH value, adds the degreasing of 100ml ethyl acetate extraction, separatory, and so the degreasing separatory is three times.
(3) aqueous solution after (2) degreasing is added yellow soda ash and regulate pH value to 12, add 60ml ethyl acetate extraction alkaloid, separatory, repetitive operation to lifeless matter alkali extracts, and merges organic phase, evaporate to dryness; Obtain biology total alkali, add 10ml acetone, heating for dissolving, with the decolouring of 0.5g aluminum oxide, heat filtering, crystallisation by cooling gets sophocarpidine 3.5g.
(4) crystallization that (3) are obtained is dissolved in ethanol, silica gel appendix Ni shortening, control pressure is 0.1 normal atmosphere, 80 ℃, feeds hydrogen hydrogenation 3h, filter, filtrate concentrates, and is soluble in water, uses 5% hydrogen peroxide oxidation, temperature is that 50 ℃ of reactions are extremely complete, adds the excessive hydrogen peroxide of S-WAT reaction.
(5) the solution decompression distillation that (4) is obtained, drying obtains Oxymatyine crude product 3.0g.
(6) the crude product heating that (5) is obtained is dissolved in 12ml acetone, crystallisation by cooling; Obtain the crystallization heating and be dissolved in 4ml ethanol, crystallisation by cooling gets transparent crystals 2.3g, and through liquid-phase chromatographic analysis, content is 98.0% Oxymatyine.
Embodiment 2:
(1) 40～80 purpose Lightyellow Sophora Root 100g adds the aqueous sulfuric acid 600ml of pH=4, and 40 ℃ of supersound extraction 20min filter, and filter residue repeats to extract twice, merging filtrate.
(2) it is 1 that the filtrate that (1) is obtained adds the sulphur acid for adjusting pH value, adds the degreasing of 100ml chloroform extraction, separatory, and so the degreasing separatory is three times.
(3) aqueous solution after (2) degreasing is added carbonacid sodium and regulate pH value to 11, add 60ml chloroform extraction alkaloid, separatory, repetitive operation to lifeless matter alkali extracts, and merges organic phase, evaporate to dryness; Obtain biology total alkali, add the 60ml ether, heating for dissolving, with the decolouring of 0.5g aluminum oxide, heat filtering, crystallisation by cooling gets sophocarpidine 3.3g.
(4) crystallization that (3) are obtained is dissolved in methyl alcohol, gac appendix Pd shortening, and control pressure is 0.3MPa, 60 ℃, feed hydrogen hydrogenation 2h, filter, filtrate concentrates, and is soluble in water, use 10% hydrogen peroxide oxidation, temperature is that 30 ℃ of reactions are extremely complete, adds the excessive hydrogen peroxide of sodium sulphite reaction.
(5) the solution decompression distillation that (4) is obtained, drying obtains Oxymatyine crude product 2.8g.
(6) the crude product heating that (5) is obtained is dissolved in 40ml ether, crystallisation by cooling; Obtain the crystallization heating and be dissolved in 4ml methyl alcohol, crystallisation by cooling gets transparent crystals 2.5g, and through liquid-phase chromatographic analysis, content is 98.5% Oxymatyine.
Embodiment 3:
(1) 80～100 purpose Lightyellow Sophora Root 100g adds the aqueous acetic acid 800ml of pH=5, and 30 ℃ of supersound extraction 20min filter, and filter residue repeats to extract twice, merging filtrate.
(2) it is 2 that the filtrate that (1) is obtained adds the vinegar acid for adjusting pH value, adds 100ml toluene extraction degreasing, separatory, and so the degreasing separatory is three times.
(3) aqueous solution after (2) degreasing is added potassium hydroxide and regulate pH value to 12, add 60ml toluene extraction alkaloid, separatory, repetitive operation to lifeless matter alkali extracts, and merges organic phase, evaporate to dryness; Obtain biology total alkali, add the 4ml ethyl acetate, heating for dissolving, with the decolouring of 0.5g aluminum oxide, heat filtering, crystallisation by cooling gets sophocarpidine 3.6g.
(4) crystallization that (3) are obtained is dissolved in ethanol, and Raney Ni shortening, control pressure are 0.2MPa, 40 ℃, feed hydrogen hydrogenation 3h, filter, filtrate concentrates, and is soluble in water, use 20% hydrogen peroxide oxidation, temperature is that 20 ℃ of reactions are extremely complete, adds the excessive hydrogen peroxide of Sulfothiorine reaction.
(5) the solution decompression distillation that (4) is obtained, drying obtains Oxymatyine crude product 3.2g.
(6) the crude product heating that (5) is obtained is dissolved in 12ml acetone, crystallisation by cooling; Obtain the crystallization heating and be dissolved in 4ml methyl alcohol, crystallisation by cooling gets transparent crystals 2.5g, and through liquid-phase chromatographic analysis, content is 98.3% Oxymatyine.
Embodiment 4:
(1) 100～120 purpose Herba Sophorae alopecuroidis powder 100g adds the aqueous nitric acid 1000ml of pH=4, and 10 ℃ of supersound extraction 60min filter, and filter residue repeats to extract twice, merging filtrate.
(2) it is 3 that the filtrate that (1) is obtained adds the nitre acid for adjusting pH value, adds the degreasing of 150ml extracted with diethyl ether, separatory, and so the degreasing separatory is three times.
(3) aqueous solution after (2) degreasing is added sodium hydroxide and regulate pH value to 13, add 60ml chloroform extraction alkaloid, separatory, repetitive operation to lifeless matter alkali extracts, and merges organic phase, evaporate to dryness; Obtain biology total alkali, add 5ml methyl alcohol, heating for dissolving is used the 0.1g activated carbon decolorizing, heat filtering, and crystallisation by cooling gets sophocarpidine 4.5g.
(4) crystallization that (3) are obtained is dissolved in methyl alcohol, aluminum oxide appendix Pt shortening, control pressure is 0.3MPa, 25 ℃, feeds hydrogen hydrogenation 3h, filter, filtrate concentrates, and is soluble in water, uses 30% hydrogen peroxide oxidation, temperature is that 10 ℃ of reactions are extremely complete, adds the excessive hydrogen peroxide of iron protochloride reaction.
(5) the solution decompression distillation that (4) is obtained, drying obtains Oxymatyine crude product 3.6g.
(6) the crude product heating that (5) is obtained is dissolved in 10ml acetone, crystallisation by cooling; Obtain the crystallization heating and be dissolved in 4ml ethanol, crystallisation by cooling gets transparent crystals 3.1g, and through liquid-phase chromatographic analysis, content is 98.0% Oxymatyine.
Embodiment 5:
(1) 40～80 purpose Herba Sophorae alopecuroidis powder 100g adds the aqueous hydrochloric acid 600ml of pH=3, and 20 ℃ of supersound extraction 30min filter, and filter residue repeats to extract twice, merging filtrate.
(2) it is 0.5 that the filtrate that (1) is obtained adds the salt acid for adjusting pH value, adds the degreasing of 100ml petroleum ether extraction, separatory, and so the degreasing separatory is three times.
(3) aqueous solution after (2) degreasing is added calcium hydroxide and regulate pH to 11, add the chloroform extraction alkaloid of 60ml, separatory, repetitive operation to lifeless matter alkali extracts, and merges organic phase, evaporate to dryness; Obtain biology total alkali, add 10ml acetone, heating for dissolving, with the decolouring of 0.5g aluminum oxide, heat filtering, crystallisation by cooling gets sophocarpidine 4.8g.
(4) crystallization that (3) are obtained is dissolved in ethanol, silica gel appendix Ni shortening, and control pressure is 0.2MPa, 60 ℃, feed hydrogen hydrogenation 2h, filter, filtrate concentrates, and is soluble in water, use 5% hydrogen peroxide oxidation, temperature is that 50 ℃ of reactions are extremely complete, adds the excessive hydrogen peroxide of S-WAT reaction.
(5) the solution decompression distillation that (4) is obtained, drying obtains Oxymatyine crude product 3.9g.
(6) the crude product heating that (5) is obtained is dissolved in 40ml ether, crystallisation by cooling; Obtain the crystallization heating and be dissolved in 4ml methyl alcohol, crystallisation by cooling gets transparent crystals 3.6g, and through liquid-phase chromatographic analysis, content is 98.8% Oxymatyine.
Claims (15)
1, a kind of method of producing high purity matrine oxide is characterized in that comprising that step is as follows:
(1) granularity 10～120 purpose kuh-sengs or Herba Sophorae alopecuroidis raw material and pH value are that 3～5 sour water mixes with 1: 3～10 part by weight, at 10～50 ℃,, filter with 19～200KHz frequency sonic oscillation, 20～60min, filter residue repeats to extract 1～3 time, filters the filtrate that obtains and merges;
(2) filtrate that (1) is obtained adds acid for adjusting pH≤3, uses the non-polar solvent degreasing;
(3) aqueous solution after (2) degreasing is added alkali and regulate pH 〉=11, being taken to water with organic solvent extracting does not have alkaloid, and the organic phase evaporate to dryness adds the recrystallisation solvent dissolving, decolouring, crystallization;
(4) crystallization that (3) are obtained adds catalyzer with ethanol or dissolve with methanol, and at 0.1～0.3MPa, 25～80 ℃, hydrogenation reaction 2～3 hours is filtered, and filtrate concentrates; Concentrated solution in 5～30% aqueous hydrogen peroxide solution 10～50 ℃ of oxidations, complete to oxidation, add the excessive hydrogen peroxide of reductive agent reduction, the solution evaporate to dryness obtains the Oxymatyine crude product;
(5) the bitter oxidation ginseng alkali crude product that (4) is obtained joins and carries out the two-step approach crystallization in the recrystallisation solvent, obtains Oxymatyine.
2, a kind of method of producing high purity matrine oxide as claimed in claim 1 is characterized in that the sour water in described (1) step is hydrochloric acid, nitric acid, acetic acid or the vitriolic aqueous solution.
3, a kind of method of producing high purity matrine oxide as claimed in claim 1 is characterized in that the acid in described (2) step is hydrochloric acid, nitric acid, acetic acid or sulfuric acid.
4, a kind of method of producing high purity matrine oxide as claimed in claim 1 is characterized in that the non-polar solvent in described (2) step is rudimentary ether, lower member ester, halohydrocarbon, aliphatic hydrocarbon or arene material.
5, a kind of method of producing high purity matrine oxide as claimed in claim 4 is characterized in that non-polar solvent is ether, ethyl acetate, sherwood oil, chloroform or toluene in described (2) step.
6, a kind of method of producing high purity matrine oxide as claimed in claim 1 is characterized in that alkali is potassium hydroxide, sodium hydroxide, calcium hydroxide, yellow soda ash or sodium bicarbonate in described (3) step.
7, a kind of method of producing high purity matrine oxide as claimed in claim 1 is characterized in that organic solvent is halohydrocarbon, lower member ester or arene material in described (3) step.
8, a kind of method of producing high purity matrine oxide as claimed in claim 7 is characterized in that described organic solvent is chloroform, ethyl acetate or toluene.
9, a kind of method of producing high purity matrine oxide as claimed in claim 1 is characterized in that the discoloring agent in described (3) step is gac or aluminum oxide.
10, a kind of method of producing high purity matrine oxide as claimed in claim 1 is characterized in that described recrystallisation solvent is ketone, ether, alcohol or Ester.
11, a kind of method of producing high purity matrine oxide as claimed in claim 10 is characterized in that described recrystallisation solvent is acetone, ether, ethanol, methyl alcohol or ethyl acetate.
12, a kind of method of producing high purity matrine oxide as claimed in claim 1 is characterized in that catalyzer is meant loading type Pt, Pd, Ni or Raney Ni in described (4) step; Support of the catalyst is silica gel, gac or aluminum oxide.
13, a kind of method of producing high purity matrine oxide as claimed in claim 1 is characterized in that reductive agent is Sulfothiorine, S-WAT, sodium sulphite or low price molysite in described (4) step.
14, a kind of method of producing high purity matrine oxide as claimed in claim 1, it is characterized in that two-step crystallization method in described (5) step, the first step crystallization solvent for use is lower ketones, rudimentary ether or rudimentary Ester, and the second step crystallization solvent for use is ethanol or methyl alcohol.
15, a kind of method of producing high purity matrine oxide as claimed in claim 14 is characterized in that the first step recrystallisation solvent is acetone or ether in described (5) step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100482448A CN100439364C (en) | 2005-12-27 | 2005-12-27 | Process for producing high purity matrine oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100482448A CN100439364C (en) | 2005-12-27 | 2005-12-27 | Process for producing high purity matrine oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1793143A true CN1793143A (en) | 2006-06-28 |
| CN100439364C CN100439364C (en) | 2008-12-03 |
Family
ID=36804805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100482448A Expired - Fee Related CN100439364C (en) | 2005-12-27 | 2005-12-27 | Process for producing high purity matrine oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100439364C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101129455B (en) * | 2007-09-18 | 2010-06-16 | 新疆维吾尔自治区药物研究所 | Sophora extractive and method of preparing the same and application of the same |
| CN102850351A (en) * | 2012-08-30 | 2013-01-02 | 陕西力拓植物化工有限责任公司 | Method for extraction of sparteine from Thermopsis lanceolata |
| CN103664942A (en) * | 2013-12-16 | 2014-03-26 | 广西大学 | Method for extracting matrine by coupling molecular imprinting with ultrasonic extraction |
| CN111777610A (en) * | 2020-07-31 | 2020-10-16 | 西藏德康生物科技有限公司 | Method for separating and purifying oxymatrine from sophora moorcroftiana extract |
| CN114591329A (en) * | 2022-03-03 | 2022-06-07 | 北京岳达生物科技有限公司 | Mutual transformation method of sophora flavescens effective components |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1148370C (en) * | 1999-06-22 | 2004-05-05 | 内蒙古苦参生化集团有限责任公司 | Technology for preparing oxymatrine from sophora alopecuroide |
| CN1172933C (en) * | 2003-05-22 | 2004-10-27 | 王答祺 | Prepn of matrine, oxymatrine and sophoxidine from flavescent sophora root |
-
2005
- 2005-12-27 CN CNB2005100482448A patent/CN100439364C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101129455B (en) * | 2007-09-18 | 2010-06-16 | 新疆维吾尔自治区药物研究所 | Sophora extractive and method of preparing the same and application of the same |
| CN102850351A (en) * | 2012-08-30 | 2013-01-02 | 陕西力拓植物化工有限责任公司 | Method for extraction of sparteine from Thermopsis lanceolata |
| CN103664942A (en) * | 2013-12-16 | 2014-03-26 | 广西大学 | Method for extracting matrine by coupling molecular imprinting with ultrasonic extraction |
| CN103664942B (en) * | 2013-12-16 | 2015-10-21 | 广西大学 | A kind of molecular imprinting and ultrasonic coupling extract the method for matrine |
| CN111777610A (en) * | 2020-07-31 | 2020-10-16 | 西藏德康生物科技有限公司 | Method for separating and purifying oxymatrine from sophora moorcroftiana extract |
| CN114591329A (en) * | 2022-03-03 | 2022-06-07 | 北京岳达生物科技有限公司 | Mutual transformation method of sophora flavescens effective components |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100439364C (en) | 2008-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100439363C (en) | Process for producing high purity matrine oxide by kuh-seng | |
| CN101560201B (en) | Technique for extracting puerarin and diverse medical ingredients from root of kudzuvine | |
| CN110845328A (en) | Method for preparing high-purity carnosic acid from rosemary oil paste by-product | |
| CN1793143A (en) | Process for producing high purity matrine oxide | |
| CN101049328A (en) | Technique for producing extractive of olive growing leaves | |
| CN102078341B (en) | High-purity ginkgo flavone and composition thereof | |
| CN104557967B (en) | A kind of production method of high-purity mibemycin | |
| CN108117571B (en) | Preparation method of gentiopicroside monomer | |
| CN101143887A (en) | Method for separating and preparing corosolicacid in loquat leaf | |
| CN102391337A (en) | Method for extracting rhoifolin from turpinia formosana leaves | |
| CN111875482B (en) | Method for extracting quebrachitol from artemisia plants | |
| CN111018819B (en) | Preparation method of luteolin | |
| CN102286031A (en) | Method for extracting and purifying corilagin | |
| CN102078342A (en) | Preparation method of water-soluble ginkgo biloba extract (GBE) | |
| CN102558253A (en) | Method for extracting syringin from ovate leaf holly bark | |
| CN102199159A (en) | Method for separating and purifying ginkgolide C in ginkgo root bark | |
| CN102321143A (en) | Method for preparing high-purity betulin | |
| CN111217787B (en) | Method for purifying daidzein in radix Puerariae | |
| CN1932022B (en) | Process of preparing high purity solanesol with potato leaf as material | |
| CN110903168B (en) | Method for subcritical extraction of solanesol in waste tobacco leaves | |
| US20230219872A1 (en) | Industrial extraction method of cannabidiol | |
| CN111978366A (en) | Method for extracting dioscin from fenugreek | |
| CN111138433A (en) | Method for extracting and purifying matrine from sophora moorcroftianain | |
| CN103288791A (en) | Method for preparing murrayone by murraya paniculata leaves | |
| CN114288705B (en) | Method for removing ginkgolic acid from ginkgo leaf extract |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081203 Termination date: 20181227 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |