CN101302548B - Preparation of icaritin - Google Patents
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- CN101302548B CN101302548B CN2007100990251A CN200710099025A CN101302548B CN 101302548 B CN101302548 B CN 101302548B CN 2007100990251 A CN2007100990251 A CN 2007100990251A CN 200710099025 A CN200710099025 A CN 200710099025A CN 101302548 B CN101302548 B CN 101302548B
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- C12P19/44—Preparation of O-glycosides, e.g. glucosides
- C12P19/60—Preparation of O-glycosides, e.g. glucosides having an oxygen of the saccharide radical directly bound to a non-saccharide heterocyclic ring or a condensed ring system containing a non-saccharide heterocyclic ring, e.g. coumermycin, novobiocin
- C12P19/605—Preparation of O-glycosides, e.g. glucosides having an oxygen of the saccharide radical directly bound to a non-saccharide heterocyclic ring or a condensed ring system containing a non-saccharide heterocyclic ring, e.g. coumermycin, novobiocin to a 1-benzopyran-2-on (or the chalcones and hydrogenated chalcones thereof, e.g. coumermycin, novobiocin, novenamin)
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Abstract
The invention relates to a method for preparing icaritin and is characterized in that: the icaritin is prepared by icariin which is subject to the enzymolysis reaction by beta-glycosidase. The method adopts the beta-glycosidase to perform the enzymolysis reaction for the icariin, the beta-glycosidase has complete deglycolysis and high yield, a self-designed method for extracting the icariin from Herba Epimedii is adopted, the whole technical process has simple and convenient operation, the treatment is convenient after the reaction, and the purity of the product fully meets the pharmaceutical standard.
Description
Technical field
The present invention relates to the field of Chinese medicines, particularly relate to the extracting method of the effective constituent Icaritin in a kind of Chinese medicine Herba Epimedii.
Background technology
Herba Epimedii is the Chinese medicinal materials of using always, it is the ground drying nest of Berberidaceae (Berberridaceae) Epimedium (Epimedium genus) various plants, Pharmacopoeia of People's Republic of China (2000 editions) has been included following five kinds of epimedium herbs, i.e. Herba Epimedii (Epimedium brevicornum Maxim)), arrow leaf Herba Epimedii (Epimedium sagittatum), pubescence Herba Epimedii (Epimedium pubescens), Epimedium wushanense (Epimedium wushanenes), Herba Epimedii (Epimediumkoreanum Nakai) etc.Herba Epimedii has the effect of kidney invigorating and YANG supporting, strengthening the muscles and bones, the dehumidifying of Eradicates wind, is usually used in treating impotence erectile problem, dripping, the weakness of the waist and knees of urine and diseases such as coronary heart disease, chronic bronchitis, neurasthenia and poliomyelitis.Modern pharmacological research proves that Herba Epimedii contains special chemical ingredients and significant biological activity, and at present, separation and Extraction obtains this chemical ingredients and is icarin from Herba Epimedii.The molecular structure of icarin is:
Chemical name is: 3,5, and 7-trihydroxy--4 ' methoxyl group-8-isoamylene radical chromocor-3-O-α-L-pyrans rhamnosyl-7-O-β-D-glucopyranoside.
Discover, because icarin contains two glycosyls, i.e. glucosyl group on the 3-position and the rhamanopyranosyl on the 7-position, its activity is very poor, and the activity of the desaccharification hydrolysis products Icaritin of icarin is then very high.Domestic most acid hydrolysis method that adopts, yet hydrochloric acid hydrolysis easily with the 8-substituting group on two keys formation additions, it is big low and do not have use value to cause into product yield, and sulphuric acid hydrolysis can only remove the glycosyl on the 7-position, and the glycosyl on the 3-position not facile hydrolysis fall, the result can only obtain the icarin of low glycosyl, its activity and icarin ratio, higher, but compare with Icaritin or fall far short.Patent application (application number 031336353) " enzymatic hydrolysis icariine glycosyl prepares the method for low sugar icariine or glucoside unit ", it adopts with the Herba Epimedii is the enzymatic production inductor of bacterial classification, the enzyme that the extraction of fermentation back obtains is used for the syrup of icariine and separates, but the result shows, its enzymolysis product is a kind of low sugar, desaccharification, different icariine or the glucoside unit that replaces, and illustrates that it is not fine that its desaccharification is separated efficient.
Summary of the invention
The invention provides a kind of preparation method of Icaritin, its desaccharification is separated and is reacted completely, and yield is very high, whole simple operation of process, and post-reaction treatment is convenient, and purifying is simple.
The preparation method of Icaritin is characterized in that: with the icarin beta-glucosidase, carry out enzyme digestion reaction and make.
The weight ratio of described beta-glucoside enzyme dosage and icarin is 1:1-10, and the enzyme digestion reaction condition is to react 20-30 hour in 40-60 ℃ alcohol-water solution.
Preferred beta-glucoside enzyme dosage is 1:5 with the weight ratio of icarin, and the enzyme digestion reaction condition is to react 24 hours in 50 ℃ the alcohol-water solution, and described alcohol is ethanol.
The centrifugal treating method is adopted in the aftertreatment of the reaction mixture behind the described enzyme digestion reaction, and described centrifugal treating method is that the reaction mixture centrifugal treating is abandoned supernatant liquor, again with centrifugal treating behind the acetone solution, filters, and abandons filter residue, the filtrate evaporate to dryness.
The preparation method of described Icaritin comprises that also the purifying of Icaritin, described purifying are to adopt the acetone-water recrystallization.
The preparation method of Icaritin also comprises the preparation process of icarin, the preparation process of described icarin comprises the extraction of Herba Epimedii total flavones and the purifying of icarin, the extraction step of described Herba Epimedii total flavones comprises that (1) provides Herba Epimedium Water Extract, (2) concentrating the back adsorbs with the D101 macroporous resin column, successively water, 30% ethanol, 50% ethanol elution wash reuse with 90% ethanol, water respectively again, and (3) collect 50% ethanol elution part, concentrate drying.
Solution content after described the concentrating is 0.2g Herba Epimedii raw medicinal herbs/ml.
The 1-2 that described D101 macroporous resin consumption is the Herba Epimedii raw medicinal herbs times, the last column flow rate of concentrated solution is 5 column volume/h, and the elutriant consumption is a 3-4 column volume.
The purifying of described icarin comprises the silica gel column chromatography column separating purification method that adopts, comprising adopting 10:0,9:1,8:1,7:1, the trichloromethane of 6:1-methyl alcohol gradient elution; Detect with the TLC method, concentrate the cut step that contains icarin.
The purifying of described icarin also comprises the enriched material recrystallizing methanol that obtains above-mentioned, leaches thing and uses acetone, methanol wash successively.
From the icarin to the Icaritin, key is will be with the 3-of icarin, sugared substituting group hydrolysis on the 7-is fallen, the contriver has done long term studies and exploration, the discovery beta-glucosidase (β-Glycosidase) above-mentioned two locational sugared substituting group one one-step hydrolysis can be fallen, while its enzymolysis yield higher (reaching about 55%), and its aftertreatment is simple and direct, whole enzymolysis process is simple, is easy to suitability for industrialized production.
The add-on of beta-glucosidase and the weight ratio of reactant are 1:1-10, the enzyme digestion reaction condition is to react 20-30 hour in 40-60 ℃ alcohol-water solution, because icarin can be dissolved in the alcohol, therefore select for use alcohol solution as reaction solution, alcohol is selected ethanol commonly used for use, its cost is low, and pollutes little.Because hydrolysis reaction carries out in ethanol, enzyme is inactivation easily, so the reaction times is unsuitable long, so selects for use the time at 20-30 hour, at this moment desaccharification is separated reaction and finished substantially.Preferred β-Glycosidase consumption is 1:5 with the weight ratio of icarin, and the enzyme digestion reaction condition is to react 24 hours in 50 ℃ the alcohol-water solution.
The present invention only uses behind enzyme digestion reaction the reaction mixture centrifugal treating is abandoned supernatant liquor, again with centrifugal treating behind the acetone solution, filters, and abandons filter residue, and the filtrate evaporate to dryness promptly obtains Icaritin, and is very simple and convenient, is easy to suitability for industrialized production.Icaritin can also utilize during the method for recrystallization is further purified, and obtains highly purified product, and recrystallization solvent adopts the acetone-water mixed solvent.The present invention reaches 55% through the yield of gained Icaritin behind the purifying.
The present invention can adopt commercially available icarin to carry out enzymolysis, can also from epimedium herb, extract voluntarily voluntarily simultaneously, the benefit of Ti Quing is to save cost voluntarily, can also monitor foreign matter content simultaneously, thereby specific aim adopts variety of way to remove some impurity.
The preparation of icarin comprises the extraction of Herba Epimedii total flavones and the purifying of icarin, the extraction step of described Herba Epimedii total flavones comprises with water boil and extracts Herba Epimedii, united extraction liquid is concentrated into 0.2g Herba Epimedii raw medicinal herbs/ml then, (D101 macroporous resin column some organic solvents that it will be adsorbed above before use clean up and refill post with D101 macroporous resin column absorption, D101 macroporous resin consumption is 1-2 a times of Herba Epimedii raw medicinal herbs, the last column flow rate of concentrated solution is 5 column volume/h, the elutriant consumption is a 3-4 column volume, makes separating effect better.), use the alcohol-water gradient elution.Wash with water earlier to elutriant to faint yellow, use 30% ethanol elution again, about 4 posts, 50% ethanol elution then, this elutriant is the Herba Epimedii total flavones product, collects to concentrate, and productive rate is about 2% (being that the 100g epimedium herb can obtain the Herba Epimedii total flavones about 2g).Again with 90% ethanol, the reuse of water flushing D101 macroporous resin column.Herba Epimedii total flavones detects through HPLC, contains icarin about 25%, and carry out enzyme digestion reaction need be further purified.
The purifying of icarin adopts silica gel column chromatography column separating purification method, adopts 10:0,9:1,8:1,7:1, the trichloromethane of 6:1-methyl alcohol gradient elution; Detect with the TLC method, developping agent is selected trichloromethane for use: methyl alcohol: formic acid=8:2:0.2, the Rf value is between 0.5-0.6, collects to contain the icarin fraction, concentrates.The gained icarin also needs to be further purified, and uses recrystallizing methanol, leaches thing and uses acetone, methanol wash successively.The purity of the product icarin that obtains like this reaches about 95%, satisfies the requirement of next step enzyme digestion reaction fully.
It is that icarin carries out enzyme digestion reaction that the present invention adopts beta-glucosidase, and its desaccharification is separated fully, and yield is very high, that adopts design voluntarily extracts icarin from epimedium herb, whole simple operation of process, post-reaction treatment is convenient, and product purity meets medicinal standard fully.
Description of drawings
The epimedium aglucone that Fig. 1 embodiment 1 makes (Icaritin) HPLC collection of illustrative plates
The Icaritin HPLC collection of illustrative plates that Fig. 2 embodiment 2 makes
Fig. 3 Herba Epimedii total flavones HPLC collection of illustrative plates
Fig. 4 icarin HPLC collection of illustrative plates
The Icaritin HPLC collection of illustrative plates that Fig. 5 embodiment 3 makes
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
(embodiment the 1, the 2nd, and the icarin that adopts is the commercially available prod, and purity is more than 98%, and embodiment 3 icarin are homemade product, and (β-Glycosidase) is an amano enzyme preparation company product to beta-glucosidase.)
Embodiment 1
1. the enzymolysis icarin 100g of icarin adds 20% ethanol 5000ml, and stirring and dissolving adds the 10g beta-glucosidase, 60 ℃ of following hydrolysis reaction 20 hours.
2. the aftertreatment of reaction solution: reaction solution is carried out centrifugal treating, abandoning supernatant.Precipitation is used the 2500ml acetone solution, and solution carries out centrifugal treating, takes out supernatant liquor, filters, and abandons or adopts insolubles, the supernatant liquor evaporate to dryness.
3. the pure product preparation of Icaritin (aglycon):
Add acetone-water (1:1) 1500ml recrystallization, place, crystallization filters, and drying promptly gets the pure product 29g of epimedium aglucone.Detecting purity through HPLC reaches more than 98%.(as Fig. 1) HPLC condition is acetonitrile-1% glacial acetic acid aqueous solution 70:30, detects wavelength 273nm.Fusing point: be higher than 250 ℃.
Total yield: 53.3%.
Embodiment 2
1. the enzymolysis icarin 100g of icarin adds 20% ethanol 5000ml, and stirring and dissolving adds the 100g beta-glucosidase, 40 ℃ of following hydrolysis reaction 30 hours.
2. the aftertreatment of reaction solution: reaction solution is carried out centrifugal treating, abandoning supernatant.Precipitation is used the 2500ml acetone solution, and solution carries out centrifugal treating, takes out supernatant liquor, filters, and abandons or adopts insolubles, and supernatant liquor steams to every gram 25ml (with respect to icarin).
The pure product preparation of 3 epimedium aglucones:
Get spissated supernatant liquor, add the water recrystallization of equivalent, place, crystallization filters, and drying promptly gets the pure product 30.2g of epimedium aglucone.Detecting purity through HPLC reaches more than 98%.(as Fig. 2) HPLC condition is acetonitrile-1% glacial acetic acid aqueous solution 70:30, detects wavelength 273nm..
Total yield 55.5%.
Because when aftertreatment, use solvent acetone, and use solvent acetone during recrystallization, therefore can save some more step, save time the process time.
Embodiment 3
3.1 the extraction of Herba Epimedii total flavones
3.1.1 pulverize: dry medicinal material 10000g pulverizes with Herba Epimedii, in the extractor of packing into.
3.1.2 extract: add 16 times of water gagings and decoct 3 times, 2h for the first time, later on each 1.5h.Merge 3 times extracting solution, filter, be evaporated to the solution of 0.2g raw medicinal herbs/ml.
3.1.3 resin purification: extracting solution adsorbs total flavones by the D101 macroporous resin column of anticipating, and (resin demand is about 1.5 times of medicinal material.)。The flow velocity of extracting solution upper prop is 5 column volume/h.The first water in absorption back is eluted to water elution liquid and is faint yellow, and about 4 column volumes are used 30% ethanol more respectively, about 4 column volumes, and 50% ethanol, about 4 column volumes after 90% Ethanol Treatment, are washed standby.
3.1.4 concentrate: decompression concentrates 50% ethanol elution part down, and 60 ℃ of following vacuum-dryings are pulverized, and promptly get the 200g product.
3.1.5 measure: the yield of total flavones: about 2% (being that the 100g medicinal material can obtain the 2g total flavones), it is content about 25% that the HPLC method is measured icarin.As Fig. 3. (measuring method is referring to first one 229 pages of 2005 editions Chinese Pharmacopoeias)
3.2 the purifying of icarin
3.2.1 sample: epimedium herb 50% ethanol extraction 200g (product of step 3.1), methanol-water dissolving, with 60-100 order silica gel mixed sample (sample (g): silica gel (g)=1:2), dry, it is standby to be ground into fine powder.
3.2.2 dress post: wet method dress post.Filler and sample ratio are about 1:10 (weight ratio), soak silica gel with trichloromethane, and the chromatography column of packing into is till balance columns bed to post bed height no longer changes.
3.2.3 last sample: sample on the dry method.
3.2.4 wash-out: (10:0,9:1,8:1,7:1,6:1) gradient elution, TLC follow the tracks of the detection icarin, and whether wash-out comes out with trichloromethane-methyl alcohol.Wherein, 10:0, two gradients of 9:1,10 column volumes of each gradient elution.The 8:1 gradient begins to detect icarin, wash-out 20 column volumes.7:1 and each wash-out of 6:1 gradient are until 30 column volumes of wash-out.
3.2.5 be further purified: detect through TLC, trichloromethane-methyl alcohol-formic acid 8:2:0.2 launches, and Rf value 0.6 merges the cut that contains icarin, and evaporated under reduced pressure is transferred to solid in the triangular flask with hot methanol, places until separating out pale yellow powder, suction filtration.The solid that obtains is used acetone successively, and methanol wash finally obtains the crude product 20g of the icarin about 95%.
Result such as Fig. 4 .HPLC condition acetonitrile-1% glacial acetic acid aqueous solution 28:72.Fusing point: 230～232 ℃.
The yield of this step icarin is about 10%.(being that the 100g total flavones can obtain the 10g icarin)
3.3 the preparation of Icaritin
3.3.1 icarin enzyme digestion reaction:
Icarin crude product 20g, 50 extraordinarily go into 20% ethanol, and 50 ℃ are stirred 1h down, through beta-glucosidase (enzyme dosage and substrate amount ratio are respectively 1:5), 50 ℃ of following hydrolysis reaction 24h.
3.3.2 the aftertreatment of reaction solution:
Reaction solution is carried out centrifugal treating, abandoning supernatant.Precipitation is measured acetone solutions with 25 times, and solution carries out centrifugal treating, takes out supernatant liquor, filters, and abandons or adopts insolubles, and supernatant liquor steams to every gram 25ml (with respect to icarin).
3.3.3 the pure product preparation of epimedium aglucone:
Get spissated supernatant liquor, add the water recrystallization of equivalent, place, crystallization filters, and drying promptly gets the pure product 6g of epimedium aglucone.Liquid Detection result such as Fig. 5 .HPLC condition: acetonitrile-1% glacial acetic acid aqueous solution 70:30, detect wavelength 280nm fusing point: be higher than 250 ℃. this step yield: this step yield is 55%.
Adopt homemade icarin, only with being controlled to more than 95%, its enzymolysis product is also very complete for its purity, and the icarin that makes can reach medicinal standard fully.The total recovery of this technology is 2% * 10% * 55%=0.11%.
Claims (9)
1. the preparation method of Icaritin, it is characterized in that: icarin is carried out enzyme digestion reaction with beta-glucosidase make, the weight ratio of wherein said beta-glucoside enzyme dosage and icarin is 1: 1-10, the enzyme digestion reaction condition is to react 20-30 hour in 40-60 ℃ alcohol-water solution.
2. the preparation method of Icaritin according to claim 1, the weight ratio of described beta-glucoside enzyme dosage and icarin is 1: 5, and the enzyme digestion reaction condition is reaction 24 hours in 50 ℃ the alcohol-water solution, and described alcohol is ethanol.
3. the preparation method of Icaritin according to claim 2, the centrifugal treating method is adopted in the aftertreatment of the reaction mixture behind the described enzyme digestion reaction, and described centrifugal treating method is that the reaction mixture centrifugal treating is abandoned supernatant liquor, again with centrifugal treating behind the acetone solution, filter, abandon filter residue, the filtrate evaporate to dryness.
4. the preparation method of Icaritin according to claim 1 also comprises the purifying of Icaritin, and described purifying is to adopt the acetone-water recrystallization.
5. the preparation method of Icaritin according to claim 1, the preparation process that also comprises icarin, the preparation process of described icarin comprises the extraction of Herba Epimedii total flavones and the purifying of icarin, the extraction step of described Herba Epimedii total flavones comprises that (1) provides Herba Epimedium Water Extract, (2) concentrating the back adsorbs with the D101 macroporous resin column, priority water, 30% ethanol, 50% ethanol elution, again respectively with 90% ethanol, water flushing reuse, (3) collect 50% ethanol elution part, concentrate drying.
6. the preparation method of Icaritin according to claim 5, the solution content after concentrating in the wherein said step (2) is 0.2g Herba Epimedii raw medicinal herbs/ml.
7. the preparation method of Icaritin according to claim 6, the 1-2 that described D101 macroporous resin consumption is the Herba Epimedii raw medicinal herbs doubly, the last column flow rate of concentrated solution is 5 column volume/h, the elutriant consumption is a 3-4 column volume.
8. the preparation method of Icaritin according to claim 5, the purifying of described icarin comprises the silica gel column chromatography column separating purification method that adopts, comprising adopting 10: 0,9: 1,8: 1,7: 1,6: 1 trichloromethane-methyl alcohol gradient elution; Detect with the TLC method, concentrate the cut step that contains icarin.
9. the preparation method of Icaritin according to claim 8, the purifying of described icarin also comprises the enriched material recrystallizing methanol, leaches thing and uses acetone, methanol wash successively.
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| CN2007100990251A CN101302548B (en) | 2007-05-09 | 2007-05-09 | Preparation of icaritin |
| PCT/CN2008/070723 WO2008138243A1 (en) | 2007-05-09 | 2008-04-16 | A preparation method of icaritin |
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| CN102718819B (en) * | 2012-07-10 | 2013-07-03 | 刘志强 | Process for preparing icariin |
| CN103305564B (en) * | 2013-07-05 | 2014-10-15 | 西安瑞天生物科技有限公司 | Method for converting icariin to herba epimedii |
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| CN104711301B (en) * | 2015-03-24 | 2018-07-24 | 北京盛诺基医药科技有限公司 | A kind of preparation method of icariine |
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| CN110143942B (en) * | 2019-05-30 | 2021-04-09 | 苏州禾研生物技术有限公司 | Method for preparing icaritin and rhamnose syrup by organic acid hydrolysis of icariin |
| CN110699263B (en) * | 2019-10-29 | 2021-05-11 | 浙江工业大学 | Aspergillus niger YH-6 and application thereof in improving content of icaritin in epimedium |
| CN111560409B (en) * | 2020-05-08 | 2023-04-28 | 陕西嘉禾生物科技股份有限公司 | Preparation method of icariin |
| CN112553264A (en) * | 2020-12-16 | 2021-03-26 | 金凤燮 | Method for efficiently preparing icariin through enzyme conversion |
| CN112961891B (en) * | 2021-03-25 | 2024-01-26 | 西安巨子生物基因技术股份有限公司 | Method for preparing icariin by using biphasic enzymatic reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2808016A1 (en) | 2013-05-31 | 2014-12-03 | Beijing Shenogen Pharma Group Ltd. | Use of icaritin for the preparation of a composition for treating cancer |
| CN112138017A (en) * | 2020-08-27 | 2020-12-29 | 上海中医药大学 | Enzymolysis product of icariin and medical application of main component baohuoside I thereof |
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| WO2008138243A1 (en) | 2008-11-20 |
| CN101302548A (en) | 2008-11-12 |
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