CN101851221A - Method for preparing dihydroquercetin from larches - Google Patents
Method for preparing dihydroquercetin from larches Download PDFInfo
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- CN101851221A CN101851221A CN 201010184375 CN201010184375A CN101851221A CN 101851221 A CN101851221 A CN 101851221A CN 201010184375 CN201010184375 CN 201010184375 CN 201010184375 A CN201010184375 A CN 201010184375A CN 101851221 A CN101851221 A CN 101851221A
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Abstract
The invention relates to a method for preparing dihydroquercetin from larches, which is characterized by comprising the following steps: carrying out reflux extraction on larch wood flour as raw material by using an alcohol solution for one time and filtering to obtain an extraction liquid; adding strong acid ion exchange resin and a chlorinated solvent to the extraction liquid; carrying out reflux hydrolysis to convert bound dihydroquercetin into free dihydroquercetin; separating a chlorinated solvent phase after the reaction is ended; concentrating to dryness; and recrystallizing to obtain the product. The operation process is mainly characterized in that the energy consumption is less, the hydrolysis and the extraction are simultaneously completed, the production cost is low and the yield is high; the catalytic hydrolysis process of the strong acid ion exchange resin does not generate pollution, and all solvents can be recycled, and thereby, the industrial scale production becomes convenient.
Description
Affiliated technical field:
The present invention relates to the natural product chemistry field, particularly relate to a kind of method that from tamarack, prepares dihydroquercetin,
Background technology:
Dihydroquercetin is a kind of important flavanone alcohol compound that occurring in nature exists, and also claims vitamin P, has the woods source activity material of multiple important biologic activity.Pure product are pale yellow powder; has superpower resistance of oxidation; keep human recycle system's function aspects play a part special; it is because of having anticancer, blood fat reducing, protection cardiovascular and cerebrovascular; liver; visual function, and, anti-oxidant, delay senility, diminish inflammation and a series of effect such as anti-diabetic and receiving much concern.
The content of dihydroquercetin in tamarack is about about 0.3～5.7%, dihydroquercetin is extracted from confierophyte Chamaecyparis obtusa (Sieb.et Zucc.) Endl. leaf by Japanese scholar Fukui the earliest, is a kind of aglycon of glucoside.Subsequently he studied it again the 3-O-glucoside in confierophyte distribution and bacterium in the presence of the hydrolysis of glycosidic bond.There is the people from various plants, to isolate dihydroquercetin and derivative thereof later on again, in plant, exists with aglycon or two kinds of forms of glycosides.
United States Patent (USP) (US2744919A) has introduced water or big slightly alcohol or the ketone of polarity extracts dihydroquercetin from bark, the concentrating under reduced pressure solvent obtains a kind of crude extract that contains tannin, carbohydrate and coloring matter, then with low polar alcohol, ketone or ether extraction, remove paste behind the solvent and carry out crystallization purifying with hot water and make the dihydroquercetin crude product.The medicinal extract solution that obtains after this method solvent extraction contains more impurity, improves not obvious and the crystallization number of times is more at crystalline process moderate purity.
Canadian Patent (CA532804A) has been introduced with hot water and extracted dihydroquercetin from bark, cool off centrifugal after-filtration, concentrate and obtain a kind of crude extract that contains tannin, carbohydrate and coloring matter, then with low polar alcohol, ketone or ether extraction, remove paste behind the solvent and carry out crystallization purifying with hot water and make the dihydroquercetin crude product.Because this method adopts hot water extraction, so the solvent recuperation cost is higher.
It is the method that raw material extracts dihydroquercetin with the tamarack wood powder that Russ P (RU2184561C1) has been introduced a kind of, with wood powder and organic solvent Hybrid Heating to 110～120 ℃ extraction, cooled and filtered, concentrating under reduced pressure solvent straight 10%, regulate filtrate pH value straight 5～6,90～98 ℃ of heating make glycosides be hydrolyzed to the form of aglycon, and crystallization obtains thick product under acidic conditions then.Though this method has improved the yield of dihydroquercetin, do not pass through extracting operation, the purity after the very difficult raising crystallization.
Publication number is that the Chinese patent of CN1844095 has been introduced a kind of method of extracting dihydroquercetin from tamarack, this method is extraction agent with water, the larch in Xinanlin area that contains dihydroquercetin is extracted, aqueous extraction liquor to gained is that extraction agent carries out liquid-liquid extraction with the methyl tertiary butyl ether, adopt gac or atlapulgite that the methyl tertiary butyl ether extraction liquid is carried out adsorption bleaching, the back methyl tertiary butyl ether extraction liquid that decolours is carried out removing of solvent under vacuum condition, remove paste water behind the solvent and carry out crystallization purifying and make the dihydroquercetin raw product.The used extraction solvent of this method is a methyl tertiary butyl ether, and price is expensive; And the decolorization of gac or atlapulgite is non-enclosed operating process, is not easy to continuity production.
Publication number is that the Chinese patent of CN1858046 has been introduced a kind of method that adopts absorption method to extract dihydroquercetin from tamarack, this method is extraction agent with water, the larch in Xinanlin area that contains dihydroquercetin is extracted, adopt gac or atlapulgite that extracting solution is decoloured, thereafter, aqueous extraction liquor to gained is that sorbent material adsorbs with polyamide powder earlier, carry out desorb with desorption solvent again, the gained stripping liquid carries out solvent removal under vacuum condition, the white or the little yellow powdered dihydroquercetin raw product that obtain.This method adopts twice adsorption operations in leaching process, the enrichment of once decolouring has not only increased the cost of sorbent material, has also extended the production cycle, has increased extraction cost.
Publication number is that the Chinese patent of CN101333203 and CN101333204 has been introduced a kind of method for preparing dihydroquercetin from the tamarack wood chip, tamarack wood chip and ethanolic soln joined in the extractor fully mix, both add-ons are 50 kilograms of tamarack wood chips, 500～800 liters of 50% ethanolic solns, extract after-filtration, through extracting for the second time, merging filtrate, extraction, collect organic solution, to doing, used hot water dissolving's residue in 10: 1 by weight with vacuum-evaporator underpressure distillation organic phase, use activated carbon decolorizing, crystallization under 3-5 ℃ of temperature is separated out dihydro Quercetin product, again through vacuum-drying, pulverize and be finished product.The tamarack wood chip that this method is used causes the inconvenience of filter operation because particle is less and inhomogeneous; Because the wood chip lighter weight floats on the solvent top, needs to consume a large amount of solvents in stirring and immersion process, has increased the burden of solvent recuperation for follow-up underpressure distillation.
Publication number be the patent of CN101054369 introduced a kind of from Folium Engelhardia roxburghina the method for extraction separation dihydroquercetin, be raw material with the Folium Engelhardia roxburghina, by extract, concentrate, column chromatography, crystallization, hydrolysis, obtain a kind of needle crystal, the dihydroquercetin of off-white color.The used column chromatography cost of this method height, the production cycle is long.
Summary of the invention:
The object of the present invention is to provide a kind of method that from tamarack, prepares dihydroquercetin.
In order to achieve the above object, the technical solution used in the present invention comprises: with the tamarack wood powder is raw material, with the ethanolic soln refluxing extraction once, filter extracting solution, strong-acid ion exchange resin and chlorinated solvents are added in the extracting solution, and back hydrolysis makes the combined dihydroquercetin be converted into the free state dihydroquercetin, and reaction is isolated the chlorinated solvents phase after finishing, be concentrated into driedly, obtain product behind the recrystallization.
Advantage of the present invention is:
1. adopt ion exchange resin to be used for combined dihydroquercetin hydrolytic process as solid acid, the efficient height than more environmental protection of liquid acid, is easy to realize cleaner production
2. hydrolysis and extraction are carried out simultaneously, have avoided the degraded of dihydroquercetin because of strong acid condition effectively, save the usage quantity of operation sequence and solvent, and production cost is low, the yield height.
Embodiment:
Below the invention process is described in further detail:
With the tamarack wood powder is raw material, with the ethanolic soln refluxing extraction once, filter extracting solution, strong-acid ion exchange resin and chlorinated solvents are added in the extracting solution, back hydrolysis makes the combined dihydroquercetin be converted into the free state dihydroquercetin, isolate the chlorinated solvents phase after reaction finishes, be concentrated into driedly, obtain product behind the recrystallization.
Refluxing extraction is 10%～85% with the volume fraction of ethanolic soln, 75～90 ℃ of refluxing extraction temperature, 1～5 hour extraction time, solid-liquid ratio 1: 6～1: 20.
Hydrolysis can be a macroporous type with strong-acid ion exchange resin, also can be gel-type, preferred gel-type, and usage quantity is that hydrolysis temperature is 50～85 ℃, hydrolysis time 0.5～4 hour in 3～20% of tamarack raw material.
Chlorinated solvents is methylene dichloride, trichloromethane, 1,1-ethylene dichloride and 1, and the mixed solvent of a kind of or its arbitrary proportion in the 2-ethylene dichloride, the ratio of chlorinated solvents and extracting solution is 7: 3～3: 7.
Below, the present invention will be further detailed with embodiment, but it is not limited to embodiment or similar example.
Embodiment:
The tamarack wood chip of 105g moisture 9.6% adds 1 liter of 50% ethanolic soln, 80 ℃ of refluxing extraction 4h, cold filtration, the concentration of dihydroquercetin is about 0.017mg/mL in the filtrate, add 10g 201 * 7 storng-acid cation exchange resins, add then isopyknic 1,80 ℃ of heating hydrolysis 2h of 2-ethylene dichloride, reaction finishes postcooling, separate 1,2-ethylene dichloride phase reclaims 1, the 2-ethylene dichloride gets liquid dope 2.56g, and dihydroquercetin content is 32.6%.
Claims (5)
1. method that from tamarack, prepares dihydroquercetin, it is characterized in that: with the tamarack wood powder is raw material, with the ethanolic soln refluxing extraction once, filter extracting solution, strong-acid ion exchange resin and chlorinated solvents are added in the extracting solution, and back hydrolysis makes the combined dihydroquercetin be converted into the free state dihydroquercetin, and reaction is isolated the chlorinated solvents phase after finishing, be concentrated into driedly, obtain product behind the recrystallization.
2. according to the described a kind of method for preparing dihydroquercetin from tamarack of claim 1, it is characterized in that: refluxing extraction is 10%～85% with the volume fraction of ethanolic soln.
3. according to the described a kind of method that from tamarack, prepares dihydroquercetin of claim 1, it is characterized in that: 75～90 ℃ of refluxing extraction temperature, 1～5 hour extraction time, solid-liquid ratio 1: 6～1: 20.
4. according to the described a kind of method that from tamarack, prepares dihydroquercetin of claim 1, it is characterized in that: hydrolysis can be a macroporous type with strong-acid ion exchange resin, it also can be gel-type, preferred gel-type, usage quantity is in 3～20% of tamarack raw material, hydrolysis temperature is 50～85 ℃, hydrolysis time 0.5～4 hour.
5. according to the described a kind of method that from tamarack, prepares dihydroquercetin of claim 1, it is characterized in that: chlorinated solvents is methylene dichloride, trichloromethane, 1,1-ethylene dichloride and 1, the mixed solvent of a kind of or its arbitrary proportion in the 2-ethylene dichloride, the ratio of chlorinated solvents and extracting solution are 7: 3～3: 7.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010184375XA CN101851221B (en) | 2010-05-27 | 2010-05-27 | Method for preparing dihydroquercetin from larches |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010184375XA CN101851221B (en) | 2010-05-27 | 2010-05-27 | Method for preparing dihydroquercetin from larches |
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| CN101851221A true CN101851221A (en) | 2010-10-06 |
| CN101851221B CN101851221B (en) | 2012-09-05 |
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| CN201010184375XA Expired - Fee Related CN101851221B (en) | 2010-05-27 | 2010-05-27 | Method for preparing dihydroquercetin from larches |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863869A (en) * | 2010-06-03 | 2010-10-20 | 东北林业大学 | Method for extracting dihydroquercetin from larch sheets |
| CN101993429A (en) * | 2010-12-08 | 2011-03-30 | 天津市尖峰天然产物研究开发有限公司 | Method for extracting dihydroquercetin from larch sawdust |
| CN102924420A (en) * | 2012-10-25 | 2013-02-13 | 沈立乾 | Method for extracting dihydroquercetin from root of dahurian larch |
| CN103402506A (en) * | 2011-06-02 | 2013-11-20 | S·Y·列什科夫 | Combination for treatment of diabetes mellitus |
| CN108524313A (en) * | 2018-07-02 | 2018-09-14 | 吉林农业科技学院 | Dihydroquercetin skin care skin-lightening cosmetic |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2744919A (en) * | 1952-09-09 | 1956-05-08 | Ervin F Kurth | Producing pure dihydroquercetin |
| CA532804A (en) * | 1956-11-06 | F. Kurth Ervin | Producing pure dihydroquercetin | |
| WO2005044021A1 (en) * | 2003-10-30 | 2005-05-19 | Loders Croklaan B.V. | Pine needle extract |
| CN1844095A (en) * | 2006-04-29 | 2006-10-11 | 广州大学 | Method for extracting dihydro-quercetin from larch |
| CN1858046A (en) * | 2006-06-02 | 2006-11-08 | 广州大学 | Method for extracting dihydro quercetin from larch using adsorption method |
| CN101054369A (en) * | 2007-06-05 | 2007-10-17 | 宋云飞 | Method for extracting and separating dihydroquercetin from engelhardtia leaves |
-
2010
- 2010-05-27 CN CN201010184375XA patent/CN101851221B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA532804A (en) * | 1956-11-06 | F. Kurth Ervin | Producing pure dihydroquercetin | |
| US2744919A (en) * | 1952-09-09 | 1956-05-08 | Ervin F Kurth | Producing pure dihydroquercetin |
| WO2005044021A1 (en) * | 2003-10-30 | 2005-05-19 | Loders Croklaan B.V. | Pine needle extract |
| CN1844095A (en) * | 2006-04-29 | 2006-10-11 | 广州大学 | Method for extracting dihydro-quercetin from larch |
| CN1858046A (en) * | 2006-06-02 | 2006-11-08 | 广州大学 | Method for extracting dihydro quercetin from larch using adsorption method |
| CN101054369A (en) * | 2007-06-05 | 2007-10-17 | 宋云飞 | Method for extracting and separating dihydroquercetin from engelhardtia leaves |
Non-Patent Citations (2)
| Title |
|---|
| 《浙江林业科技》 20040930 金建忠等 落叶松中二氢槲皮素的提取及鉴定 第15-17页 1-5 第24卷, 第5期 2 * |
| 《食品科学》 20091231 王宇等 落叶松中二氢槲皮素提取工艺研究 第141-143页 1-5 第30卷, 第24期 2 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863869A (en) * | 2010-06-03 | 2010-10-20 | 东北林业大学 | Method for extracting dihydroquercetin from larch sheets |
| CN101993429A (en) * | 2010-12-08 | 2011-03-30 | 天津市尖峰天然产物研究开发有限公司 | Method for extracting dihydroquercetin from larch sawdust |
| CN103402506A (en) * | 2011-06-02 | 2013-11-20 | S·Y·列什科夫 | Combination for treatment of diabetes mellitus |
| CN102924420A (en) * | 2012-10-25 | 2013-02-13 | 沈立乾 | Method for extracting dihydroquercetin from root of dahurian larch |
| CN102924420B (en) * | 2012-10-25 | 2013-09-04 | 沈立乾 | Method for extracting dihydroquercetin from root of dahurian larch |
| US9206152B2 (en) | 2012-10-25 | 2015-12-08 | Liqian Shen | Method for extracting dihydroquercetin from the root of larch trees |
| CN108524313A (en) * | 2018-07-02 | 2018-09-14 | 吉林农业科技学院 | Dihydroquercetin skin care skin-lightening cosmetic |
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| CN101851221B (en) | 2012-09-05 |
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Granted publication date: 20120905 Termination date: 20130527 |