CN100395222C - Method for preparing dehydrated open loop secoisolariciresinol from flax seed - Google Patents
Method for preparing dehydrated open loop secoisolariciresinol from flax seed Download PDFInfo
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- CN100395222C CN100395222C CNB2006100127008A CN200610012700A CN100395222C CN 100395222 C CN100395222 C CN 100395222C CN B2006100127008 A CNB2006100127008 A CN B2006100127008A CN 200610012700 A CN200610012700 A CN 200610012700A CN 100395222 C CN100395222 C CN 100395222C
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Abstract
The present invention relates to a method for preparing dehydrated secoisolarciresinol from flax seeds, which comprises: the flax seeds are mixed with 60 to 100 wt% of water solution of alcohol or ketone according to the weight ratio of 1:2 to 8 to extract lignan, and an extraction liquid is obtained; the extraction liquid is concentrated to 1/16 to 1/12 of the original volume and is compounded into an alkali solution with the alkali content of 1 to 3M, the alkali solution is hydrolyzed for 1 to 3 hours, the pH value of a hydrolysis liquid is adjusted to 2 to 4, and the hydrolysis liquid is extracted with a low-polar solvent until an organic phase becomes colorless, and the hydrolysis liquid is separated to obtain a water phase; the water phase is prepared into an acid solution with the acid content of 1 to 2M, the acid solution is hydrolyzed at 90 to 100 DEG C for 2 to 3 hours, the pH value of the hydrolysis liquid is adjusted to 2 to 4, the dehydrated secoisolarciresinol in the hydrolysis liquid is extracted with a low-polar solvent, and an organic phase is evaporated to dryness; and the dry product is decolored, crystallized and filtered to obtain the required product. The method has the advantages of convenient operation, simple technology, low separation cost, large processing capacity and convenient bulk production.
Description
Technical field
The present invention relates to a kind of method by linseed oil production ANHSECO.
Technical background
Lignan is a class plant female hormone, and it is polymerized by the plain bimolecular of phenylpropyl alcohol, because it has multiple physiologically active, especially antitumor, antiviral and suppress effect aspect some enzyme, has caused domestic and international many investigators' concern.Flax (Linumusitatissimum) is the geographic traditional oil crops of NORTHWEST CHINA portion, contains abundant lignan compounds, and its main bioactive ingredients is open loop secoisolariciresinoldiglucoside diglucoside (SDG).ANHSECO (ANHSECO) all is the hydrolysate of SDG with secoisolarciresinol (SECO), has the biological activity similar with SDG.Lignan is mainly derived from the product of cereal and other fiber-enriched in the human foods, and linseed oil is the abundantest source of humans and animals xylogen precursor.Lignan content in cereal is 2mg/kg～7mg/kg, and the content in linseed oil is 2mg/g～20mg/g.Because its unique physiologically active and the content that enriches in linseed oil, extraction, the Study on Purification of relevant secoisolariciresinol diglycoside becomes the emphasis that numerous researchers are paid close attention to.But the extensive separation of this compound is purified and is had certain degree of difficulty, has limited it in Application for Field such as medicine, food.
(Food chemistry 76 (2002) 207-212) such as Pernilla Johnsson utilize 1,4-dioxy hexane and alcohol mixeding liquid, extract the soluble components in the linseed oil, the hydrolysis of extract buck, separation separates with high performance liquid chromatography through column chromatography, obtain lignan---and secoisolarciresinol (secoisolariciresinol diglucoside, SDG), ferulic acid glucoside and three kinds of pure product materials of coumaric acid glucoside; AndreasDegenhardt etc. (Journal of Chromatography A, 943 (2002) 299-302) etc. extract lignan with methanol-water solution, alkaline hydrolysis then, and the efficient liquid of hydrolysate utilization-liquid convection current chromatographic purification obtains SDG; After (Lebensm-Wissu-Technol, 33,268-275 (2000)) such as Basavaraj MadhuSudhan separated linseed oil skin benevolence, the linseed oil skin directly was used as the lignan product; (Plant Physiol Biochem such as Stephane Charlet, 40 (2002) 225-229) acidolysis linseed oil lignan crude extract hydrolysis effect and influence factor have been analyzed, temperature is certain, the concentration of reaction times and acid has bigger influence to hydrolysis effect, and has proposed a kind of method of simple measurement lignan content; (Journal of Chromatography A such as Christina Eliasson, 1012 (2003) 151-159) discover that the extraction of lignan in the degreasing linseed oil powder and hydrolysis can finish in one step of buck, and relatively have better productive rate with two-step approach; (Journal of Chromatography A such as JFritsche, that 972 (2002) 195-203) utilizes anion-exchange chromatography and reverse-phase chromatography success has separated the lignan hydrolyzate, and successful separation and determined the structure of the non-corresponding isomer of SDG on the LC-NMR-MS combined instrument.Patent of invention CN 1487948A has introduced a kind of method from linseed oil extraction separation SDG, and through the supercritical co degreasing, alkaline alcohol solution extracts SDG, with slipping chromatography, the concentrated branch, obtains being rich in the cut of SDG then.SDG after patent of invention CN1162438C utilizes silica gel adsorption replacement chromatographic technique in the past to alkaline hydrolysis separates purification.Patent of invention CN1749262A adopts pure water extraction, the isolating method of absorption with macroporous adsorbent resin, obtains the enriched substance of the total glucosides 60～85% of lignan.Patent of invention CN 1749262A utilizes pure water or pure alkaline extraction lignan, purifies through resin absorption then, obtains the lignan product of content 60～80%.(Chinese oil such as Liu Dachuan, 2002 the 27th the 5th phases of volume) way that adopts triethylamine alkaline hydrolysis, column chromatography to purify obtains the secoisolariciresinol diglycoside product, and has examined or check the influence to extraction yield of extract concentration, extraction temperature, extraction time, extraction time and solid-to-liquid ratio.Though aforesaid method all obtains lignan product or enriched substance,, stratographic uses, the separation costs height, production lot is little, has limited the industrialization of lignan product; And without chromatographic separation, but lacking effective separation circuit, it is limited that gained produces brilliant purity, influences the application of product at health care, cosmetic and field of medicaments.
Summary of the invention:
The purpose of this invention is to provide the method that a kind of cost is low, purity is high by linseed oil production ANHSECO.
The present invention is to be raw material with the linseed oil, with alcohol-water or ketone-extraction with aqueous solution secoisolariciresinol diglycoside wherein, through technologies such as concentrated, basic hydrolysis, adjusting pH value, weak polar solvent extraction, acid hydrolysis, weak polar solvent extraction, crystallizations, obtain ANHSECO.
Concrete operations step of the present invention is as follows:
(1) be that the aqueous solution of 60～100% alcohol or ketone mixes by 1: 2～8 part by weight with the whole seed of linseed oil or powder and weight concentration, normal temperature time extraction lignan obtains extracting solution.
(2) extracting solution is concentrated into 1/16～1/12 of original volume, add alkali and be made into the basic solution that alkalinity is 1～3M, ordinary-temp hydrolysis 1～3 hour, hydrolyzed solution adds acid for adjusting pH to 2～4, be extracted to organic phase with weak polar solvent and be colourless, separatory obtains being rich in the water of lignan;
(3) above-mentioned water is added acid, be made into the acid solution that acid content is 1～2M, under 90～100 ℃, acidolysis 2～3 hours, it is 2～4 that hydrolyzed solution adds alkali adjusting pH value, with weak polar solvent extraction ANHSECO wherein, organic phase evaporate to dryness;
(4) the evaporate to dryness gains are dissolved in recrystallisation solvent through decolouring, and crystallization is filtered, and obtains the product of wanting.
In described (1), the aqueous solution of alcohol or ketone refers to methanol-water, alcohol-water or acetone-water solution.
In described (2), the alkali of regulating pH in the alkali that is added and described (3) is sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate or triethylamine.
In described (2), the acid that is added in the acid of adjusting pH and described (3) is concentrated hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or acetic acid etc.
In described (2) and (3), used weak polar solvent is halohydrocarbon, lower member ester, aromatic compounds or rudimentary ether etc.Preferred chloroform, methylene dichloride, tetracol phenixin, ethyl acetate, methyl acetate, toluene, benzene, ether.
In described (4), used recrystallisation solvent is one or more in lower alcohol, ketone, rudimentary ether, lower member ester, halohydrocarbon, the aromatic compounds, alcohol-water solution or ketone-aqueous solution etc.
Characteristics of the present invention
The present invention has following advantage:
1. can be fit to the linseed oil powder and also be applicable to whole seed linseed oil, wherein whole seed extracts and does not destroy other biological activeconstituents in the linseed oil, so do not influence the production of flax glue, oleum lini, makes things convenient for the comprehensive deeply exploitation of flax product.
2. do not use technology such as membrane sepn, chromatographic separation among the present invention, easy to operate, technology is simple, and separation costs is low, and treatment capacity is big, is convenient to produce in batches.
3. the present invention uses two one-step hydrolysis methods first, and utilizes the weak polar solvent extraction of two steps, and weeding of grease solubility impurity and fat insoluble impurities can obtain the higher ANHSECO of purity respectively.
Embodiment
Embodiment 1:
Taking by weighing the clean linseed oil powder of 300g, is 70% aqueous ethanolic solution normal temperature leaching 24h with 600ml concentration, filters, and filter residue repeats leaching once, and merging filtrate is evaporated to 100ml.The adding sodium bicarbonate is made into the solution of 3M, and normal temperature alkaline hydrolysis 3h adds hydrochloric acid, and regulating the pH value is 3, and it is colourless to be extracted to organic phase repeatedly with ethyl acetate.Water adds concentrated hydrochloric acid, is made into the solution that concentration is 1M, and at 100 ℃ of acidolysis 3h, regulating pH with sodium bicarbonate is 3, adds ethyl acetate extraction, and the organic phase evaporate to dryness adds an amount of 80% aqueous ethanolic solution, uses activated carbon decolorizing, and crystallization obtains white solid.
Embodiment 2:
Taking by weighing the clean linseed oil of 300g, is 60% aqueous acetone solution normal temperature leaching 24h with 1000ml concentration, filters, and filter residue repeats leaching once, and merging filtrate is evaporated to 150ml.Adding yellow soda ash is made into the solution of 2M, and normal temperature alkaline hydrolysis 3h adds sulfuric acid, and regulating the pH value is 2, and it is colourless to be extracted to organic phase repeatedly with chloroform.Water adds the vitriol oil, is made into the solution that concentration is 1M, and at 100 ℃ of acidolysis 2h, regulating pH with yellow soda ash is 2, adds chloroform extraction, and the organic phase evaporate to dryness adds an amount of toluene, uses activated carbon decolorizing, and crystallization obtains white solid.
Embodiment 3:
Taking by weighing the clean linseed oil powder of 300g, is 80% methanol aqueous solution normal temperature leaching 24h with 1500ml concentration, filters, and filter residue repeats leaching once, and merging filtrate is evaporated to 200ml.Adding sodium hydroxide is made into the solution of 2M, and normal temperature alkaline hydrolysis 1h adds nitric acid, and regulating the pH value is 4, and it is colourless to be extracted to organic phase repeatedly with toluene.Water adds nitric acid, is made into the solution that concentration is 2M, and at 100 ℃ of acidolysis 1h, regulating pH with sodium hydroxide is 4, adds the toluene extraction, and the organic phase evaporate to dryness adds an amount of methyl alcohol, uses activated carbon decolorizing, and crystallization obtains white solid.
Embodiment 4:
Taking by weighing the clean linseed oil of 300g, is 90% methanol aqueous solution normal temperature leaching 24h with 2400ml concentration, filters, and filter residue repeats leaching once, and merging filtrate is evaporated to 300ml.Adding potassium hydroxide is made into the solution of 1M, and normal temperature alkaline hydrolysis 3h adds phosphoric acid, and regulating the pH value is 3, and it is colourless to be extracted to organic phase repeatedly with ether.Water adds phosphoric acid, is made into the solution that concentration is 2M, and at 100 ℃ of acidolysis 2.5h, regulating pH with sodium hydroxide is 3, adds extracted with diethyl ether, and the organic phase evaporate to dryness adds an amount of 50% aqueous acetone solution, uses activated carbon decolorizing, and crystallization obtains white solid.
Embodiment 5:
Taking by weighing the clean linseed oil of 300g, is 95% aqueous acetone solution normal temperature leaching 24h with 2000ml concentration, filters, and filter residue repeats leaching once, and merging filtrate is evaporated to 300ml.The adding triethylamine is made into the solution of 2M, and normal temperature alkaline hydrolysis 2h adds acetic acid, and regulating the pH value is 4, and it is colourless to be extracted to organic phase repeatedly with methylene dichloride.Water adds acetic acid, is made into the solution that concentration is 2M, and at 100 ℃ of acidolysis 2h, regulating pH with yellow soda ash is 4, adds dichloromethane extraction, and the organic phase evaporate to dryness adds proper amount of acetone, and with the aluminum oxide decolouring, crystallization obtains white solid.
Embodiment 6:
Taking by weighing the clean linseed oil powder of 300g, is 70% aqueous ethanolic solution normal temperature leaching 24h with 1200ml concentration, filters, and filter residue repeats leaching once, and merging filtrate is evaporated to 150ml.Adding sodium hydroxide is made into the solution of 1M, and normal temperature alkaline hydrolysis 3h adds sulfuric acid, and regulating the pH value is 3, and it is colourless to be extracted to organic phase repeatedly with methyl acetate.Water adds the vitriol oil, is made into the solution that concentration is 1M, and at 100 ℃ of acidolysis 2.5h, regulating pH with sodium hydroxide is 3, adds the methyl acetate extraction, and the organic phase evaporate to dryness adds an amount of chloroform, and with the aluminum oxide decolouring, crystallization obtains white solid.
Embodiment 7:
Taking by weighing the clean linseed oil powder of 300g, is 70% aqueous ethanolic solution normal temperature leaching 24h with 1500ml concentration, filters, and filter residue repeats leaching once, and merging filtrate is evaporated to 180ml.Adding sodium hydroxide is made into the solution of 1M, and normal temperature alkaline hydrolysis 3h adds hydrochloric acid, and regulating the pH value is 3, and it is colourless to be extracted to organic phase repeatedly with benzene.Water adds sulfuric acid, is made into the solution that concentration is 1M, and at 100 ℃ of acidolysis 2.5h, regulating pH with sodium hydroxide is 3, adds the benzene extraction, and the organic phase evaporate to dryness adds an amount of ethyl acetate, and with the aluminum oxide decolouring, crystallization obtains white solid.
Embodiment 8:
Taking by weighing the clean linseed oil of 300g, is 80% methanol aqueous solution normal temperature leaching 24h with 800ml concentration, filters, and filter residue repeats leaching once, and merging filtrate is evaporated to 100ml.Adding sodium hydroxide is made into the solution of 1M, and normal temperature alkaline hydrolysis 3h adds sulfuric acid, and regulating the pH value is 3, and it is colourless to be extracted to organic phase repeatedly with tetracol phenixin.Water adds the vitriol oil, is made into the solution that concentration is 1M, and at 100 ℃ of acidolysis 2.5h, regulating pH with sodium hydroxide is 3, add carbon tetrachloride extraction, the organic phase evaporate to dryness, add an amount of ethyl acetate and ether mixed solution (1: 1, v/v), with the aluminum oxide decolouring, crystallization obtains white solid.
Claims (7)
1. one kind prepares the method for ANHSECO by linseed oil, it is characterized in that comprising the steps:
(1) be that the aqueous solution of 60～100% alcohol or ketone mixes by 1: 2～8 part by weight with the whole seed of linseed oil or powder and weight concentration, normal temperature time extraction lignan obtains extracting solution;
(2) extracting solution is concentrated into 1/16～1/12 of original volume, add alkali and be made into the basic solution that alkalinity is 1～3M, ordinary-temp hydrolysis 1～3 hour, hydrolyzed solution adds acid for adjusting pH to 2～4, be extracted to organic phase with weak polar solvent and be colourless, separatory obtains being rich in the water of lignan;
(3) above-mentioned water is added acid, be made into the acid solution that acid content is 1～2M, under 90～100 ℃, acidolysis 2～3 hours, it is 2～4 that hydrolyzed solution adds alkali adjusting pH value, with weak polar solvent extraction ANHSECO wherein, organic phase evaporate to dryness;
(4) the evaporate to dryness gains are dissolved in recrystallisation solvent through decolouring, and crystallization is filtered, and obtains the product of wanting;
Described weak polar solvent is: halohydrocarbon, ethyl acetate, methyl acetate, aromatic compounds or ether.
2. as claimed in claim 1ly a kind ofly prepare the method for ANHSECO by linseed oil, the aqueous solution that it is characterized in that described alcohol is methanol-water or ethanol-water solution.
3. as claimed in claim 1ly a kind ofly prepare the method for ANHSECO by linseed oil, the aqueous solution that it is characterized in that described ketone is acetone-water solution.
4. as claimed in claim 1ly a kind ofly prepare the method for ANHSECO, it is characterized in that described alkali is sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate or triethylamine by linseed oil.
5. as claimed in claim 1ly a kind ofly prepare the method for ANHSECO, it is characterized in that described acid is concentrated hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or acetic acid by linseed oil.
6. as claimed in claim 1ly a kind ofly prepare the method for ANHSECO by linseed oil, it is characterized in that described halohydrocarbon is chloroform, methylene dichloride or tetracol phenixin, aromatic compounds is toluene or benzene.
7. a kind of method for preparing ANHSECO by linseed oil as claimed in claim 1, it is characterized in that described recrystallisation solvent is that methyl alcohol, ketone, ethyl acetate and ether volume ratio are one or more in 1: 1 the mixture, ethyl acetate, halohydrocarbon, aromatic compounds, alcohol-water solution or ketone-aqueous solution.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004034A (en) * | 2014-05-14 | 2014-08-27 | 中国科学院华南植物园 | Method for preparing secoisolariciresinol 9'-O-beta-xyloside |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239995B (en) * | 2008-03-13 | 2010-09-15 | 成都圆大生物科技有限公司 | Method for preparing flax lignins |
| CN101759731B (en) * | 2008-12-25 | 2011-10-19 | 中国科学院兰州化学物理研究所 | Extraction method of linseed gum and secoisolariciresin-ol diglucoside |
| CN101538294B (en) * | 2009-04-28 | 2013-04-17 | 中国科学院山西煤炭化学研究所 | Method for preparing SDG and ferulic acid glucoside or ester thereof |
| CN101955892B (en) * | 2009-07-21 | 2012-04-18 | 北京大学 | Klebsiella and application thereof |
| CN105145806A (en) * | 2015-10-22 | 2015-12-16 | 仇颖超 | Method for preparing fruit antioxidant by efficiently extracting flax lignans |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394865A (en) * | 2001-07-11 | 2003-02-05 | 北京万博力科技发展有限公司 | Method for extracting, separating and purifying linolenic lignan by using linseed cake |
| CN1487948A (en) * | 2001-01-22 | 2004-04-07 | 芬兰农业食品研究公司 | Process for is olating and purifying secoisolarisiresinol diglycoside (SDG) from flaxseed |
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- 2006-05-12 CN CNB2006100127008A patent/CN100395222C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1487948A (en) * | 2001-01-22 | 2004-04-07 | 芬兰农业食品研究公司 | Process for is olating and purifying secoisolarisiresinol diglycoside (SDG) from flaxseed |
| CN1394865A (en) * | 2001-07-11 | 2003-02-05 | 北京万博力科技发展有限公司 | Method for extracting, separating and purifying linolenic lignan by using linseed cake |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004034A (en) * | 2014-05-14 | 2014-08-27 | 中国科学院华南植物园 | Method for preparing secoisolariciresinol 9'-O-beta-xyloside |
| CN104004034B (en) * | 2014-05-14 | 2016-02-03 | 中国科学院华南植物园 | One prepares the method for Secoisolariciresinol 9 '-O-β-xyloside |
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