CN103275049A - Method for preparing myricetin by using vine tea and application of pyrosulfite - Google Patents
Method for preparing myricetin by using vine tea and application of pyrosulfite Download PDFInfo
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- CN103275049A CN103275049A CN2013101897575A CN201310189757A CN103275049A CN 103275049 A CN103275049 A CN 103275049A CN 2013101897575 A CN2013101897575 A CN 2013101897575A CN 201310189757 A CN201310189757 A CN 201310189757A CN 103275049 A CN103275049 A CN 103275049A
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- vine tea
- ampelopsin
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Abstract
The invention discloses a method for preparing myricetin by using vine tea and an application of pyrosulfite. The method comprises the following steps of: extracting the ground vine tea with hot water, filtering while the vine tea is hot, concentrating the filter liquor and cooling to separate out sediments; carrying out suction filtration, dissolving the sediment residue with absolute ethyl alcohol, filtering to remove undissolved substances, and concentrating the ethanol solution obtained from filtration to obtain ethyl alcohol extract; adding the ethyl alcohol extract into the pyrosulfite solution for reaction, then pouring the reaction liquid into an ice-water mixture, and crystallizing, filtering, washing and drying to obtain the myricetin. According to the application, the pyrosulfite is applied to the vine tea as a dehydrogenation oxidizing agent for dehydrogenation transformation from dihydromyricetin to myricetin, and the transformation efficiency is high. By using the method, materials are low in cost and can be easily obtained. The method is simple, pollution-free and low in equipment requirement and can be widely applied to industrial production. The yield of the prepared myricetin reaches 21% in comparison with materials, and the purity reaches 96%.
Description
Technical field:
The present invention relates to prepare the method for ampelopsin and the application of pyrosulfite with vine tea, belong to extraction and the enrichment preparation field of natural product active ingredient.
Background technology
All contain flavone component ampelopsin and dibydro myricetrin in the plant of Vitaceae Ampelopsis, wherein the highest with content in the Ampelopsis grossedentata, the processed goods of Ampelopsis grossedentata cauline leaf is commonly called as vine tea, is rich in the various active composition in the vine tea, as dibydro myricetrin, ampelopsin, catechin, gallic acid, amino acid, polysaccharide etc., wherein the highest with the dihydromyricetin cellulose content, ampelopsin is lower.According to existing document and patent report, most researchs focus on the extraction and purification to the high dibydro myricetrin of content in the vine tea, and it is less to the research of ampelopsin, relevant patent documentation has: a kind of method CN200510032918.5 that extracts dibydro myricetrin from vine tea, the preparation method CN201110093346.7 of dibydro myricetrin in the vine tea, non-patent literature be more (Qin Jieping etc., Chinese Journal of New Drugs then, 2004, NO.10; Li Wei etc., Food science, 2004, NO.11, etc.).Yet at present, U.S. FDA (united States food and drug administration (U.S.Food and Drug Administration)) has been widely used in ampelopsin medicine, food, healthcare products and makeup, and be expected to it further is developed as the anti-inflammatory medication of special population, thereby alleviate the Western medicine microbiotic to the toxic side effect of human body.Source-the Hairy Waxmyrtle of ampelopsin is the peculiar resource of China, and still, owing to reasons such as extraction processes, the research to ampelopsin at present is mainly derived from vine tea, and considerably less to the research of Hairy Waxmyrtle.From some scientific research personnel's result of study, we are as can be seen: main component is dibydro myricetrin in the vine tea, its content accounts for about 25%, and ampelopsin only accounts for about 2%, even lower (guangdong agricultural science, 2012, NO.15, people such as Zhang Mingsheng obtain the mixture of dibydro myricetrin and ampelopsin by supersound extraction, and wherein the former accounts for about 25%, and the latter is less than 1%; Herbal medicine, 2003, NO.34, people such as Li Yingqi have utilized hplc simultaneous determination, and dibydro myricetrin in the vine tea and the content of ampelopsin are respectively 25%, 2%), this makes the development and utilization of ampelopsin have certain limitation.Referring to domestic and foreign literature, have only the investigator of only a few that thereby dibydro myricetrin in the vine tea is carried out the enrichment preparation that modification realizes ampelopsin up to now, relevant patent documentation has: mentioned a kind of method of extracting ampelopsin among a kind of preparation method CN200610019693.4 of ampelopsin, purity brings up to 95%, but productive rate is very low, have only 5%, the novel preparation method CN200810050893.5 of ampelopsin has mentioned a kind of conversion of dibydro myricetrin being carried out mechanism by alkaline transforming agent, obtained the higher ampelopsin of purity, but wherein the yield of ampelopsin is up to about 8%.
Summary of the invention
The present invention is directed to the ampelopsin resource shortage, prior art is low to extraction and the preparation productive rate of ampelopsin, be up to 8%, be difficult to tackle the problem of suitability for industrialized production, so purpose is being to provide a kind of cost the low method for preparing high yield, high purity ampelopsin with vine tea; This method raw material is cheap and easy to get, method is simple, pollution-free, low for equipment requirements, extensive suitability for industrialized production.
Another object of the present invention provides the application of pyrosulfite as the dehydrogenation oxidation agent, with pyrosulfite as the dehydrogenation oxidation agent can with dibydro myricetrin in the vine tea class plant almost all dehydrogenations change into ampelopsin, obtain high yield, highly purified ampelopsin.
The invention provides the method for preparing ampelopsin with vine tea, this method is the vine tea that will pulverize with 90～100 ℃ of hot water lixiviates, after the filtered while hot, with filtrate concentrating be placed on 0～5 ℃ down cooling separate out precipitation; Suction filtration, precipitation filter residue anhydrous alcohol solution refilters and removes insolubles, and the ethanolic soln that filters gained obtains ethanol extract after concentrating; Ethanol extract is joined in the pyrosulphite salts solution, 80～100 ℃ of reactions down, after reaction is finished reaction solution is poured in the mixture of ice and water, after crystallization, filtration, washing, drying, namely; Described pyrosulfite add-on is 1～3 times of vine tea quality, and wherein, the mass content of pyrosulfite is 10～40% in the pyrosulphite salts solution.
Described pyrosulfite comprises in potassium pyrosulfite, Sodium Pyrosulfite or the ammonium pyrosulfite one or more.
Described pyrosulphite salts solution is the aqueous solution of pyrosulfite.
In the aforesaid method ethanol extract is joined in the pyrosulphite salts solution, the time of reaction is 4～8h down at 80～100 ℃.
Vine tea powder in the aforesaid method: the solid-liquid ratio of hot water is 1:20～40, and unit is g/mL.
The lixiviate number of times is 2～4 times in the aforesaid method, and each extraction time is 0.5～2h.
After the lixiviate for several times, united extraction liquid carries out concentration operation again in the aforesaid method.
Filtrate is concentrated to 1/4～2/5 of former filtrate volume in the aforesaid method.
Ethanolic soln is concentrated into 1/4～2/5 of former volumes of aqueous ethanol in the aforesaid method after concentrating.
Use the frozen water repetitive scrubbing after the ampelopsin crystal filtering separation of gained is come out behind the crystallization in the aforesaid method; The pyrosulfite washes clean that unreacted is intact.
Vine tea powder in the aforesaid method: the solid-liquid ratio of dehydrated alcohol (g:mL) is 1:5～15.
Can further improve purity by recrystallization repeatedly in the aforesaid method.
Method of the present invention is applicable to any material of vegetable origin that contains dibydro myricetrin.
The present invention also provides the application of pyrosulfite, and this application is that agent is applied to dibydro myricetrin in the vine tea class plant and transforms to the dehydrogenation of ampelopsin as dehydrogenation oxidation with pyrosulfite.
Described pyrosulfite comprises in potassium pyrosulfite, Sodium Pyrosulfite or the ammonium pyrosulfite one or more.
The method that vine tea of the present invention prepares ampelopsin may further comprise the steps:
(1) with vine tea finished product crushed after being dried in vacuum drying oven, with 90～100 ℃ of hot water extraction 2～4 times, united extraction liquid, suction filtration while hot, filtrate is concentrated into 1/4～2/5 of former filtrate volume through underpressure distillation, leaves standstill at 0～5 ℃ and separates out precipitation; Suction filtration, precipitation filter residue anhydrous alcohol solution leaves standstill suction filtration to remove insoluble composition, and filtrate decompression is concentrated into 1/4～2/5 of former volumes of aqueous ethanol, obtains ethanol extract;
(2) above-mentioned gained ethanol extract is joined in the aqueous solution of pyrosulfite, under 80～100 ℃ of conditions, behind reaction 4～8h, reaction solution is poured in the mixture of ice and water, separate out crystal, suction filtration, the frozen water repetitive scrubbing, vacuum-drying namely gets the ampelopsin crystal;
Described pyrosulfite add-on is 1～3 times of vine tea quality, and wherein, the mass content of pyrosulfite is 10～40% in the pyrosulphite salts solution.
Beneficial effect of the present invention: the present invention has overcome extraction and the low defective of preparation productive rate of ampelopsin in the prior art, the dihydromyricetin cellulose content accounts for about 25wt% in the bibliographical information vine tea, and ampelopsin 2wt%, prior art from material of vegetable origin, extract or the highest yield for preparing ampelopsin 8%; The present invention finds through contriver's lot of experiments, pyrosulphite can be used as the dehydrogenation oxidation agent can make dibydro myricetrin carry out the conversion one step generation ampelopsin of structure, transformation efficiency was outstanding when conversion reaction was reacted under 80～100 ℃ temperature condition, temperature is crossed low-yield and is reduced, the too high product of temperature can be further oxided, particularly at 95～100 ℃ of transformation efficiencies best (as can be seen from Figure 3, dibydro myricetrin almost all is converted into ampelopsin); The present invention adopts and extracts and the integrated continuous processing method of dehydrogenation thaumatropy, and the plant material that will contain the cheapnesss such as vine tea of dibydro myricetrin extracts by simple method, and dehydrogenation transforms one and goes on foot directly acquisition high yield, highly purified ampelopsin again; The inventive method productive rate has reached 21%, and purity has reached more than 96%; This method is pollution-free, low for equipment requirements, extensive suitability for industrialized production.
Description of drawings
[Fig. 1] is the high performance liquid chromatography spectrogram of dibydro myricetrin and ampelopsin reference substance: 1 is dibydro myricetrin, and 2 is ampelopsin.
[Fig. 2] is the high performance liquid chromatography spectrogram of crude extract before embodiment 2 dehydrogenation reactions: 1 is dibydro myricetrin, and 2 is ampelopsin.
[Fig. 3] is the high performance liquid chromatography spectrogram of embodiment 2 ampelopsin products: 1 is dibydro myricetrin, and 2 is ampelopsin.
Embodiment
Following examples are to further specify of the present invention, rather than restriction the present invention.
Chromatographic condition: chromatographic column: Kromasil C18 post (250mm * 4.6mm, 5 μ m), moving phase: methyl alcohol: water: Glacial acetic acid=50:50:1; Detect wavelength: 292nm, 375nm; Detect column temperature: 30 ℃; Sample size: 20 μ L; Flow velocity: 1.0mLmin
– 1
1, the extraction of vine tea
Take by weighing dry vine tea powder 20g, add about 200mL water, be heated to 95 ℃ of lixiviate 1h, filtered while hot, filter residue repeats aforesaid operations twice, merges three times filtrate, be concentrated into 200mL, the back is left standstill in 0～5 ℃ and is separated out light-yellow precipitate, suction filtration, filter precipitation 300mL anhydrous alcohol solution, leave standstill suction filtration, filtrate decompression is concentrated into 100mL, obtains the ethanol extract of extract, and is standby;
2, the dehydrogenation reaction of dibydro myricetrin
Above-mentioned 100mL concentrated extract is joined the Na of 250mL20%
2S
2O
5In the aqueous solution, react 4h down at 100 ℃; Finish reaction, mixed solution is poured in the mixture of ice and water, leave standstill and separate out precipitation, suction filtration, frozen water is washing precipitation repeatedly, and drying is carried out for 40 ℃ in vacuum in the back, gets the yellow-green colour solid, i.e. ampelopsin, the product yield is 21%.
The yellow-green colour material that obtains in the aforesaid operations is ampelopsin by the thin-layer chromatography preliminary evaluation; Carry out qualitative and quantitative analysis through high performance liquid chromatography, confirm that the gained material is ampelopsin, and purity is up to 96%.
1. the extraction of vine tea:
Take by weighing dry vine tea powder 20g, add 200mL water, be heated to 95 ℃ of lixiviate 1h, filtered while hot, filter residue repeats aforesaid operations twice, merges three times filtrate, is concentrated into 200mL; The back is left standstill in 0～5 ℃ and is separated out light-yellow precipitate, suction filtration, and the filter precipitation is used the 300mL anhydrous alcohol solution, leaves standstill suction filtration, and filtrate decompression is concentrated into 100mL, obtains the ethanol extract of extract, and is standby.
2. the dehydrogenation reaction of dibydro myricetrin:
Above-mentioned 100mL concentrated extract is joined the K of 250mL20%
2S
2O
5In the aqueous solution, react 4h down at 100 ℃; Finish reaction, mixed solution is poured in the mixture of ice and water, leave standstill and separate out precipitation, suction filtration, frozen water is washing precipitation repeatedly, and drying is carried out for 40 ℃ in vacuum in the back, gets the yellow-green colour solid, i.e. ampelopsin, the product yield is 21%.
The yellow-green colour material that obtains in the aforesaid operations is ampelopsin by the thin-layer chromatography preliminary evaluation; Carry out qualitative and quantitative analysis through high performance liquid chromatography, confirm that the gained material is ampelopsin, and purity is up to 96%.
Claims (9)
1. prepare the method for ampelopsin with vine tea, it is characterized in that, with the vine tea pulverized with 90～100 ℃ of hot water lixiviates, after the filtered while hot, with filtrate concentrating be placed on 0～5 ℃ down cooling separate out precipitation; Suction filtration, precipitation filter residue anhydrous alcohol solution refilters and removes insolubles, and the ethanolic soln that filters gained obtains ethanol extract after concentrating; Ethanol extract is joined in the pyrosulphite salts solution, 80～100 ℃ of reactions down, after reaction is finished reaction solution is poured in the mixture of ice and water, after crystallization, filtration, washing, drying, namely; Described pyrosulfite add-on is 1～3 times of vine tea quality, and wherein, the mass content of pyrosulfite is 10～40% in the pyrosulphite salts solution.
2. the method for claim 1 is characterized in that, described pyrosulfite comprises in potassium pyrosulfite, Sodium Pyrosulfite, the ammonium pyrosulfite one or more.
3. the method for claim 1 is characterized in that, ethanol extract is joined in the pyrosulphite salts solution, and the time of reaction is 4～8h down at 80～100 ℃.
4. the method for claim 1 is characterized in that, the vine tea powder: the solid-liquid ratio of hot water is 1:20～40, and unit is g/mL.
5. method as claimed in claim 4 is characterized in that, the lixiviate number of times is 2～4 times, and each extraction time is 0.5～2h.
6. the method for claim 1 is characterized in that, filtrate is concentrated to 1/4～2/5 of former filtrate volume; Ethanolic soln is concentrated into 1/4～2/5 of former volumes of aqueous ethanol after concentrating.
7. as each described method of claim 1～6, it is characterized in that, use the frozen water repetitive scrubbing after the ampelopsin crystal filtering separation of gained is come out behind the crystallization.
8. the application of pyrosulfite is characterized in that, agent is applied to dibydro myricetrin in the vine tea and transforms to the dehydrogenation of ampelopsin as dehydrogenation oxidation with pyrosulfite.
9. application as claimed in claim 8 is characterized in that, described pyrosulfite comprises in potassium pyrosulfite, Sodium Pyrosulfite, the ammonium pyrosulfite one or more.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586409A (en) * | 2018-04-12 | 2018-09-28 | 铜仁学院 | A kind of preparation method being converted into myricetin with efficient dihydromyricetin |
| CN111903812A (en) * | 2020-07-20 | 2020-11-10 | 上海中医药大学 | Instant strawberry tea extract, preparation method and application thereof |
| WO2021068501A1 (en) * | 2019-10-12 | 2021-04-15 | 宋昆元 | Method for synthesizing myricetin |
| CN112851614A (en) * | 2020-12-28 | 2021-05-28 | 江苏天晟药业股份有限公司 | Preparation method of myricetin |
Citations (4)
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| CN1887881A (en) * | 2006-07-20 | 2007-01-03 | 广西中医学院 | Myricitrin preparing process |
| WO2008111796A1 (en) * | 2007-03-12 | 2008-09-18 | Sungkyunkwan University Foundation For Corporate Collaboration | Polyphenol compounds with modulating neurotransmitter release |
| CN102532329A (en) * | 2010-12-29 | 2012-07-04 | 天津市轻工业化学研究所 | Preparation method of low-viscosity octenyl succinic anhydride modified starch |
| CN102584766A (en) * | 2011-12-31 | 2012-07-18 | 郁建平 | Method for simultaneously separating dihydromyricetin and myricetin from ampelopsis plant |
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2013
- 2013-05-21 CN CN201310189757.5A patent/CN103275049B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887881A (en) * | 2006-07-20 | 2007-01-03 | 广西中医学院 | Myricitrin preparing process |
| WO2008111796A1 (en) * | 2007-03-12 | 2008-09-18 | Sungkyunkwan University Foundation For Corporate Collaboration | Polyphenol compounds with modulating neurotransmitter release |
| CN102532329A (en) * | 2010-12-29 | 2012-07-04 | 天津市轻工业化学研究所 | Preparation method of low-viscosity octenyl succinic anhydride modified starch |
| CN102584766A (en) * | 2011-12-31 | 2012-07-18 | 郁建平 | Method for simultaneously separating dihydromyricetin and myricetin from ampelopsis plant |
Non-Patent Citations (1)
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| 李卫等: "逆流法提取二氢杨梅素研究", 《食品科学》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586409A (en) * | 2018-04-12 | 2018-09-28 | 铜仁学院 | A kind of preparation method being converted into myricetin with efficient dihydromyricetin |
| WO2021068501A1 (en) * | 2019-10-12 | 2021-04-15 | 宋昆元 | Method for synthesizing myricetin |
| US11773073B2 (en) | 2019-10-12 | 2023-10-03 | Shanghai Yinsheng Consulting Corporation (Limited Liability Partnership) | Method for synthesizing myricetin |
| CN111903812A (en) * | 2020-07-20 | 2020-11-10 | 上海中医药大学 | Instant strawberry tea extract, preparation method and application thereof |
| CN112851614A (en) * | 2020-12-28 | 2021-05-28 | 江苏天晟药业股份有限公司 | Preparation method of myricetin |
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