CN106928290B - Preparation method of high-content rutin - Google Patents

Preparation method of high-content rutin Download PDF

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CN106928290B
CN106928290B CN201710119884.6A CN201710119884A CN106928290B CN 106928290 B CN106928290 B CN 106928290B CN 201710119884 A CN201710119884 A CN 201710119884A CN 106928290 B CN106928290 B CN 106928290B
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rutin
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suction filtration
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alkali
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CN106928290A (en
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姜玉钦
曹晓慧
穆开蕊
张丹丹
张玮玮
徐桂清
李伟
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Henan Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
    • C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
    • C07H17/06—Benzopyran radicals
    • C07H17/065—Benzo[b]pyrans
    • C07H17/07—Benzo[b]pyran-4-ones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C07H1/06—Separation; Purification

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Abstract

The invention discloses a preparation method of high-content rutin, and belongs to the technical field of pharmaceutical chemistry. The technical scheme provided by the invention has the key points that: a preparation method of high-content rutin comprises the following specific steps: dissolving crude rutin in aqueous solution of alkali; heating to dissolve, adding diatomite for adsorption, and performing suction filtration while the solution is hot; adjusting the pH value of the filtrate to 3-7 by using an acid solution; cooling, standing and crystallizing; and carrying out suction filtration to obtain high-content rutin. The invention adopts water as solvent, thus being green and environment-friendly; the purity of the obtained rutin can reach more than 99.0 percent; the yield of rutin obtained by the method is high, the stability is kept at 93-96%, the cost for producing rutin is far lower than the production cost of high-content rutin in reported patents and documents, and the method is suitable for industrial application.

Description

Preparation method of high-content rutin
Technical Field
The invention belongs to the technical field of pharmaceutical chemistry, and particularly relates to a preparation method of high-content rutin.
Background
Rutin (Rutin) is called Rutin or Rutin, vitamin P, and is yellow or yellowish green powder or superfine microneedle crystal; no odor and no taste; easily go bad when exposed to light, gradually darken in air, and have a molecular formula of C27H30O16CAS number 153-18-4, molecular weight 610.51, melting point 190-:
Figure DEST_PATH_IMAGE002
rutin is a flavonoid compound with wide sources, has the effects of reducing the permeability and brittleness of capillary vessels, and can maintain and restore the normal elasticity of the capillary vessels; clinically used for preventing and treating cerebral hemorrhage, hypertension, diabetes, retinal hemorrhage, purpura, acute hemorrhagic nephritis, etc.; can also be used as food antioxidant and pigment; the natural sun-screening agent has good radiation-resistant and free radical-resistant effects on skin and extremely strong absorption effect on ultraviolet rays and X rays, and is used as a natural sun-screening agent, 10wt% of rutin is added, and the absorption rate of the ultraviolet rays is as high as 98%; has obvious effect of eliminating active oxygen free radicals of cells. In the domestic and foreign medical industry, rutin is used as a raw material to produce rutin tablets, troxerutin, rutin magnesium chromium salt, vitamin D-hydroxy-butyl-rutin, quercetin and other medicines, so that the application range and the market of the rutin are expanded.
Rutin is easily soluble in boiling methanol, soluble in hot ethanol and alkaline solution, slightly soluble in hot water and cold methanol, and insoluble in cold water, ethanol, chloroform, petroleum ether, acetone and ethyl acetate. Rutin is widely contained in flos Sophorae Immaturus (flower bud of flos Sophorae), semen Fagopyri Esculenti, herba Cymbopogonis, fructus Hippophae, fructus crataegi, folium Eucalypti Globueli and tobacco leaf, wherein the content of flos Sophorae Immaturus, semen Fagopyri Esculenti and folium Eucalypti Globueli is the highest, and can be used as raw material for extracting rutin. In addition, it is also found in ilex pubescens of Aquifoliaceae, forsythia suspensa of Oleaceae, sophorae fructus of Leguminosae, tobacco, jujube, apricot, orange peel, tomato, etc.
At present, the rutin in China is mainly extracted by taking sophora flower buds as raw materials. Because rutin is easily dissolved in alkali liquor and is separated out after acid is added, rutin is extracted in laboratory and enterprise production by a common alkali extraction and acid precipitation method. Because a large amount of flavonoid substances exist in the sophora flower bud and the structure of the sophora flower bud is similar to that of rutin, the rutin content is difficult to reach high by a conventional rutin extraction method, the HPLC content is generally 90-95%, the quality of rutin raw material medicines and the quality of troxerutin prepared by taking rutin as a raw material are influenced by the existence of impurities in crude rutin, and the preparation of high-content rutin is particularly important.
The rutin refining method comprises the following steps: (1) zhaowen, et al reported the molecular size separation method, which comprises dissolving rutin in methanol, adding into the top of Sephadex column, eluting with methanol, collecting methanol solution, concentrating, and crystallizing. The principle is that the macromolecules can not enter the sephadex, so that the macromolecules are eluted firstly, and the micromolecules are eluted later, so that components with different molecular sizes are separated. (2) Quqianzhi et al reported that rutin was dissolved in alcohol at room temperature, filtered, the filtrate was crystallized by standing, and the mother liquor was concentrated and then crystallized again to obtain high-content rutin. The method converts two-dimensional planar structure of rutin into three-dimensional structure, facilitates solvent molecule entry, increases solubility, and can remove impurities dissolved in alcohol after heating. (3) Shenhong et al report that rutin is purified by deproteinization using trichloroacetic acid method and deproteinization using improved Sevage method, the method is simple to operate and labor-saving, but the reagent used is highly toxic and has a purity of only 90%, which is difficult to meet the current demand for high-content rutin. (4) The report of the Qianlouhua and the like adopts high-speed counter-current chromatography to refine the high-purity rutin, and is characterized in that a water-containing and multi-component organic solvent system is adopted, and the characteristics of non-irreversible adsorption, high recovery rate and high separation efficiency of the high-speed counter-current chromatography are utilized to refine the high-purity rutin to obtain the high-content rutin. The purity of the rutin prepared by the method can reach more than 98 percent, but various organic solvents are used, so the method has certain influence on the environment, and meanwhile, the preparation is only gram-order, the cost is higher, and the method is not beneficial to industrial production. (5) The method is characterized in that rutin is refined by resin column chromatography, and the obtained rutin is rinsed with deionized water and dried for 10-14 h at 80-90 ℃, so that partial rutin is easily oxidized or decomposed when the rutin is dried at a higher temperature for a long time, especially in the presence of air or illumination, and certain defects exist.
In the prior report, the method for refining rutin with the purity of more than 98 percent needs chromatography, or has complicated operation; or excessive toxic organic solvent is adopted, which is not beneficial to environmental protection; or high cost, which is not suitable for industrialization.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of high-content rutin, tests show that diatomite has better adsorption capacity on rutin impurities and better effect than adsorption reagents such as active carbon, hydroxyapatite and the like, and the rutin prepared by the method has the advantages of high yield, high purity, simple and convenient steps, low cost, economy, environmental protection, suitability for industrialization and the like, and is a refining method with industrial production value.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the high-content rutin is characterized by comprising the following specific steps:
(1) dissolving crude rutin in aqueous solution of alkali;
(2) heating to dissolve, adding diatomite for adsorption, and performing suction filtration while the solution is hot;
(3) adjusting the pH value of the filtrate to 3-7 by using an acid solution;
(4) cooling, standing and crystallizing;
(5) and carrying out suction filtration to obtain high-content rutin.
Further preferably, the crude rutin in step (1) is common rutin sold in the market, and the HPLC content is 92-95%.
Further preferably, the base in step (1) is one or more of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide or potassium ethoxide.
Further preferably, the ratio of the volume of the water in the aqueous solution of the alkali to the crude rutin in the step (1) is 15-25L: 1 Kg, and the molar ratio of the alkali to the crude rutin in the aqueous solution of the alkali is 0.5-2: 1.
Further preferably, the heating temperature in the heating and dissolving process in the step (2) is 60 to 100 ℃.
Further preferably, the dosage of the diatomite in the step (2) is 2-10% of the mass of the crude rutin.
Further preferably, the acid solution in step (3) is one or more of hydrochloric acid, sulfuric acid, nitric acid or acetic acid.
Compared with the prior art, the invention has the following advantages: the invention adopts water as solvent, thus being green and environment-friendly; the purity of the obtained rutin can reach more than 99.0 percent; the yield of rutin obtained by the method is high, the stability is kept at 93-96%, the cost for producing rutin is far lower than the production cost of high-content rutin in reported patents and documents, and the method is suitable for industrial application.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
264 g (6.6 mol) of sodium hydroxide is added into 30L of distilled water, stirred and dissolved, then 2 Kg (3.3mol) of crude rutin is added, 90 is stirred and dissolved, 100 g of diatomite is added, and the clear filtrate is obtained by suction filtration while the solution is hot. The filtrate was adjusted to pH 5.0 with hydrochloric acid. Slowly cooling to room temperature, controlling the cooling time at 3 h, standing at room temperature for 4 h, performing suction filtration, leaching a filter cake with 4L of water, wherein the yield is 95.1%, and the purity is 99.0%.
Example 2
Adding 185 g (3.3mol) of potassium hydroxide into 40L of distilled water, stirring for dissolving, adding 2 Kg (3.3mol) of crude rutin, stirring for dissolving at 80 ℃, adding 160 g of diatomite, and performing suction filtration while hot to obtain clear filtrate. The filtrate was adjusted to pH 5.0 with hydrochloric acid. Slowly cooling to room temperature, controlling the cooling time at 3 h, standing at room temperature for 4 h, performing suction filtration, leaching a filter cake with 14L of water, wherein the yield is 95.2%, and the purity is 99.2%.
Example 3
Adding 132 g (3.3mol) of sodium hydroxide into 50L of distilled water, stirring for dissolving, adding 2 Kg (3.3mol) of crude rutin, stirring at 100 ℃ for dissolving, adding 40 g of diatomite, and performing suction filtration while hot to obtain clear filtrate. The filtrate was adjusted to pH 3.0 with nitric acid. Slowly cooling to room temperature, controlling the cooling time at 3 h, standing for 4 h at room temperature, performing suction filtration, leaching the filter cake with 20L of water, wherein the yield is 94.3%, and the purity is 99.3%.
Example 4
265 g (4.9 mol) of sodium methoxide is added into 40L of distilled water, stirred and dissolved, then 2 Kg (3.3mol) of crude rutin is added, stirred at 75 ℃ until dissolved, 200 g of diatomite is added, and the clear filtrate is obtained by suction filtration while the solution is hot. The filtrate was adjusted to pH 7.0 with hydrochloric acid. Slowly cooling to room temperature, controlling the cooling time at 3 h, standing for 4 h at room temperature, performing suction filtration, leaching a filter cake with 14L of water, wherein the yield is 95.0%, and the purity is 99.8%.
Example 5
198 g (4.9 mol) of sodium hydroxide is added into 30L of distilled water, stirred and dissolved, then 2 Kg (3.3mol) of crude rutin is added, stirred and dissolved at 90 ℃, 160 g of diatomite is added, and the clear filtrate is obtained by suction filtration while the solution is hot. The filtrate was adjusted to pH 6.0 with hydrochloric acid. Slowly cooling to room temperature, controlling the cooling time at 3 h, standing for 4 h at room temperature, performing suction filtration, leaching a filter cake with 10L of water, wherein the yield is 94.8%, and the purity is 99.3%.
Example 6
264 g (6.6 mol) of sodium hydroxide is added into 40L of distilled water, stirred and dissolved, then 2 Kg (3.3mol) of crude rutin is added, stirred at 100 ℃ until dissolved, 160 g of diatomite is added, and the clear filtrate is obtained by suction filtration while the solution is hot. The filtrate was adjusted to pH 5.0 with sulfuric acid. Slowly cooling to room temperature, controlling the cooling time at 3 h, standing for 4 h at room temperature, performing suction filtration, leaching a filter cake with 10L of water, wherein the yield is 93.1%, and the purity is 99.2%.
Example 7
Adding 66 g (1.6 mol) of sodium hydroxide into 50L of distilled water, stirring for dissolving, adding 2 Kg (3.3mol) of crude rutin, stirring for dissolving at 60 ℃, adding 200 g of diatomite, and performing suction filtration while hot to obtain clear filtrate. The filtrate was adjusted to pH 6.0 with acetic acid. Slowly cooling to room temperature, controlling the cooling time at 3 h, standing for 4 h at room temperature, performing suction filtration, leaching a filter cake with 20L of water, wherein the yield is 93.9%, and the purity is 99.1%.
Example 8
198 g (4.9 mol) of sodium hydroxide is added into 40L of distilled water, stirred and dissolved, then 2 Kg (3.3mol) of crude rutin is added, stirred and dissolved at 60 ℃, 100 g of diatomite is added, and the clear filtrate is obtained by suction filtration while the solution is hot. The filtrate was adjusted to pH 5.0 with hydrochloric acid. Slowly cooling to room temperature, controlling the cooling time at 3 h, standing for 4 h at room temperature, performing suction filtration, leaching a filter cake with 20L of water, wherein the yield is 94.8%, and the purity is 99.4%.
Example 9
Adding 264 g (6.6 mol) of sodium hydroxide into 50L of distilled water, stirring for dissolving, adding 2 Kg (3.3mol) of crude rutin, stirring at 90 ℃ for dissolving, adding 200 g of diatomite, and performing suction filtration while hot to obtain clear filtrate. The filtrate was adjusted to pH 6.0 with hydrochloric acid. Slowly cooling to room temperature, controlling the cooling time at 3 h, standing for 4 h at room temperature, performing suction filtration, leaching a filter cake with 20L of water, wherein the yield is 94.4%, and the purity is 99.8%.
Example 10
Adding 264 g (6.6 mol) of sodium hydroxide into 50L of distilled water, stirring for dissolving, adding 2 Kg (3.3mol) of crude rutin, stirring at 90 ℃ for dissolving, adding 200 g of activated carbon, and performing suction filtration while hot to obtain clear filtrate. The filtrate was adjusted to pH 6.0 with hydrochloric acid. Slowly cooling to room temperature, controlling the cooling time at 3 h, standing for 4 h at room temperature, performing suction filtration, leaching the filter cake with 20L of water, wherein the yield is 90.0%, and the purity is 94.2%.
Example 11
Adding 264 g (6.6 mol) of sodium hydroxide into 50L of distilled water, stirring for dissolving, adding 2 Kg (3.3mol) of crude rutin, stirring at 90 ℃ for dissolving, adding 200 g of hydroxyapatite, and performing suction filtration while hot to obtain clear filtrate. The filtrate was adjusted to pH 6.0 with nitric acid. Slowly cooling to room temperature, controlling the cooling time at 3 h, standing for 4 h at room temperature, performing suction filtration, leaching a filter cake with 20L of water, wherein the yield is 90.0%, and the purity is 93.5%.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.

Claims (1)

1. A preparation method of high-content rutin is characterized by comprising the following specific steps:
(1) dissolving crude rutin in an aqueous solution of alkali, wherein the crude rutin is commercially available common rutin, the HPLC content of the crude rutin is 92-95%, the alkali is one or more of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide or potassium ethoxide, the mass ratio of the volume of water in the aqueous solution of the alkali to the crude rutin is 15-25L: 1 Kg, and the molar ratio of the alkali in the aqueous solution of the alkali to the crude rutin is 0.5-2: 1;
(2) heating to dissolve, adding diatomite for adsorption, and performing suction filtration while the solution is hot, wherein the heating temperature in the heating and dissolving process is 60-100 ℃, and the dosage of the diatomite is 2-10% of the mass of the crude rutin;
(3) adjusting the pH value of the filtrate to 3-7 by using an acid solution, wherein the acid solution is one or more of hydrochloric acid, sulfuric acid, nitric acid or acetic acid;
(4) cooling, standing and crystallizing;
(5) high-content rutin is obtained by suction filtration, the purity of the obtained rutin can reach more than 99.0 percent, and the obtained rutin has higher yield and is stably kept between 93 and 96 percent.
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Publication number Priority date Publication date Assignee Title
CN108329369B (en) * 2018-04-08 2021-02-12 河南师范大学 Preparation method of high-content rutin
CN115010776B (en) * 2022-06-24 2024-04-19 山西助潞腾飞数智科技有限公司 Extraction method of tartary buckwheat rutin

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1410423A (en) * 2001-09-28 2003-04-16 张杰克 Technical method of extracting rutin
CN101045720A (en) * 2007-03-20 2007-10-03 陕西师范大学 Method for extracting buckwheat flavone from buckwheat shell
CN103833808A (en) * 2013-12-03 2014-06-04 西安应化生物技术有限公司 Method for extraction separation of rutin of tartary buckwheat
CN106397513A (en) * 2016-10-27 2017-02-15 广西禅方药业股份有限公司 Method for refining rutin having content more than or equal to 98%

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1410423A (en) * 2001-09-28 2003-04-16 张杰克 Technical method of extracting rutin
CN101045720A (en) * 2007-03-20 2007-10-03 陕西师范大学 Method for extracting buckwheat flavone from buckwheat shell
CN103833808A (en) * 2013-12-03 2014-06-04 西安应化生物技术有限公司 Method for extraction separation of rutin of tartary buckwheat
CN106397513A (en) * 2016-10-27 2017-02-15 广西禅方药业股份有限公司 Method for refining rutin having content more than or equal to 98%

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