CN109180759B - Method for separating and purifying formononetin from liquorice waste residue - Google Patents
Method for separating and purifying formononetin from liquorice waste residue Download PDFInfo
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- CN109180759B CN109180759B CN201811241989.XA CN201811241989A CN109180759B CN 109180759 B CN109180759 B CN 109180759B CN 201811241989 A CN201811241989 A CN 201811241989A CN 109180759 B CN109180759 B CN 109180759B
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- 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
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Abstract
The invention relates to the technical field of medicine extraction, and discloses a method for separating and purifying formononetin from liquorice waste residue. Adding a first solvent into the waste residue of the liquorice for reflux extraction, filtering, adding hydrogen peroxide into filtrate for oxidation, concentrating, adding silica gel into the obtained enriched substance for adsorption, drying to obtain formononetin adsorption silica gel, adding a second solvent, stirring, filtering, concentrating and drying the obtained filtrate to obtain a crude product of the formononetin; adding solvent III into the crude product, heating and refluxing to completely dissolve, cooling and crystallizing to obtain a pure product. According to the method, tetrahydrofuran and other suitable solvents form a solvent system for separating and purifying the formononetin, a hydrogen peroxide oxidation link is added, the preparation process of the formononetin with higher purity and yield is realized through a simple and effective solvent extraction process, the requirements on equipment and reagents are low, the used reagents are common and easy to obtain, the equipment is simple, the process is easy to realize standardization and automation, and industrial production can be realized.
Description
Technical Field
The invention relates to the technical field of medicine extraction, and particularly relates to a method for separating and purifying formononetin from liquorice waste residue.
Background
The effective components of Glycyrrhrizae radix are triterpenes, flavonoids and polysaccharides. Wherein, the formononetin is a monomer compound of licorice flavonoids, and the structural formula is as follows:
studies show that the formononetin is used as one of licoflavone, and has multiple effects: (1) CN104107184A discloses that formononetin can obviously resist potassium chloride induced rat arterial contraction ring, has vasodilatation effect, and can be used for preparing vasodilatation medicine. (2) CN106336438A discloses that succinylformononetin, a derivative thereof, can be used in the aspect of cardiovascular disease medicines, in particular to the preparation of anti-myocardial ischemia medicines. (3) Studies of Zhang Wei et al find that the formononetin can inhibit the growth of pathogenic bacteria enterococcus and enterobacteria and promote the growth of beneficial bifidobacteria and lactobacilli.
The reports of preparing the formononetin from the liquorice waste residue are less: (1) cold crystallization, etc. using licorice decoction pieces as material, reflux extracting with 95% alcohol, and extracting the concentrated liquid with petroleum ether, ethyl acetate and n-butanol successively. Wherein the n-butanol fraction is subjected to silica gel column chromatography, gradient elution is carried out with dichloromethane-methanol at different ratios (100: 1 → 0: 1), and after thin layer chromatography analysis, the fraction is further separated and purified by multiple medium pressure silica gel column chromatography, ODS column chromatography, high performance liquid preparative chromatography and other means to obtain formononetin; (2) yuanqiang, etc. is reflux extracted with 70% ethanol, the obtained extract is dissolved in hot water, and petroleum ether and ethyl acetate are used for extraction in sequence. Wherein the extract obtained by ethyl acetate extraction is treated by polyamide resin, and then is further separated by high-speed counter-current chromatography to prepare the formononetin. (3) Zhangjie et al use Glycyrrhrizae radix as raw material, reflux-extract with 70% methanol, dissolve concentrated solution with warm water, sequentially extract with petroleum ether-ethyl acetate (1:1) and n-butanol, wherein n-butanol extract is subjected to silica gel column chromatography, specific fraction is subjected to Sephadex LH-20, liquid phase preparation and recrystallization to obtain formononetin.
In conclusion, the several methods for preparing the formononetin provide good reference for separating and purifying the formononetin. However, the existing technology has the defects of long time consumption, high requirement on equipment, high production cost, complicated steps, insufficient and effective utilization of raw materials, incapability of realizing industrial production and the like.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for separating and purifying formononetin from licorice waste residue, so that the method of the present invention can obtain high yield and high purity of formononetin from licorice waste residue by a simple and easy process.
The invention also aims to provide a method for separating and purifying the formononetin from the liquorice waste residue, so that the high-purity finished product of more than 92 percent of the crude product of the formononetin can be obtained only by one-time recrystallization.
In order to achieve the above purpose, the invention provides the following technical scheme:
a method for separating and purifying formononetin from waste residue of liquorice comprises the following steps:
step 1, adding a first solvent into the waste residue of the liquorice for reflux extraction, filtering, adding hydrogen peroxide into filtrate to oxidize impurities, and concentrating to obtain an formononetin enrichment substance;
step 3, adding a solvent III into the crude product of the formononetin, heating and refluxing until the crude product is completely dissolved, cooling and crystallizing to obtain a pure product of the formononetin;
wherein, the first solvent is tetrahydrofuran or a mixed solvent of tetrahydrofuran and alkane;
the second solvent is selected from one or more than two of acetonitrile and chlorinated hydrocarbon solvents;
the third solvent is a mixed solvent of water and any one of methanol, ethanol and isopropanol.
Aiming at the problems that the existing process for extracting and separating the formononetin from the waste residue of the liquorice is generally complicated and complex and has low purity and yield, the invention takes tetrahydrofuran as a main extraction solvent for enrichment, and simultaneously uses hydrogen peroxide to oxidize impurities, so that the structural properties of the oxidized impurities are changed, the impurities are easy to separate from the product, and the purposes of oxidizing the impurities and retaining the target formononetin can be achieved; finally, the proper solvent combination is used for carrying out coarse crystallization and recrystallization, so that the aim of obtaining the formononetin with high yield and high purity by a simple process is fulfilled.
Among them, the alkane is preferably one or more of pentane, hexane, heptane and nonane, and pentane or heptane can be selected in the specific embodiment of the invention;
preferably, the volume ratio of tetrahydrofuran to alkane is 1 (1-5), more preferably 1: (2-4); in a specific embodiment of the invention, the volume ratio of tetrahydrofuran to alkane is 1:2, 1:3 or 1: 4.
Preferably, the mass volume ratio of the licorice waste residue to the solvent I is 1g (1-30) mL (namely 1-30mL of the solvent I is added into 1g of the licorice waste residue, and the ratio can be converted into any form in equal proportion), more preferably 1g: (10-20) mL; in a specific embodiment of the invention, the mass-to-volume ratio of the licorice waste residue to the first solvent is 1:10, 1:15 or 1: 20. Preferably, the reflux extraction time in the step 1 is 0.5-2.5 h.
Preferably, the mass percentage concentration of the hydrogen peroxide in the filtrate in the step 1 is 0.1-0.5%, and more preferably 0.2-0.4%; in a specific embodiment of the present invention, the concentration of the hydrogen peroxide in the filtrate in step 1 is 0.1%, 0.2%, 0.3%, 0.4% or 0.5%. In a specific embodiment of the invention, the oxidizing impurities are oxidized at 30-60 ℃ for 3-6 h; more specifically, the oxidized impurities are oxidized at 30-45 ℃ for 3-6 h.
Preferably, the mass ratio of the enriched substance to the silica gel is 1 (3-10), more preferably 1: (5-8); in a specific embodiment of the invention, the mass ratio of the concentrate to the silica gel is 1:5, 1:6 or 1: 8.
Preferably, the chlorinated hydrocarbon solvent includes dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, chlorobutane and chlorobenzene; in a specific embodiment of the invention, the second solvent can be selected from acetonitrile and any one of the chlorinated hydrocarbon solvents for use in combination, and the volume ratio of the acetonitrile to the chlorinated hydrocarbon solvent is acetonitrile: chlorinated hydrocarbons ═ 1-10: (1-10), more preferably (3-5): 1; in a specific embodiment of the invention, the acetonitrile: a chlorinated hydrocarbon is 3:1, 4:1 or 5: 1; more specifically, the second solvent is a mixture of acetonitrile and dichloromethane, a mixture of acetonitrile and trichloromethane or a mixture of acetonitrile and chloroform;
preferably, the volume usage amount of the second solvent is 5-20 times of that of the formononetin adsorption silica gel, and more preferably 5-15 times; in a specific embodiment of the invention, the volume usage amount of the second solvent is 5 times, 10 times or 15 times of that of the formononetin adsorption silica gel.
Preferably, the volume consumption of the solvent III is 1-10 times of that of the crude product of the formononetin; in a specific embodiment of the invention, the volume of the solvent III is 5 times of that of the crude product of the formononetin.
Preferably, the volume percentage of methanol, ethanol or isopropanol to water in the solvent III is 1:99-99:1, and more preferably 20:80-30: 70.
Preferably, the cooling crystallization time is 1-20h, more preferably 10-20 h; in the specific embodiment of the invention, the cooling crystallization time is 10h, 15h or 20 h.
In the comparative experiments of the invention on different extraction solvents, the results show that higher yield and purity of the formononetin enrichment can be simultaneously realized only under the oxidation of the first solvent and hydrogen peroxide. Meanwhile, the invention unexpectedly discovers through comparative experiments that the second solvent influences the recrystallization times and purity of the third solvent, and related experiments prove that under the condition of the combination of the second solvent and the third solvent defined by the invention, the purity of more than 92 percent can be achieved by only one recrystallization, but other conventional solvent combinations cannot achieve the excellent effect.
According to the technical scheme, the solvent system for separating and purifying the formononetin is formed by tetrahydrofuran and other suitable solvents, the step of oxidizing hydrogen peroxide is added, the preparation process of the formononetin with higher purity and yield is realized through a simple and effective solvent extraction process, the whole method has low requirements on equipment and reagents, the used reagents are common and easy to obtain, the equipment is simple, the process is easy to realize standardization and automation, and industrial production can be realized.
Drawings
FIG. 1 shows a map of a reference for the detection of formononetin;
FIG. 2 shows the profile of the formononetin detection sample.
Detailed Description
The invention discloses a method for separating and purifying formononetin from liquorice waste residue, and a person skilled in the art can use the content for reference and appropriately improve process parameters to realize the method. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications of the methods described herein, as well as appropriate variations and combinations of the methods described herein, may be made to implement and use the techniques of the present invention without departing from the spirit and scope of the invention.
In the invention, the licorice waste residue is a leftover in the production process of preparing monoammonium salt from glycyrrhizic acid powder.
In the comparative tests of the specific examples, the process conditions were kept consistent for the different treatment groups except for the differences that should be observed.
The method for separating and purifying formononetin from waste residue of licorice provided by the present invention is further described below.
Example 1: the method of the invention
(1) Extraction: weighing the waste residue of liquorice, adding a mixed solution of tetrahydrofuran-pentane (1:2) in an amount which is 20 times that of the waste residue, carrying out reflux extraction for 1 hour, filtering, adding hydrogen peroxide to enable the concentration of the hydrogen peroxide to be 0.4%, oxidizing for 3 hours at 45 ℃, concentrating to obtain an formononetin enrichment, adding silica gel in an amount which is 8 times that of the enrichment, adsorbing, and drying for later use.
(2) And (3) purification: adding 5 times of acetonitrile/dichloromethane (5:1) into the formononetin adsorption silica gel obtained in the step (1), stirring, filtering to obtain filtrate, concentrating and drying the filtrate to obtain a crude product of the formononetin, adding 5 times of 30% isopropanol aqueous solution (the volume ratio of isopropanol to water is 30:70) into the crude product, heating, refluxing and dissolving, cooling for 20 hours, crystallizing, filtering and drying to obtain white solid formononetin, wherein the purity is 95.6%, and the weight yield is 0.41%.
The product is identified as formononetin by HPLC, as shown in figure 1 and figure 2.
Example 2: the method of the invention
(1) Extraction: weighing the waste residue of liquorice, adding 15 times of mixed solution of tetrahydrofuran-pentane (1:4), carrying out reflux extraction for 0.5h, filtering, adding hydrogen peroxide to enable the concentration to be 0.2%, oxidizing for 5h at 30 ℃, concentrating to obtain an formononetin enrichment, adding 5 times of silica gel by weight into the enrichment to adsorb, and drying for later use.
(2) And (3) purification: adding 5 times of acetonitrile/dichloromethane (4:1) into the formononetin adsorption silica gel obtained in the step (1), stirring, filtering to obtain filtrate, concentrating and drying the filtrate to obtain a crude product of the formononetin, adding 5 times of 20% methanol aqueous solution (methanol: water volume ratio is 20:80) into the crude product, heating, refluxing and dissolving, cooling for 10 hours, crystallizing, filtering and drying to obtain white solid formononetin, wherein the purity is 94.6%, and the weight yield is 0.4%.
The product was identified as formononetin by HPLC, and the spectrum was in accordance with FIG. 2.
Example 3: the method of the invention
(1) Extraction: weighing the waste residue of liquorice, adding 10 times of mixed solution of tetrahydrofuran-heptane (1:3), extracting under reflux for 1h, filtering, adding hydrogen peroxide to make the concentration of the hydrogen peroxide 0.3%, oxidizing at 30 ℃ for 3h, concentrating to obtain an formononetin enrichment, adding 8 times of silica gel to the enrichment for adsorption, and drying for later use.
(2) And (3) purification: adding 10 times of acetonitrile/chloroform (5:1) into the formononetin adsorption silica gel obtained in the step (1), stirring, filtering to obtain filtrate, concentrating and drying the filtrate to obtain a crude product of the formononetin, adding 5 times of 25% isopropanol water solution (the volume ratio of isopropanol to water is 25:75) into the crude product, heating, refluxing and dissolving, cooling for 10 hours, crystallizing, filtering and drying to obtain white solid formononetin, wherein the purity is 95.1%, and the weight yield is 0.39%.
The product was identified as formononetin by HPLC, and the spectrum was in accordance with FIG. 2.
Example 4: the method of the invention
(1) Extraction: weighing the waste residue of liquorice, adding 10 times of mixed solution of tetrahydrofuran-pentane (1:3), extracting under reflux for 1h, filtering, adding hydrogen peroxide to make the concentration of the hydrogen peroxide 0.2%, oxidizing for 6h at 30 ℃, concentrating to obtain an formononetin enrichment, adding 6 times of silica gel by weight into the enrichment to adsorb, and drying for later use.
(2) And (3) purification: adding 15 times of acetonitrile/chloroform (3:1) into the formononetin adsorption silica gel obtained in the step (1), stirring, filtering to obtain a filtrate, concentrating and drying the filtrate to obtain a crude product of the formononetin, adding 5 times of 20% ethanol aqueous solution (isopropanol: water volume ratio is 20:80) into the crude product, heating, refluxing and dissolving, cooling for 15 hours, crystallizing, filtering and drying to obtain white solid formononetin, wherein the purity is 96.3%, and the weight yield is 0.33%.
The product was identified as formononetin by HPLC, and the spectrum was in accordance with FIG. 2.
Example 5: influence of different solvent extraction on extraction rate and purity of formononetin enrichment
Referring to the method of step 1 in example 1, different solvents were used for enrichment, and the extraction rate and the enriched product purity were counted, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the extraction with the solvent I of the present invention in combination with hydrogen peroxide has significant advantages over the conventional solvent extraction, both in extraction yield and in formononetin purity.
Example 6: influence of different solvent purification on recrystallization times and purity of pure formononetin product
Referring to the method of example 1, except that the solvent No. two and the solvent No. three were different, the number of recrystallization times required to achieve higher purity of the pure product was verified, and the results are shown in Table 2.
TABLE 2
As can be seen from Table 2, after the second solvent and the third solvent defined by the invention are purified, the purity of the crude product of the formononetin can directly reach more than 60% by one-time purification, and the purity of the crude product of the formononetin can not reach 60% by other solvents; in addition, after the crystal is crystallized once by using a third solvent, the invention can ensure that the purity of the formononetin can directly reach more than 92 percent; and the purity of other solvents still does not reach more than 90 percent after repeated recrystallization, and the highest purity is 85 percent.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A method for separating and purifying formononetin from licorice waste residue is characterized by comprising the following steps:
step 1, adding a first solvent into the waste residue of the liquorice for reflux extraction, filtering, adding hydrogen peroxide into filtrate to oxidize impurities, and concentrating to obtain an formononetin enrichment substance;
step 2, adding silica gel into the enriched substance for adsorption, drying to obtain formononetin adsorption silica gel, then adding a second solvent, stirring, filtering, concentrating and drying the obtained filtrate to obtain a crude product of the formononetin;
step 3, adding a solvent III into the crude product of the formononetin, heating and refluxing until the crude product is completely dissolved, cooling and crystallizing to obtain a pure product of the formononetin;
wherein, the first solvent is tetrahydrofuran or a mixed solvent of tetrahydrofuran and alkane, and the alkane is one or more than two of pentane, hexane, heptane and nonane; the volume ratio of tetrahydrofuran to alkane is 1 (1-5), the mass ratio of the licorice waste residue to the first solvent is 1 (1-30), and the mass percentage concentration of hydrogen peroxide in the filtrate in the step 1 is 0.1-0.5%;
the second solvent is selected from one or more than two of acetonitrile and chlorinated hydrocarbon solvents;
the third solvent is a mixed solvent of any one of methanol, ethanol and isopropanol and water;
the waste licorice residue is a leftover in the production process of preparing monoammonium salt from glycyrrhizic acid powder.
2. The method of claim 1, wherein the chlorinated hydrocarbon solvent comprises dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, chlorobutane, and chlorobenzene.
3. The method of claim 1, wherein the mass ratio of the concentrate to the silica gel is 1 (3-10).
4. The method as claimed in claim 1, wherein the second solvent is used in an amount of 5-20 times by volume of the formononetin-adsorbing silica gel.
5. The method as claimed in claim 1, wherein the amount of the solvent III is 1-10 times of the amount of the crude product of formononetin.
6. The method according to claim 1, wherein the volume percentage of methanol, ethanol or isopropanol to water in the solvent III is 1:99-99: 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU727199A1 (en) * | 1978-05-03 | 1980-04-15 | Харьковский государственный фармацевтический институт | Ononine producing method |
| CN105753917A (en) * | 2016-04-14 | 2016-07-13 | 青海省青海湖药业有限公司 | Separating purifying method of liquiritin |
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2018
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU727199A1 (en) * | 1978-05-03 | 1980-04-15 | Харьковский государственный фармацевтический институт | Ononine producing method |
| CN105753917A (en) * | 2016-04-14 | 2016-07-13 | 青海省青海湖药业有限公司 | Separating purifying method of liquiritin |
Non-Patent Citations (2)
| Title |
|---|
| 甘草化学成分研究;刘育辰，等;《药物分析杂志》;20111231;第31卷(第7期);第1251-1255页 * |
| 甘草根和根茎的化学成分研究;张杰，等;《中国药业》;20170620;第26卷(第12期);第16、18页 * |
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Denomination of invention: A kind of method for separating and purifying formononetin from licorice waste residue Effective date of registration: 20220920 Granted publication date: 20201201 Pledgee: Qinghai Beili licorice Technology Development Co.,Ltd. Pledgor: QINGHAI LAKE PHARMACEUTICAL CO.,LTD. Registration number: Y2022630000003 |