CN116903575A - Method for separating and extracting licoxidine from plant liquorice - Google Patents
Method for separating and extracting licoxidine from plant liquorice Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 244000303040 Glycyrrhiza glabra Species 0.000 title abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000002904 solvent Substances 0.000 claims abstract description 48
- LPLVUJXQOOQHMX-QWBHMCJMSA-N glycyrrhizinic acid Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@@H]1C([C@H]2[C@]([C@@H]3[C@@]([C@@]4(CC[C@@]5(C)CC[C@@](C)(C[C@H]5C4=CC3=O)C(O)=O)C)(C)CC2)(C)CC1)(C)C)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O LPLVUJXQOOQHMX-QWBHMCJMSA-N 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000000047 product Substances 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- LPLVUJXQOOQHMX-UHFFFAOYSA-N glycyrrhetinic acid glycoside Natural products C1CC(C2C(C3(CCC4(C)CCC(C)(CC4C3=CC2=O)C(O)=O)C)(C)CC2)(C)C2C(C)(C)C1OC1OC(C(O)=O)C(O)C(O)C1OC1OC(C(O)=O)C(O)C(O)C1O LPLVUJXQOOQHMX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229960004949 glycyrrhizic acid Drugs 0.000 claims abstract description 30
- UYRUBYNTXSDKQT-UHFFFAOYSA-N glycyrrhizic acid Natural products CC1(C)C(CCC2(C)C1CCC3(C)C2C(=O)C=C4C5CC(C)(CCC5(C)CCC34C)C(=O)O)OC6OC(C(O)C(O)C6OC7OC(O)C(O)C(O)C7C(=O)O)C(=O)O UYRUBYNTXSDKQT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 235000019410 glycyrrhizin Nutrition 0.000 claims abstract description 30
- 239000004378 Glycyrrhizin Substances 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 238000002791 soaking Methods 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 24
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 0.000 claims abstract description 22
- 238000002425 crystallisation Methods 0.000 claims abstract description 22
- 229930003944 flavone Natural products 0.000 claims abstract description 22
- 150000002212 flavone derivatives Chemical class 0.000 claims abstract description 22
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- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000008025 crystallization Effects 0.000 claims abstract description 19
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- 238000003756 stirring Methods 0.000 claims abstract description 17
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- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000003480 eluent Substances 0.000 claims abstract description 9
- 238000000605 extraction Methods 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 53
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 51
- 235000006200 Glycyrrhiza glabra Nutrition 0.000 claims description 40
- 241000202807 Glycyrrhiza Species 0.000 claims description 33
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- 229940010454 licorice Drugs 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
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- 229910021641 deionized water Inorganic materials 0.000 claims description 24
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- 238000010828 elution Methods 0.000 claims description 11
- 238000011068 loading method Methods 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 238000007865 diluting Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 238000003809 water extraction Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 12
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- 239000012043 crude product Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 235000011477 liquorice Nutrition 0.000 description 14
- 238000004128 high performance liquid chromatography Methods 0.000 description 11
- 241000196324 Embryophyta Species 0.000 description 7
- -1 flavonoid compound Chemical class 0.000 description 7
- ZKLPARSLTMPFCP-UHFFFAOYSA-N Cetirizine Chemical compound C1CN(CCOCC(=O)O)CCN1C(C=1C=CC(Cl)=CC=1)C1=CC=CC=C1 ZKLPARSLTMPFCP-UHFFFAOYSA-N 0.000 description 6
- 229960001803 cetirizine Drugs 0.000 description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 6
- 229930003935 flavonoid Natural products 0.000 description 6
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- 238000000746 purification Methods 0.000 description 6
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- 230000000630 rising effect Effects 0.000 description 5
- VTAJIXDZFCRWBR-UHFFFAOYSA-N Licoricesaponin B2 Natural products C1C(C2C(C3(CCC4(C)CCC(C)(CC4C3=CC2)C(O)=O)C)(C)CC2)(C)C2C(C)(C)CC1OC1OC(C(O)=O)C(O)C(O)C1OC1OC(C(O)=O)C(O)C(O)C1O VTAJIXDZFCRWBR-UHFFFAOYSA-N 0.000 description 4
- 239000001685 glycyrrhizic acid Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 150000002215 flavonoids Chemical class 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 208000025721 COVID-19 Diseases 0.000 description 2
- 241000711573 Coronaviridae Species 0.000 description 2
- FURUXTVZLHCCNA-UHFFFAOYSA-N Liquiritigenin Natural products C1=CC(O)=CC=C1C1OC2=CC(O)=CC=C2C(=O)C1 FURUXTVZLHCCNA-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- HONIICLYMWZJFZ-UHFFFAOYSA-N azetidine Chemical compound C1CNC1 HONIICLYMWZJFZ-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- JBQATDIMBVLPRB-UHFFFAOYSA-N isoliquiritigenin Natural products OC1=CC(O)=CC=C1C1OC2=CC(O)=CC=C2C(=O)C1 JBQATDIMBVLPRB-UHFFFAOYSA-N 0.000 description 2
- FURUXTVZLHCCNA-AWEZNQCLSA-N liquiritigenin Chemical compound C1=CC(O)=CC=C1[C@H]1OC2=CC(O)=CC=C2C(=O)C1 FURUXTVZLHCCNA-AWEZNQCLSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- GSZUGBAEBARHAW-UHFFFAOYSA-N sophoraflavone B Natural products OC1C(O)C(O)C(CO)OC1OC1=CC=C(C=2OC3=CC(O)=CC=C3C(=O)C=2)C=C1 GSZUGBAEBARHAW-UHFFFAOYSA-N 0.000 description 2
- 241001251200 Agelas Species 0.000 description 1
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- 206010052360 Colorectal adenocarcinoma Diseases 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 240000008917 Glycyrrhiza uralensis Species 0.000 description 1
- 235000000554 Glycyrrhiza uralensis Nutrition 0.000 description 1
- MVAUGMLUJKTORM-UHFFFAOYSA-N Licoricidin Natural products COc1cc2OCC(Cc2cc1CC=C(C)C)c3ccc(O)c(CC=C(C)C)c3O MVAUGMLUJKTORM-UHFFFAOYSA-N 0.000 description 1
- 208000025157 Oral disease Diseases 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 241000605862 Porphyromonas gingivalis Species 0.000 description 1
- 206010060862 Prostate cancer Diseases 0.000 description 1
- 208000000236 Prostatic Neoplasms Diseases 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 241000194019 Streptococcus mutans Species 0.000 description 1
- 101710098414 Tyrosine-protein phosphatase Proteins 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 210000000593 adipose tissue white Anatomy 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QKUSRAKPUWQSJS-UHFFFAOYSA-N diazanium 3-ethyl-2H-1,3-benzothiazole-6-sulfonate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)C1=CC=C2N(CC)CSC2=C1.[O-]S(=O)(=O)C1=CC=C2N(CC)CSC2=C1 QKUSRAKPUWQSJS-UHFFFAOYSA-N 0.000 description 1
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 210000002919 epithelial cell Anatomy 0.000 description 1
- 238000002481 ethanol extraction Methods 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000002950 fibroblast Anatomy 0.000 description 1
- 239000001947 glycyrrhiza glabra rhizome/root Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- GBRZTUJCDFSIHM-KRWDZBQOSA-N licoricidin Chemical compound C1([C@@H]2COC=3C=C(O)C(CC=C(C)C)=C(C=3C2)OC)=CC=C(O)C(CC=C(C)C)=C1O GBRZTUJCDFSIHM-KRWDZBQOSA-N 0.000 description 1
- GBRZTUJCDFSIHM-UHFFFAOYSA-N licorisoflavan B Natural products C1C=2C(OC)=C(CC=C(C)C)C(O)=CC=2OCC1C1=CC=C(O)C(CC=C(C)C)=C1O GBRZTUJCDFSIHM-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 208000030194 mouth disease Diseases 0.000 description 1
- 201000001245 periodontitis Diseases 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004262 preparative liquid chromatography Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000019491 signal transduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
The invention discloses a method for separating and extracting glycyrrhizin from plant liquorice, which comprises the following steps: extracting Glycyrrhrizae radix residue with water, soaking in ethanol, and concentrating; adsorbing the concentrated solution on a macroporous resin column, and concentrating the eluent to obtain flavone crude product powder; treating the flavone crude powder by using a solvent I and a solvent II, stirring to obtain turbid liquid, filtering, heating filtrate to volatilize the solvent I, cooling the filtrate to a low temperature condition at a speed of 1-3 ℃/min, and filtering to obtain the licolor product after complete crystallization. The heating temperature is 30-60 ℃, and the ratio of the solvent I to the solvent II is 1:2-1:15. The invention is a high-purity glycyrrhizin separation and extraction method with simple process conditions, low equipment requirements, low material cost, high product quality and easy industrialization.
Description
Technical Field
The invention relates to the technical field of separation and purification of natural active substances of plants, in particular to a method for separating and extracting a flavonoid compound of licoxidine from plant liquorice.
Background
Licorice (Licoricidin) is a flavonoid active ingredient in Glycyrrhrizae radix, and has molecular formula of C 26 H 32 O 5 The molecular weight is 424.53, and the structural formula is as follows:
researches show that the licoxidine has remarkable antibacterial activity on pathogenic bacteria of oral diseases such as porphyromonas gingivalis, streptococcus mutans and the like, and has no obvious cytotoxicity on oral epithelial cells and gingival fibroblasts; the licoxidine can significantly remove ABTS free radical (2, 2-diaza-di (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt) and ROS free radical (reactive oxygen species); liquiritidine has the potential to treat characteristic dermatitis and periodontitis. Furthermore, it is also possible to inhibit migration and expression of mouse breast cancer cells, human prostate cancer cells, human colorectal adenocarcinoma cells. Recent studies have found that it promotes energy expenditure by activating the cAmp-PKA signaling pathway, inducing white fat beige; the novel coronavirus COVID-19 can inhibit the activity of tyrosine protein phosphatase and plays a certain role in antagonizing the novel coronavirus COVID-19 in a protease inhibition mode.
The licocetirizine has great market potential and development prospect in the fields of medicines and health products. However, the liquorice has complex components, and a plurality of active components similar to the physical properties of the liquorice are present, so that the separation difficulty is high, and the liquorice is difficult to separate efficiently; the content of the glycyrrhizin in the liquorice is very low, about 0.08%, and the impurity content is high, and complicated steps or equipment are needed to separate the glycyrrhizin. The price of the liquiritigenin extract with the purity of more than 95% in the market is about hundreds of thousands yuan per gram, and the price is high, so the high-purity liquiritigenin extract prepared by taking the liquorice slag with low cost as the raw material has larger market demand.
Through searching, the prior literature and patents about the preparation of high-purity glycyrrhizic acid are few, a silica gel column separation method is mostly adopted, and the steps are complex. For example, application number CN201910379619.0A method for extracting isopentenyl flavonoids from Glycyrrhrizae radix by using ionic liquid comprises mixing Glycyrrhrizae radix with pure ionic liquid, ultrasonic extracting, and collecting licoxidine in supernatant with content of 224.5 μg/g. The reaction temperature required by the process is higher, the process for synthesizing the ionic liquid is more complex, the cost is higher, and the subsequent recovery process is more complex. The application number of the patent CN201510918824.1 is that ethanol extraction and ethyl acetate extraction are used in the Chinese patent application of the isopentenyl isoflavone compound in liquorice, and the liquorice is obtained after silica gel column chromatography, ethanol-water gradient elution, polyamide column chromatography and dichloromethane-methanol gradient elution, and the obtained liquorice is 900mg/35kg in quantification. The preparation process is complex, the cost is high, and the yield is low. In the literature, "research of the flavonoid components of the glycyrrhiza uralensis root isopentenyl", ethyl acetate and petroleum ether are used for extraction, then silica gel column gradient separation is carried out, and then polyamide chromatographic column separation and semi-preparative separation are carried out. The silica gel column chromatography is difficult to meet the market demand in terms of product quality, and has low yield and complex steps; the semi-preparative liquid chromatography has small preparation amount and is difficult to meet the industrial requirement. Supercritical CO is used in Chinese patent No. CN200880023333.9, glycyrrhrizae radix extract anti-microbial and anti-inflammatory isolate 2 Extracting Glycyrrhrizae radix cetirizine. This method is to convert CO 2 Extracting Glycyrrhrizae radix after loading into supercritical state, and extracting with CO 2 The method has the characteristic of recycling, but has higher requirements on extraction conditions, expensive equipment and certain potential safety hazards in high-temperature or high-pressure experimental conditions.
And the yield of the glycyrrhizin product obtained in the prior art is not high. For example, chinese patent CN201910379619.0, a method for extracting isopentenyl flavonoid compounds from liquorice by using ionic liquid, has the total yield of 0.02%; chinese patent CN201510918824.1, new medical application of isopentenyl isoflavone compound in liquorice, total yield is 0.005%; the literature on study of flavonoid chemical composition in Glycyrrhiza glabra root shows that the total yield is 0.0004%.
Disclosure of Invention
The invention aims to fully utilize licorice slag and provide a high-purity separation and extraction method of the licolor with simple process conditions, low equipment requirements, low material cost, high product yield and easy industrialization.
According to the invention, licorice slag is subjected to alcohol extraction, and partial impurities in the alcohol extract are removed by using macroporous resin treatment, so that a flavone crude product is obtained. Then an improved crystallization method is used for separating out high-purity glycyrrhizic acid, reaction conditions are controlled to improve crystallization effect, and finally a product with the purity of more than 95% can be obtained through one-time crystallization. The specific technical scheme of the invention is as follows:
a method for separating and extracting glycyrrhizin from plant Glycyrrhrizae radix comprises the following steps:
step 1): weighing licorice residue, soaking the licorice residue in deionized water at normal temperature, and carrying out suction filtration to obtain licorice residue after water extraction; soaking the licorice residue after water extraction at normal temperature by using absolute ethyl alcohol, wherein the feed liquid ratio of the licorice residue (before soaking) to the absolute ethyl alcohol is 1:10-1:15 (g/mL), and the extraction time is 10-16 h; collecting the soaking solution, and concentrating under reduced pressure to obtain an absolute ethanol concentrated solution;
step 2): diluting the absolute ethyl alcohol concentrated solution obtained in the step 1) with deionized water, and loading the diluted absolute ethyl alcohol concentrated solution on a macroporous resin column for adsorption, wherein the loading flow rate is 1BV/h, and the macroporous resin is nonpolar or weak polar resin; after the column is finished, carrying out gradient elution by using 50% -85% ethanol aqueous solution, wherein the elution amount of the gradient elution of the ethanol aqueous solution is 8-10 BV, and the flow rate is 1-1.5 BV/h; concentrating the eluent of the last time to obtain coarse flavone powder;
step 3): treating the flavone crude powder obtained in the step 2) by using a solvent I and a solvent II, and stirring to obtain turbid liquid; filtering the turbid liquid, heating the filtrate to volatilize the solvent I, then cooling the filtrate to a low temperature condition at a speed of 1-3 ℃/min, and filtering to obtain a licolor product after complete crystallization; the solvent I is any one of acetone, diethyl ether and dichloromethane, and the solvent II is any one of cyclohexane, n-hexane, petroleum ether and carbon tetrachloride; heating at 30-60 deg.c with the volume ratio of solvent I to solvent II being 1 to 2-1 to 15; the low temperature condition is 4 ℃ to-15 ℃.
As the crude flavone powder obtained in step 2) is treated with solvent I and solvent II in an optimized manner, there are two schemes:
(1) mixing the solvent I and the solvent II according to a certain proportion, dissolving the flavone crude product powder, fully stirring, filtering the turbid liquid, heating the filtrate at a certain temperature to volatilize the solvent I, cooling the solution to a low temperature condition at a speed of 1-3 ℃/min, and filtering to obtain the licoxetine product after complete crystallization.
(2) Dissolving the flavone crude powder by using a solvent I, then adding a solvent II, and fully stirring to obtain turbid liquid. Filtering the turbid liquid, heating the solution at a certain temperature to volatilize the solvent I, cooling the solution to a low temperature at a speed of 1-3 ℃/min, and filtering to obtain the licolor product after complete crystallization.
Further optimizing, wherein the ratio of the deionized water to the soaking liquid in the step 1) is 1:5-1:15 (g/mL), and the soaking time is 5-14 hours.
Further, the normal temperature is 18 to 25 ℃.
Further, the nonpolar or weakly polar resin in the step 2) is of the type LSA-10, D101, LX-T28, D101B or AB-8, and the resin amount is 200-300 g.
Further, in the step 2), the absolute ethyl alcohol concentrated solution is diluted by deionized water until the volume fraction of the ethyl alcohol is 45-55%, and then the ethyl alcohol concentrated solution is adsorbed by a macroporous resin column.
Further, the concentration of the crude flavone powder in the step 3) in the solvent I is 80-400 mg/mL.
Further, the cooling rate of the solution in the step 3) is 1 ℃/min.
The invention has the beneficial effects that:
1) According to the invention, the separation and purification of the glycyrrhizin in the plant liquorice are carried out by combining the alcohol extraction, macroporous resin impurity removal and crystallization modes, the separation and extraction technology is innovative, and the crystallization effect is improved by improving the crystallization mode, so that the time required by separation and purification is greatly shortened, and the yield and purity of the preparation process of the glycyrrhizin are improved.
2) The invention extracts the licoxidine by using the liquorice slag as the raw material, fully utilizes liquorice resources and saves cost.
3) According to the invention, the nonpolar or weak polar macroporous resin is used for purifying the liquorice concentrated solution, so that impurities with larger polarity difference from that of the licoxidine are effectively removed, the resin is environment-friendly and easy to regenerate for recycling, and the ethanol aqueous solution is used as an eluent, so that the toxicity is low and the cost is low.
4) The purification route of the invention is simple, the crystallization technology is firstly applied to separate and purify the glycyrrhizic acid, the silica gel column gradient separation method which is mostly used for separating the glycyrrhizic acid at present is avoided, the equipment requirement is low, the period is short, and the industrial production is easy to expand.
5) The crystallization method of the invention utilizes the solubility difference of the glycyrrhizin in different solvents, simultaneously precisely controls the temperature change and optimizes the crystallization mode. The liquorice cetirizine product with the purity more than 95 percent can be obtained only by one-time crystallization. Compared with the common crystallization method, the invention uses two solvents for crystallization; the invention controls the temperature in the heating process, volatilizes one solvent in the mixed solution, controls the cooling speed, and ensures that the glycyrrhizin crystals are separated out to the greatest extent, thereby greatly improving the purity and the yield in the whole process and achieving better purification effect. With reference to the comparative example, crystallization using only one solvent did not achieve a good purification effect. By adjusting the above conditions, a large amount of crystals of the target compound of high purity can be obtained in a short time, and long-time drying is not required in the subsequent steps.
6) The total yield of the invention can reach more than 0.7 percent, which is far greater than the yield reported by the prior art.
Total yield = (mass of pure glycyrrhizin obtained after crystallization/mass of licorice residue) ×100%
The invention will be described in further detail with reference to the drawings and the detailed description.
Drawings
FIG. 1 is a flow chart of a technical route of the method of the invention;
FIG. 2 is a liquid chromatogram of the soaking solution after soaking licorice residue in deionized water in example 3;
FIG. 3 is a liquid chromatogram of the soaking solution after soaking licorice residue in ethanol in example 3;
FIG. 4 is a liquid chromatogram of the macroporous resin loading solution of example 3;
FIG. 5 is a liquid chromatogram of the final eluate of the macroporous resin of example 3;
FIG. 6 is a liquid chromatogram of the product obtained after crystallization of example 3;
FIG. 7 is a liquid chromatogram of the product obtained in comparative example 1;
FIG. 8 is a liquid chromatogram of the product obtained in comparative example 2;
FIG. 9 is a liquid chromatogram of the product of comparative example 3;
FIG. 10 is a liquid chromatogram of the product obtained in comparative example 6.
Detailed Description
Example 1
A method for separating and extracting glycyrrhizin from plant Glycyrrhrizae radix comprises the following steps:
step 1), taking 500g of licorice residues, adding 6L of deionized water at normal temperature for soaking for 5 hours, and carrying out suction filtration on the deionized water to obtain water extracted licorice residues; adding 5L of absolute ethyl alcohol at normal temperature for soaking for 14 hours, and concentrating under reduced pressure to obtain an absolute ethyl alcohol concentrated solution.
Step 2) diluting the obtained absolute ethyl alcohol concentrated solution with deionized water until the volume fraction of the ethyl alcohol is 45%, adsorbing by D101 macroporous resin, and loading the sample at a flow rate of 1BV/h; gradient elution is carried out by using 55% -75% ethanol water solution with the volume of 10 times of the column volume, the elution flow rate is 1.5BV/h, and the elution quantity is 10BV; collecting the eluent of the last time, and concentrating under reduced pressure to obtain crude flavone dry powder.
Step 3) dissolving the dry powder with dichloromethane at a concentration of 400mg/mL, adding cyclohexane into the dichloromethane solution, stirring thoroughly, and filtering to obtain a turbid solution, wherein the volume ratio of dichloromethane to cyclohexane is 1:7. Heating the filtrate at 38deg.C, slowly rising the temperature, cooling the solution to 4deg.C at a speed of 1deg.C/min after the dichloromethane is basically volatilized, crystallizing for 24 hr, and filtering to obtain Glycyrrhrizae radix cetirizine product. The purity of the product was 96.7% as measured by HPLC, and the yield in this step was 51.66%. The overall yield of this example was 0.736%.
The conditions for the HPLC analysis used for the experiment were as follows: the Shimadzu LC-15C analysis system chromatographic column is Agela Venusil XBP C (L) (4.6X250 mm,5 μm), the mobile phase is acetonitrile-0.1% acetic acid aqueous solution (60:40), the flow rate is 1mL/min, the column temperature is 35 ℃, and the ultraviolet detection wavelength is 282nm. The following examples are the same.
Example 2
A method for separating and extracting glycyrrhizin from plant Glycyrrhrizae radix comprises the following steps:
step 1), 400g of licorice residues are taken, 4L of deionized water is added at normal temperature for soaking for 8 hours, and the deionized water is filtered by suction to obtain water extracted licorice residues; adding 4L of absolute ethyl alcohol at normal temperature for soaking for 16 hours, and concentrating under reduced pressure to obtain an absolute ethyl alcohol concentrated solution.
Step 2) diluting the obtained concentrated solution with deionized water until the volume fraction of ethanol is 50%, adsorbing with D101-B macroporous resin, and loading at a flow rate of 1BV/h; sequentially eluting with 60% -70% ethanol water solution with the volume of 10 times of the column volume, wherein the eluting flow rate is 1.5BV/h, and the eluting amount is 9BV; collecting the eluent of the last time, and concentrating under reduced pressure to obtain crude flavone dry powder.
Step 3) mixing acetone and petroleum ether at a volume ratio of 1:10, and dissolving the crude powder (the concentration of the crude powder in acetone is 80 mg/mL) with the mixed solution. Filtering the turbid liquid after fully stirring, heating the filtrate at 55 ℃, slowly rising the temperature, cooling the solution to-2 ℃ at the speed of 2 ℃/min after the acetone is basically volatilized, crystallizing for 4 hours, and filtering to obtain the licoxedine product. The purity of the product was 95.9% as measured by HPLC, and the yield in this step was 53.33%. The overall yield of this example was 0.743%.
Example 3
A method for separating and extracting glycyrrhizin from plant Glycyrrhrizae radix comprises the following steps:
step 1), taking 500g of licorice residues, adding 5L of deionized water at normal temperature for soaking for 12 hours, and carrying out suction filtration on the deionized water to obtain water extracted licorice residues; adding 5L of absolute ethyl alcohol at normal temperature for soaking for 16 hours, and concentrating under reduced pressure to obtain an absolute ethyl alcohol concentrated solution.
Step 2), diluting the obtained absolute ethyl alcohol concentrated solution with deionized water until the volume fraction of the ethyl alcohol is 55%, and adsorbing by AB-8 macroporous resin, wherein the loading flow rate is 1BV/h; gradient eluting with 60% -80% ethanol water solution with the volume of 10 times of the column volume, wherein the eluting flow rate is 1BV/h, and the eluting amount is 8BV; collecting the eluent of the last time, and concentrating under reduced pressure to obtain crude flavone dry powder.
Step 3) dissolving the dry powder with diethyl ether at the concentration of 200mg/mL, adding cyclohexane into the diethyl ether solution, and filtering the turbid liquid after fully stirring, wherein the volume ratio of diethyl ether to cyclohexane is 1:15. Heating the filtrate at 34 deg.C, slowly rising the temperature, cooling the solution to-5deg.C at a speed of 2deg.C/min after the diethyl ether is basically volatilized, crystallizing for 2 hr, and filtering to obtain Glycyrrhrizae radix cetirizine product. The purity of the product was 95.1% as measured by HPLC, and the yield in this step was 49.76%. The overall yield of this example was 0.729%.
Example 4
A method for separating and extracting glycyrrhizin from plant Glycyrrhrizae radix comprises the following steps:
step 1), taking 600g of licorice residues, adding 5L of deionized water at normal temperature for soaking for 12 hours, and carrying out suction filtration on the deionized water to obtain water extracted licorice residues; adding 5L of absolute ethyl alcohol at normal temperature for soaking for 16 hours, and concentrating under reduced pressure to obtain an absolute ethyl alcohol concentrated solution.
Step 2), diluting the obtained absolute ethyl alcohol concentrated solution with deionized water until the volume fraction of the ethyl alcohol is 50%, adsorbing by AB-8 macroporous resin, and the loading flow rate is 1BV/h; gradient eluting with 55% -70% ethanol water solution with the volume of 10 times of the column volume, wherein the eluting flow rate is 1BV/h, and the eluting amount is 10BV; collecting the eluent of the last time, and concentrating under reduced pressure to obtain crude flavone dry powder.
Step 3) diethyl ether and petroleum ether were mixed in a volume ratio of 1:6, and the crude powder was dissolved with the mixed solution (the concentration of the crude powder in diethyl ether was 150 mg/mL). Filtering the turbid liquid after fully stirring, heating the filtrate at 34 ℃, slowly rising the temperature, cooling the solution to-2 ℃ at a speed of 1.5 ℃/min after diethyl ether is basically volatilized, crystallizing for 2 hours, and filtering to obtain the licoxedine product. The purity of the product was 96.3% by HPLC, and the yield in this step was 47.83%. The overall yield for this example was 0.702%.
Example 5
A method for separating and extracting glycyrrhizin from plant Glycyrrhrizae radix comprises the following steps:
step 1), taking 800g of licorice residues, adding 6L of deionized water at normal temperature for soaking for 10 hours, and carrying out suction filtration on the deionized water to obtain water extracted licorice residues; adding 10L of absolute ethyl alcohol at normal temperature for soaking for 16 hours, and concentrating under reduced pressure to obtain absolute ethyl alcohol concentrated solution;
step 2) diluting the obtained absolute ethyl alcohol concentrated solution with deionized water until the volume fraction of the ethyl alcohol is 50%, adsorbing with LSA-10 macroporous resin, and loading at a flow rate of 1BV/h; gradient eluting with 70% -80% ethanol water solution with the volume of 10 times of the column volume, wherein the eluting flow rate is 1BV/h, and the eluting amount is 10BV; collecting the eluent of the last time, and concentrating by reduced pressure distillation to obtain crude flavone dry powder;
step 3) dissolving the dry powder with dichloromethane with the concentration of 200mg/mL, adding n-hexane into the dichloromethane solution, and filtering the turbid liquid after fully stirring, wherein the volume ratio of the dichloromethane to the n-hexane is 1:6. Heating the filtrate at 38deg.C, slowly rising the temperature, cooling the solution to 2deg.C at a speed of 1.5deg.C/min after the dichloromethane is basically volatilized, crystallizing for 24 hr, and filtering to obtain Glycyrrhrizae radix cetirizine product. The purity of the product was 97.5% by HPLC, and the yield in this step was 50.47%. The overall yield of this example was 0.719%.
Comparative example 1
This comparative example is the comparative example of example 1, and compared to example 1, only the low temperature crystallization operation in step 3) is absent. The other operations were the same as in example 1.
In the step 3), the dry powder is dissolved with methylene chloride with the concentration of 400mg/mL, then cyclohexane is added into the methylene chloride solution, the solvent ratio of methylene chloride to cyclohexane is 1:7, and the turbid liquid is filtered after being fully stirred. The filtrate is heated at 38 ℃, the temperature is slowly increased, and after the dichloromethane is basically volatilized, the filtrate is filtered and dried to obtain the product. The purity of the product was 50.07% by HPLC, and the yield in this step was 9.52%.
Comparative example 2
This comparative example is a comparative example of example 3, and the cooling rate was not controlled as compared to example 3. The other operations were the same as in example 3.
In the step 3), the dry powder is dissolved by diethyl ether with the concentration of 200mg/mL, then cyclohexane is added into the diethyl ether solution, the solvent ratio of diethyl ether to cyclohexane is 1:15, and the turbid liquid is filtered after full stirring. Heating the filtrate at 34 deg.C, slowly increasing the temperature, cooling the solution to-5deg.C after diethyl ether is basically volatilized, crystallizing for 2 hr, and filtering to obtain Glycyrrhrizae radix cetirizine product. The purity of the product was 89.39% as measured by HPLC, and the yield in this step was 15.37%.
Comparative example 3
The comparative example is a comparative example of example 1, and compared with example 1, the comparative example was a single solvent crystal without adding solvent II. The other operations were the same as in example 3.
And 3) dissolving the dry powder with methylene dichloride with the concentration of 400mg/mL, uniformly stirring, placing the solution into a water bath with the temperature of 38 ℃ for condensation and reflux, cooling the solution to the temperature of 4 ℃ at the speed of 1 ℃/min, crystallizing for 24 hours, and filtering to obtain the glycyrrhizic azetidine product. The purity of the glycyrrhizin in the product is 24.10% by HPLC detection, and the yield of the step is 45.45%.
Comparative example 4
This comparative example is a comparative example of example 2, and the added solvent II is not within a preferable range as compared with example 2. The other operations were the same as in example 2.
Step 3) acetone and benzene were mixed in a volume ratio of 1:10, and the crude powder was dissolved with the mixed solution (the concentration of the crude powder in acetone was 80 mg/mL). After stirring thoroughly, the turbid liquid is filtered, the filtrate is heated at 55 ℃, the temperature is slowly increased, and after the acetone is basically volatilized, the solution is cooled to-2 ℃ at a speed of 2 ℃/min, and no glycyrrhizin crystals appear.
Comparative example 5
This comparative example is a comparative example of example 4, and the solvent I added is not within a preferable range as compared with example 4. The other operations were the same as in example 4.
Step 3) mixing ethanol and petroleum ether at a volume ratio of 1:6, and dissolving the crude powder (the concentration of the crude powder in ethanol is 150 mg/mL) with the mixed solution. After stirring thoroughly, the turbid liquid was filtered, the filtrate was heated at 34 ℃, the temperature was slowly increased, and then the solution was cooled to-2 ℃ at a rate of 1.5 ℃/min, without the occurrence of licocetirizine crystals.
Comparative example 6
This example is a comparative example of example 5, and the other operations are the same as example 5, except that example 5 is different in the water bath temperature in step 3) only.
And 3) dissolving the dry powder with dichloromethane with the concentration of 200mg/mL, adding normal hexane into dichloromethane solution with the solvent ratio of dichloromethane to normal hexane of 1:6, fully stirring, filtering the turbid liquid, heating the filtrate at 25 ℃, cooling the solution to 2 ℃ at the speed of 1.5 ℃/min, crystallizing for 24 hours, and filtering to obtain the glycyrrhizic azetidine product. The purity of the product was 39.93% as measured by HPLC, and the yield in this step was 15.47%.
Comparative example 7
This example is a comparative example to example 2, except that the macroporous resin was selected differently, and all other things were the same as example 2. The macroporous resin is LXD-762. The HPLC detection shows that the yield is only 3.58%, and the purity of the licolor in the flavone dry powder obtained by concentration is only 9.81%. The treatment should therefore be carried out with the preferred resin, which would otherwise affect the subsequent crystallization.
The above examples are only a part of the present invention and not all the embodiments of the present invention are covered, and those skilled in the art can obtain more embodiments without any inventive effort on the basis of the above examples and the accompanying drawings, and therefore, all embodiments obtained without any inventive effort are included in the scope of the present invention.
Claims (8)
1. A method for separating and extracting glycyrrhizin from plant licorice, which is characterized by comprising the following steps: step 1): weighing licorice residue, soaking the licorice residue in deionized water at normal temperature, and carrying out suction filtration to obtain licorice residue after water extraction; soaking the licorice residue after water extraction at normal temperature by using absolute ethyl alcohol, wherein the feed liquid ratio of the licorice residue to the absolute ethyl alcohol is 1:10-1:15, and the extraction time is 10-16 h; collecting the soaking solution, and concentrating under reduced pressure to obtain an absolute ethanol concentrated solution; step 2): diluting the absolute ethyl alcohol concentrated solution obtained in the step 1) with deionized water, and loading the diluted absolute ethyl alcohol concentrated solution on a macroporous resin column for adsorption, wherein the loading flow rate is 1BV/h, and the macroporous resin is nonpolar or weak polar resin; after the column is finished, carrying out gradient elution by using 50% -85% ethanol aqueous solution, wherein the elution amount of the gradient elution of the ethanol aqueous solution is 8-10 BV, and the flow rate is 1-1.5 BV/h; concentrating the eluent of the last time to obtain coarse flavone powder;
step 3): treating the flavone crude powder obtained in the step 2) by using a solvent I and a solvent II, and stirring to obtain turbid liquid; filtering the turbid liquid, heating the filtrate to volatilize the solvent I, then cooling the filtrate to a low temperature condition at a speed of 1-3 ℃/min, and filtering to obtain a licolor product after complete crystallization; the solvent I is any one of acetone, diethyl ether and dichloromethane, and the solvent II is any one of cyclohexane, n-hexane, petroleum ether and carbon tetrachloride; heating at 30-60 deg.c with the volume ratio of solvent I to solvent II being 1 to 2-1 to 15; the low temperature condition is 4 ℃ to-15 ℃.
2. The method for separating and extracting glycyrrhizin from plant licorice according to claim 1, wherein: the ratio of the deionized water to the soaking liquid in the step 1) is 1:5-1:15, and the soaking time is 5-14 h.
3. The method for separating and extracting glycyrrhizin from plant licorice according to claim 1, wherein: the normal temperature is 18-25 ℃.
4. The method for separating and extracting glycyrrhizin from plant licorice according to claim 1, wherein: the nonpolar or weakly polar resin in step 2) is LSA-10, D101, LX-T28, D101B or AB-8.
5. The method for separating and extracting glycyrrhizin from plant licorice according to claim 1, wherein: and 2) diluting the absolute ethyl alcohol concentrated solution in the step 2) by deionized water until the volume fraction of the ethyl alcohol is 45-55%, and then adsorbing by a macroporous resin column.
6. The method for separating and extracting glycyrrhizin from plant licorice according to claim 1, wherein: the specific operation of treating the crude flavone powder obtained in step 2) in step 3) with solvent I and solvent II is as follows: mixing the solvent I and the solvent II, adding the coarse flavone powder, stirring, and obtaining turbid liquid.
7. The method for separating and extracting glycyrrhizin from plant licorice according to claim 1, wherein:
the specific operation of treating the crude flavone powder obtained in step 2) in step 3) with solvent I and solvent II is as follows:
dissolving the flavone crude powder by using a solvent I, adding a solvent II into the solution, and stirring to obtain turbid liquid.
8. The method for separating and extracting glycyrrhizin from plant licorice according to claim 6 or 7, characterized in that: the concentration of the flavone crude powder in the step 3) in the solvent I is 80-400 mg/mL.
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