CN117362308A - Preparation method of ultra-high purity glabridin - Google Patents
Preparation method of ultra-high purity glabridin Download PDFInfo
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- CN117362308A CN117362308A CN202311323339.0A CN202311323339A CN117362308A CN 117362308 A CN117362308 A CN 117362308A CN 202311323339 A CN202311323339 A CN 202311323339A CN 117362308 A CN117362308 A CN 117362308A
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- LBQIJVLKGVZRIW-ZDUSSCGKSA-N glabridin Chemical compound C1([C@H]2CC3=CC=C4OC(C=CC4=C3OC2)(C)C)=CC=C(O)C=C1O LBQIJVLKGVZRIW-ZDUSSCGKSA-N 0.000 title claims abstract description 92
- 229940093767 glabridin Drugs 0.000 title claims abstract description 89
- PMPYOYXFIHXBJI-ZDUSSCGKSA-N glabridin Natural products C1([C@H]2CC=3C=CC4=C(C=3OC2)CCC(O4)(C)C)=CC=C(O)C=C1O PMPYOYXFIHXBJI-ZDUSSCGKSA-N 0.000 title claims abstract description 89
- LBQIJVLKGVZRIW-UHFFFAOYSA-N glabridine Natural products C1OC2=C3C=CC(C)(C)OC3=CC=C2CC1C1=CC=C(O)C=C1O LBQIJVLKGVZRIW-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 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 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000706 filtrate Substances 0.000 claims abstract description 49
- 235000006200 Glycyrrhiza glabra Nutrition 0.000 claims abstract description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 244000303040 Glycyrrhiza glabra Species 0.000 claims abstract description 39
- 238000001914 filtration Methods 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 36
- 238000005406 washing Methods 0.000 claims abstract description 33
- 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 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 32
- 239000001685 glycyrrhizic acid Substances 0.000 claims abstract description 32
- 229960004949 glycyrrhizic acid Drugs 0.000 claims abstract description 32
- 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 32
- 235000019410 glycyrrhizin Nutrition 0.000 claims abstract description 32
- 235000011477 liquorice Nutrition 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 27
- 238000002791 soaking Methods 0.000 claims abstract description 26
- 239000012043 crude product Substances 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 230000001105 regulatory effect Effects 0.000 claims abstract description 14
- 238000005554 pickling Methods 0.000 claims abstract description 8
- 230000001376 precipitating effect Effects 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 69
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 241000202807 Glycyrrhiza Species 0.000 description 6
- 235000001453 Glycyrrhiza echinata Nutrition 0.000 description 6
- 235000017382 Glycyrrhiza lepidota Nutrition 0.000 description 6
- 229940010454 licorice Drugs 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000000287 crude extract Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DCXYFEDJOCDNAF-UHFFFAOYSA-N Asparagine Natural products OC(=O)C(N)CC(N)=O DCXYFEDJOCDNAF-UHFFFAOYSA-N 0.000 description 1
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- 102000018832 Cytochromes Human genes 0.000 description 1
- 108010052832 Cytochromes Proteins 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- DCXYFEDJOCDNAF-REOHCLBHSA-N L-asparagine Chemical compound OC(=O)[C@@H](N)CC(N)=O DCXYFEDJOCDNAF-REOHCLBHSA-N 0.000 description 1
- 102000007330 LDL Lipoproteins Human genes 0.000 description 1
- 108010007622 LDL Lipoproteins Proteins 0.000 description 1
- 102000003425 Tyrosinase Human genes 0.000 description 1
- 108060008724 Tyrosinase Proteins 0.000 description 1
- 229960001230 asparagine Drugs 0.000 description 1
- 235000009582 asparagine Nutrition 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 150000002215 flavonoids Chemical class 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010262 high-speed countercurrent chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a preparation method of ultra-high purity glabridin, which comprises the following steps of S1: soaking Glycyrrhiza glabra in pure water; s2: soaking in hydrochloric acid; s3: adding the liquorice subjected to pickling in the step S2 into a sodium hydroxide solution, and filtering to obtain a first filtrate; s4: adjusting the pH value of the first filtrate obtained in the step S3, precipitating solids, filtering to obtain a second filtrate, washing filter residues, and drying to obtain a glabridin crude product; s5: heating and concentrating the second filtrate obtained in the step S4, cooling to room temperature to precipitate solid, and filtering to obtain a third filtrate; s6: regulating the pH value of the third filtrate obtained in the step S5 by using hydrochloric acid to obtain a glycyrrhizic acid crude product; s7: purifying the crude glycyrrhizic acid obtained in the step S6 to obtain pure glycyrrhizic acid; s8: recrystallizing the crude glabridin obtained in the step S4 to obtain pure glabridin; s9: and (3) purifying the pure glabridin obtained in the step S8 to obtain the ultra-high purity glabridin.
Description
Technical Field
The invention relates to the technical field of glabridin synthesis, in particular to a preparation method of ultra-high purity glabridin.
Background
Glabridin is a special flavonoid component in glabra, is insoluble in water, and is easily dissolved in organic solvents such as acetone, ethyl acetate and the like.
Glabridin is called "whitening gold" in the reputation of people due to its strong whitening effect. It can eliminate free radical and melanin at muscle base and inhibit tyrosinase, so it is used for whitening skin and inhibiting melanin. Glabridin has strong anti-free radical oxidation effect in cytochrome oxidation system, and can obviously inhibit free radicals generated in-vivo metabolism process, so as to prevent oxidation-sensitive biomacromolecules (low density lipoprotein LDL, DNA) and cell walls and the like from being damaged by free radical oxidation. Thus, can prevent and treat certain pathological changes related to free radical oxidation, such as atherosclerosis and cell failure. Has the pharmacological effects of resisting oxidation, reducing blood pressure, reducing blood fat, resisting inflammation and the like in the medical application field.
Because of its extremely high utility value, many studies have been made on the extraction and synthesis of glabridin. In the extraction aspect, the method comprises water extraction, alcohol extraction and organic solvent extraction, and also comprises an advanced extraction method using the technology of microwaves and the like. The extraction method comprises the aspects of single solvent, mixed solvent and auxiliary extractant, but the total extraction rate is generally low, and various components are extracted together, so that the difficulty of post purification treatment is greatly increased; chemical synthesis methods, however, require continued efforts by researchers due to their technical difficulties and high cost of synthesis.
CN 110551137B discloses a method for extracting and purifying glabridin and application thereof in cosmetics, the method comprises the following steps: (1) extraction of licorice residues: extracting the licorice residue with 95% ethanol to obtain a licorice residue crude extract; (2) Preparing a glabridin-rich licorice residue concentrate by a high-speed countercurrent chromatography one-step method: the solvent system is dichloromethane, acetone, n-butanol and water (7:5:8:4, V/V), wherein the above phases are mobile phases, the lower phase is stationary phase, the above crude extract of licorice residue is dissolved by an upper phase and lower phase mixed solvent mixed in equal volume ratio, and the mixed solvent is used as a sample solution, the flow rate of the mobile phase is 3mL/min, the temperature is 25 ℃, and the rotating speed is 850r/min, so as to obtain the enriched product of licorice residue rich in glabridin; (3) recrystallization. The method can refine the glabridin with the purity of more than 98 percent from the liquorice slag. However, the chromatographic separation method is difficult to industrialize.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the ultra-high purity glabridin, which has the advantages of simple technical process, convenient product purification and high purity, and has good popularization and application values.
The invention provides a preparation method of ultra-high purity glabridin, which is characterized by comprising the following steps:
s1: drying and pulverizing Glycyrrhiza glabra, soaking in pure water, filtering to obtain Glycyrrhiza glabra soaked in pure water, and purifying with pure water
Soaking to wash out polysaccharide and water-soluble small molecular compound;
s2: soaking the Glycyrrhiza glabra L after pure water soaking in the step S1 with 1wt% hydrochloric acid, filtering, washing, and drying to obtain the Glycyrrhiza glabra L after pickling, soaking with hydrochloric acid to remove alkaline substances, and further washing to remove water-soluble substances easily dissolved in water
A substance;
s3: adding the liquorice after pickling in the step S2 into a sodium hydroxide solution with the concentration of 1-5wt%, cooling to 0-10deg.C, rapidly stirring for 2-4 h, adding 95% ethanol, continuously stirring for 1h, and filtering to obtain a first filter
The filter residue is three-paste saponin, asparagine and the like;
s4: introducing carbon dioxide into the first filtrate obtained in the step S3, regulating the pH value to 3-5, precipitating solids, filtering to obtain a second filtrate, washing and drying filter residues to obtain a glabridin crude product, and comparing the acidity of carbonic acid with that of glabridin by utilizing the carbonic acid
The glabridin is strong and weaker than glycyrrhizic acid, and can selectively separate out crude glabridin;
s5: heating and concentrating the second filtrate obtained in the step S4, cooling to room temperature to precipitate solid, filtering to obtain a third filtrate, heating and concentrating to remove ethanol in the solution, reducing the solubility of organic matters in the second filtrate, filtering, and feeding
The organic matter content in the third filtrate is reduced in one step, and the purity of the glycyrrhizic acid is improved;
s6: regulating pH value of the third filtrate obtained in the step S5 to 0-1 with hydrochloric acid, separating out solid, filtering and washing
Washing and drying to obtain a glycyrrhizic acid crude product;
s7: purifying the crude glycyrrhizic acid obtained in the step S6 to obtain pure glycyrrhizic acid;
s8: recrystallizing the crude glabridin obtained in the step S4 to obtain pure glabridin;
s9: and (3) purifying the pure glabridin obtained in the step S8 to obtain the ultra-high purity glabridin.
Further, the mass of the pure water in the step S1 is 2-4 times of that of the Glycyrrhiza glabra, and the soaking time is 5-10 minutes.
Further, in the step S2, the mass of hydrochloric acid is 2-4 times that of the Glycyrrhiza glabra, and the soaking time is 5-10 minutes.
Further, in the step S3, the mass of 95% ethanol is 30% of the mass of the sodium hydroxide solution, and after adding ethanol, the solubility of the organic matters is increased, so that the remaining glycyrrhizic acid and glabridin in the glabra and a small amount of other organic matters can be transferred into the sodium hydroxide solution.
Further, the pH of the first filtrate in the step S3 is greater than 13.
Further, the second filtrate in the step S5 is heated and concentrated to 80% of the original volume.
Further, the glycyrrhizic acid purification method in the step S7 comprises the following steps: dissolving the glycyrrhizic acid crude product in a mixed solution of water and ethanol with the mass of 4-6 times, heating, concentrating, cooling, crystallizing, washing and drying to obtain a glycyrrhizic acid pure product, wherein the mass ratio of the water to the ethanol is 1:4.
Further, the recrystallization method of the crude glabridin step S8 comprises the following steps: dissolving the glabridin crude product in a mixed solution of water and ethanol, which is 5-8 times of the glabridin crude product in mass, heating, concentrating, cooling, crystallizing, washing and drying to obtain the pure glabridin, wherein the mass ratio of the water to the ethanol is 1:6.
Further, the purification method of glabridin in the step S9 is as follows: adding pure water 3-5 times of pure glabridin at 0-10 ℃, starting stirring, adding sodium hydroxide solid, adjusting the pH value of the solution to 10-11, introducing excessive carbon dioxide, adjusting the pH value of the solution to 3-5, precipitating solid, filtering, washing and drying to obtain the ultra-high purity glabridin. The pH value is regulated by adopting carbon dioxide without hydrochloric acid, the addition of water in the solution is reduced, the yield can be improved, meanwhile, the solubility of sodium bicarbonate generated by the carbon dioxide and sodium hydroxide is lower, the salting-out effect is realized in the crystallization process, the effect is obvious, and the purity of the finally obtained ultra-high purity glabridin is very high.
Further, the purity of the pure glycyrrhizic acid is more than 85%, and the purity of the ultra-high purity glabridin is more than 99%.
Drawings
FIG. 1 is a liquid chromatography of ultra-high purity glabridin of example 2
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments, but not all embodiments, of the present invention, and all other embodiments obtained by those skilled in the art without making any inventive effort are within the scope of the present invention.
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The preparation method of the ultra-high purity glabridin is characterized by comprising the following steps of:
s1: drying and pulverizing Glycyrrhiza glabra, soaking in pure water, and filtering to obtain Glycyrrhiza glabra soaked in pure water, and pure water
2 times of the liquorice, and the soaking time is 10 minutes;
s2: soaking Glycyrrhrizae radix in pure water in step S1 with 1wt% hydrochloric acid, filtering, washing, and drying to obtain
The quality of hydrochloric acid of the liquorice after pickling is 2 times that of the liquorice, and the soaking time is 5 minutes;
s3: adding the Glycyrrhiza glabra L obtained after pickling in the step S2 into a sodium hydroxide solution with the concentration of 1wt%, cooling to 5-10 ℃, rapidly stirring for 2h, adding 95% ethanol, continuously stirring for 1h, and filtering to obtain a first filtrate, wherein the first filtrate is prepared by
The pH value of the first filtrate is more than 13, and the mass of 95% ethanol is 30% of the mass of the sodium hydroxide solution;
s4: introducing carbon dioxide into the first filtrate obtained in the step S3, regulating the pH value to be between 4 and 5, separating out solids,
filtering to obtain a second filtrate, washing filter residues, and drying to obtain a glabridin crude product;
s5: heating and concentrating the second filtrate obtained in the step S4, cooling to room temperature to precipitate solid, and filtering to obtain a third filtrate, wherein the second filtrate is heated and concentrated to 80% of the original volume;
s6: regulating the pH value of the third filtrate obtained in the step S5 to be between 0 and 1 by using hydrochloric acid, separating out solid, filtering, washing and drying to obtain a glycyrrhizic acid crude product;
s7: dissolving the glycyrrhizic acid crude product obtained in the step S6 in a mixed solution of water and ethanol, which is 5 times of the glycyrrhizic acid crude product in mass, heating, concentrating, cooling, crystallizing, washing and drying to obtain a glycyrrhizic acid pure product, wherein the mass ratio of water to ethanol is 1:4, and the mixed solution of water and ethanol is prepared by adopting condensate liquid obtained by heating, concentrating and steaming in the step S5 and pure water;
s8: dissolving the glabridin crude product obtained in the step S7 in a mixed solution of water and ethanol with the mass of 6 times, heating, concentrating, cooling, crystallizing, washing and drying to obtain pure glabridin, wherein the mass ratio of water to ethanol is 1:6;
s9: adding pure water which is 3 times the mass of the glabridin obtained in the step S8 into the glabridin at the temperature of 5-10 ℃, starting stirring, adding sodium hydroxide solid, adjusting the pH value of the solution to be 10-11, then introducing excessive carbon dioxide, adjusting the pH value of the solution to be 4-5, separating out solid, filtering, washing and drying to obtain the ultra-high purity glabridin with the purity of 99.2% and the purification yield of 91.2%.
Example 2
The preparation method of the ultra-high purity glabridin is characterized by comprising the following steps of:
s1: drying and crushing the liquorice, soaking the liquorice in pure water, and filtering to obtain the liquorice after the liquorice is soaked in the pure water, wherein the quality of the pure water is 3 times that of the liquorice, and the soaking time is 5 minutes;
s2: soaking the liquorice after being soaked in the pure water in the step S1 by adopting 1wt% hydrochloric acid, filtering, washing and drying to obtain the liquorice after being pickled, wherein the quality of the hydrochloric acid is 3 times that of the liquorice, and the soaking time is 10 minutes;
s3: adding the liquorice after pickling in the step S2 into a sodium hydroxide solution with the concentration of between 2 weight percent, cooling to between 0 and 5 ℃, rapidly stirring for 3 hours, then adding 95 percent ethanol, continuously stirring for 1 hour, and filtering to obtain a first filtrate, wherein the pH value of the first filtrate is more than 13, and the mass of the 95 percent ethanol is 30 percent of the mass of the sodium hydroxide solution;
s4: introducing carbon dioxide into the first filtrate obtained in the step S3, regulating the pH value to 3-4, precipitating solids, filtering to obtain second filtrate, washing filter residues, and drying to obtain crude glabridin;
s5: heating and concentrating the second filtrate obtained in the step S4, cooling to room temperature to precipitate solid, and filtering to obtain a third filtrate, wherein the second filtrate is heated and concentrated to 80% of the original volume;
s6: regulating the pH value of the third filtrate obtained in the step S5 to be between 0 and 1 by using hydrochloric acid, separating out solid, filtering, washing and drying to obtain a glycyrrhizic acid crude product;
s7: dissolving the glycyrrhizic acid crude product obtained in the step S6 in a mixed solution of water and ethanol with the mass of 6 times, heating, concentrating, cooling, crystallizing, washing and drying to obtain a glycyrrhizic acid pure product with the purity of 86.1%, wherein the mass ratio of water to ethanol is 1:4; s8: dissolving the glabridin crude product obtained in the step S7 in a mixed solution of water and ethanol with the mass of 6 times, heating, concentrating, cooling, crystallizing, washing and drying to obtain pure glabridin, wherein the mass ratio of water to ethanol is 1:6;
s9: adding pure water with the mass of 5 times of that of the glabridin obtained in the step S8 at the temperature of between 0 and 5 ℃, starting stirring, adding sodium hydroxide solid, regulating the pH value of the solution to be between 10 and 11, introducing excessive carbon dioxide, regulating the pH value of the solution to be between 3 and 4, separating out solid, filtering, washing and drying to obtain the ultra-high purity glabridin with the purity of 99.8 percent and the purification yield of 90.8 percent.
Example 3
The preparation method of the ultra-high purity glabridin is characterized by comprising the following steps of:
s1: drying and crushing the liquorice, soaking the liquorice in pure water, and filtering to obtain the liquorice after the liquorice is soaked in the pure water, wherein the quality of the pure water is 4 times that of the liquorice, and the soaking time is 10 minutes;
s2: soaking the liquorice after being soaked in the pure water in the step S1 by adopting 3wt% hydrochloric acid, filtering, washing and drying to obtain the liquorice after being pickled, wherein the quality of the hydrochloric acid is 4 times that of the liquorice, and the soaking time is 10 minutes;
s3: adding the liquorice after pickling in the step S2 into a sodium hydroxide solution with the concentration of between 1 percent by weight, cooling to between 5 and 8 ℃, rapidly stirring for 3 hours, then adding 95 percent ethanol, continuously stirring for 1 hour, and filtering to obtain a first filtrate, wherein the pH value of the first filtrate is more than 13, and the mass of the 95 percent ethanol is 30 percent of the mass of the sodium hydroxide solution;
s4: introducing carbon dioxide into the first filtrate obtained in the step S3, regulating the pH value to 3-4, precipitating solids, filtering to obtain second filtrate, washing filter residues, and drying to obtain crude glabridin;
s5: heating and concentrating the second filtrate obtained in the step S4, cooling to room temperature to precipitate solid, and filtering to obtain a third filtrate, wherein the second filtrate is heated and concentrated to 80% of the original volume;
s6: regulating the pH value of the third filtrate obtained in the step S5 to be between 0 and 1 by using hydrochloric acid, separating out solid, filtering, washing and drying to obtain a glycyrrhizic acid crude product;
s7: dissolving the glycyrrhizic acid crude product obtained in the step S6 in a mixed solution of water and ethanol with the mass being 4 times that of the glycyrrhizic acid crude product, heating, concentrating, cooling, crystallizing, washing and drying to obtain a glycyrrhizic acid pure product with the purity of 85.3%, wherein the mass ratio of water to ethanol is 1:4;
s8: dissolving the glabridin crude product obtained in the step S7 in a mixed solution of water and ethanol with the mass of 6 times, heating, concentrating, cooling, crystallizing, washing and drying to obtain pure glabridin, wherein the mass ratio of water to ethanol is 1:6;
s9: adding pure water which is 4 times the mass of the glabridin obtained in the step S8 at the temperature of 3-8 ℃, starting stirring, adding sodium hydroxide solid, adjusting the pH value of the solution to be 10-11, then introducing excessive carbon dioxide, adjusting the pH value of the solution to be 3-4, separating out solid, filtering, washing and drying to obtain the ultra-high purity glabridin with the purity of 99.1% and the purification yield of 91.1%.
Comparative example 1
Step S2 in embodiment 2 is omitted, and the details are not repeated in the same manner as in embodiment 2. The purity of glycyrrhizic acid in the final step S7 is 83.7%, and the purity of ultra-high purity glabridin in the step S9 is 97.6%.
Comparative example 2
Step S5 in embodiment 2 is omitted, and the details are not repeated in embodiment 2. The purity of glycyrrhizic acid in the final step S7 is 79.7%, the purity of ultra-high purity glabridin in the step S9 is 92.1%, the impurity organic matter content in the second filtrate is high in the step S5, and the purity of the subsequent step is reduced.
Comparative example 3
The carbon dioxide with the pH adjusted in step S9 in example 2 is changed to hydrochloric acid, and the details are not repeated in the same manner as in example 2. In the final S9 step, the purity of the ultra-high purity glabridin is 98.4%, the purity is slightly reduced, but the purification yield is reduced by 5%.
Comparative example 4
The temperature of step S3 in example 2 was reduced to between 0 and 10℃and changed to between 20 and 30, and the purity of ultra-high purity glabridin in the final step S9 was 88.2%, the purity was significantly reduced, and the yield was reduced, indicating that the temperature was high, resulting in side reactions such as glabridin ring opening.
Comparative example 5
Step S8 in embodiment 2 is omitted, and the details are not repeated in embodiment 2. The purity of ultra-high purity glabridin in the final S9 step is 96.1%.
Claims (10)
1. The preparation method of the ultra-high purity glabridin is characterized by comprising the following steps of:
s1: drying and pulverizing Glycyrrhiza glabra, soaking in pure water, and filtering to obtain Glycyrrhiza glabra after soaking in pure water;
s2: soaking the liquorice after being soaked in the pure water in the step S1 by adopting 1 weight percent hydrochloric acid, filtering, washing and drying to obtain the liquorice after being pickled;
s3: adding the liquorice subjected to pickling in the step S2 into a sodium hydroxide solution with the concentration of 1-5wt%, cooling to 0-10deg.C, rapidly stirring for 2-4 h, adding 95% ethanol, continuously stirring for 1h, and filtering to obtain a first filtrate;
s4: introducing carbon dioxide into the first filtrate obtained in the step S3, regulating the pH value to 3-5, precipitating solids, filtering to obtain second filtrate, washing filter residues, and drying to obtain crude glabridin;
s5: heating and concentrating the second filtrate obtained in the step S4, cooling to room temperature to precipitate solid, and filtering to obtain a third filtrate;
s6: regulating the pH value of the third filtrate obtained in the step S5 to be between 0 and 1 by using hydrochloric acid, separating out solid, filtering, washing and drying to obtain a glycyrrhizic acid crude product;
s7: purifying the crude glycyrrhizic acid obtained in the step S6 to obtain pure glycyrrhizic acid;
s8: recrystallizing the crude glabridin obtained in the step S4 to obtain pure glabridin;
s9: and (3) purifying the pure glabridin obtained in the step S8 to obtain the ultra-high purity glabridin.
2. The method for preparing ultra-high purity glabridin according to claim 1, wherein the mass of pure water in the step S1 is 2 to 4 times that of glabridin, and the soaking time is 5 to 10 minutes.
3. The method for preparing ultra-high purity glabridin according to claim 1, wherein the mass of hydrochloric acid in the step S2 is 2-4 times that of glabridin, and the soaking time is 5-10 minutes.
4. The method for preparing ultra-high purity glabridin according to claim 1, wherein the mass of 95% ethanol in step S3 is 30% of the mass of sodium hydroxide solution.
5. The method for preparing ultra-high purity glabridin according to claim 1, wherein the pH of the first filtrate in step S3 is greater than 13.
6. The method for preparing ultra-high purity glabridin according to claim 1, wherein the second filtrate in step S5 is concentrated to 80% of the original volume by heating.
7. The method for preparing ultra-high purity glabridin according to claim 1, wherein the method for purifying glycyrrhizic acid in step S7 comprises: dissolving the glycyrrhizic acid crude product in a mixed solution of water and ethanol with the mass of 4-6 times, heating, concentrating, cooling, crystallizing, washing and drying to obtain a glycyrrhizic acid pure product, wherein the mass ratio of the water to the ethanol is 1:4.
8. The method for preparing ultra-high purity glabridin according to claim 1, wherein the method for recrystallizing crude glabridin in step S8 comprises: dissolving the glabridin crude product in a mixed solution of water and ethanol, which is 5-8 times of the glabridin crude product in mass, heating, concentrating, cooling, crystallizing, washing and drying to obtain the pure glabridin, wherein the mass ratio of the water to the ethanol is 1:6.
9. The method for preparing ultra-high purity glabridin according to claim 1, wherein the method for purifying glabridin in step S9 comprises: adding pure water 3-5 times of pure glabridin at 0-10 ℃, starting stirring, adding sodium hydroxide solid, adjusting the pH value of the solution to 10-11, introducing excessive carbon dioxide, adjusting the pH value of the solution to 3-5, precipitating solid, filtering, washing and drying to obtain the ultra-high purity glabridin.
10. The method for preparing ultra-high purity glabridin according to claim 1, wherein the purity of the pure glabridin is more than 85%, and the purity of the ultra-high purity glabridin is more than 99%.
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