CN101585863B - Method for preparing yamogenin - Google Patents
Method for preparing yamogenin Download PDFInfo
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- CN101585863B CN101585863B CN2009100404714A CN200910040471A CN101585863B CN 101585863 B CN101585863 B CN 101585863B CN 2009100404714 A CN2009100404714 A CN 2009100404714A CN 200910040471 A CN200910040471 A CN 200910040471A CN 101585863 B CN101585863 B CN 101585863B
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Abstract
The present invention discloses a method for preparing a yamogenin, including slicing a fresh dong leaf Chinese yam, decocting in water, centrifuging, merging water extract, pole-separating by adding a resin bed, eluting by using a 95% of ethanol after rinshing by 0.8-1.5 of pole volume, collecting an ethanol eluent, or drying the dong leaf Chinese yam and comminuting, refluxing and extracting by the ethanol, centrifuging, merging the extract, concentrating, pole-separating by adding the resin bed, eluting by using the 95% of ethanol after rinshing by 0.8-1.5 of pole volume, collecting the ethanol eluent' hydrolyzing by an alcaine ethanol solution, and coolting until a room temperature; regulating the pH value to 7, filtrating and concentrating; adding a mineral ether to the concentrated filtrate, refluxing and extracting, cooling, concentrating, fetching a crystallization, drying, then a product will be obtained. The method of the invention is capable of reducing a usage amount of an acid and an adding amount of the sodium hydrate greatly; there is not discharged acid water, which reduces a pollution of a river and lake water source; a product yield achieve 1.19% by using the fresh Chinese yam as a raw material, which is higher than an original technique by 0.71%; a product yield is 3% by using the drying Chinese yam as a raw material. A purity of the yamogenin is more than 95% by a HPLC mensuration.
Description
Technical field
The invention belongs to the field of Chinese medicines, particularly a kind of novel method of from Rhizome of Peltate Yam, extracting the preparation diosgenin.
Background technology
Diosgenin is synthetic multiple steroid hormone and the more satisfactory precursor of contraceptive steroid, and steroid hormone is a raw material with it 60% or more, and steroid hormone is widely used, and development is rapid, is to be only second to an antibiotic key areas in the pharmaceutical production.Diosgenin also has reducing blood-fat, platelet aggregation-against, promotion choleresis, induces human erythroleukemia cell and multiple efficacies such as human leukemia cell's differentiation and inhibition growth of tumour cell.The export volume of China's diosgenin is only second to Mexico and occupies the second in the world.Rhizome of Peltate Yam is the endemic plant of China, this plant diosgenin mainly is present in underground rhizome, content from 1.01% to 16.15%, average out to 2.5%, be one of the highest plant of sapogenin content, become the main medicinal plant that China produces diosgenin.The production technique of China's diosgenin mainly comprises processes such as acid hydrolysis, filtration, extraction, recrystallize at present, a large amount of acid waste waters have been discharged, produce one ton of diosgenin and will discharge kiloton acid waste water, serious environment pollution is all used this explained hereafter diosgenin at present and China produces 1000000 tons of Rhizome of Peltate Yam per year.The main product ground of Chinese yam in Shaanxi, the middle and upper reaches in the Yellow River such as Sichuan, Hubei, the Changjiang river, a large amount of sewage discharge centering downstream water resources cause very big harm.South, Shaanxi Province of enrichment in the end of the year 2008 sapogenin manufacturer is owing to be located in one of source of the south water to north, and the manufacturer of tame sapogenin more than 100 overwhelming majority closes by Policy Conditions, and a large amount of Chinese yam raw materials do not have institute to be used, the while in a large number workmans lose the post.
The existing technology key step of producing diosgenin from Rhizome of Peltate Yam comprises hydrolysis cut-out glycosidic link, slightly carries aglycon, recrystallize, and wherein hydrolysis process is the committed step of decision yield.Hydrolysis process mainly contains chemical hydrolysis (directly acid hydrolysis, pre-fermentation-acid hydrolysis) and biological hydrolysis process (enzymolysis or microbial fermentation).Though the biological hydrolysis process condition is relatively gentleer, the sapogenin yield is higher, but because chemical hydrolysis equipment is simple relatively, adds that the residing China of Rhizome of Peltate Yam planting site central and west regions technical force is backward relatively, manufacturer's scale is less relatively, and the present stage practical application is more general.Report has the supercritical CO 2 extraction process to prepare the method for diosgenin in addition, but is difficult for realizing industrially scalable, and cost is higher.So, now producer adopt with hydrochloric acid or aqueous sulfuric acid to the broken directly acid hydrolysis of fresh Chinese yam (or directly acid hydrolysis after short period of time spontaneous fermentation), filter (sour water directly discharges), pulp water be washed till neutrality, oven dry, No. 200 gasoline extractions, crystalline explained hereafter diosgenin.1 ton of diosgenin of the every production of above-mentioned technology consumes about 140 tons of fresh Chinese yams (about yield 0.71%), more than the discharging acid waste water kiloton, causes the rivers and lakes severe contamination.
Therefore, seek low sour water or do not have the sour water discharging, technology diosgenin production technique simple, with low cost has crucial social effect and economic worth.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, the object of the present invention is to provide the method for preparing diosgenin that a kind of cost is low, technology simple, no sour water discharges.
Purpose of the present invention is achieved through the following technical solutions: a kind of method for preparing diosgenin comprises following operation steps:
(1) with fresh Rhizome of Peltate Yam section, use water boiling and extraction, centrifugal, merge aqueous extract; With resin chromatography column on the aqueous extract, behind the water elution, be 95% ethanol elution with concentration of volume percent, collect ethanol eluate;
Or, use alcohol reflux with the pulverizing of exsiccant Rhizome of Peltate Yam, centrifugal, united extraction liquid concentrates; With resin chromatography column on the concentrated solution, behind the water elution, be 95% ethanol elution with concentration of volume percent, collect ethanol eluate;
(2) add hydrochloric acid to step (1) gained ethanol eluate, make ethanol solution hydrochloride and be hydrolyzed, hydrolyzed solution is cooled to room temperature;
(3) regulate pH to 7, filter, concentrate, get concentrated filtrate;
(4) add sherwood oil to concentrated filtrate, reflux extraction, cooling concentrates, and gets crystallization, and drying gets the diosgenin finished product.
The described alcohol reflux of step (1) is to be 95% alcohol reflux with concentration of volume percent.
Stir in the time of the described water boiling and extraction of step (1); Stir in the time of described alcohol reflux.
The number of times of the described water boiling and extraction of step (1) is 2～3 times, and each time of extracting is 1～2 hour, and the amount of at every turn extracting institute's water is 4～5 liters of/kilogram Chinese yams; The temperature of described alcohol reflux is 55 ℃～65 ℃, and the number of times of extraction is 2～3 times, and each time of extracting is 1～2 hour, and extract used alcoholic acid amount is 4～5 liters of/kilogram Chinese yams at every turn; Described resin chromatography column is the macroporous resin chromatography column.Described macroporous resin chromatography column is macroporous adsorbent resin AB-8 or macroporous adsorbent resin X-5.
The described water elution of step (1) is to carry out water elution with 0.8～1.5 column volume.
The temperature of the described hydrolysis of step (2) is 80～100 ℃, and the time of hydrolysis is 10～16 hours; The concentration of described ethanol solution hydrochloride is 3～3.5mol/L.
The described adjusting of step (3) pH is that adding sodium hydrate solid or potassium hydroxide solid are regulated.
The volume add-on of the described sherwood oil of step (4) is 1～1.5 times of spissated filtrate volume; The temperature of described reflux extraction is 50～60 ℃, and the time is 8～12 hours; Described drying is vacuum-drying, and drying temperature is 50～60 ℃, and be 2～3 hours time of drying.
In order to guarantee that degree of purity of production satisfies the needs that use, measure diosgenin purity with high performance liquid chromatography (HPLC), when diosgenin does not satisfy the demands, in product, add sherwood oil repeating step (4), meet the requirements until product purity.
The present invention has following advantage and effect with respect to prior art:
(1) use the ethanol solution hydrochloride hydrolysis first in diosgenin production, the hydrolysis of dioscin sugar chain is more thorough, and yield improves; The fresh Rhizome of Peltate Yam of product yield can be greater than 1%, and is higher than former technology 0.71%; Purity measures＞95% through HPLC; The sapogenin yield is 3% in the dry Rhizome of Peltate Yam.
(2) no sour water discharging reduces greatly to the middle and upper reaches pollution of waterhead in rivers and lakes especially the Yellow River, the Changjiang river; Ethanol and sherwood oil reclaim and use, and the slag solid behind the poach can be made organic fertilizer.Meet national energy-saving and emission-reduction policy.
(3) and in existing containing and the report ratio of technology, hydrochloric acid and sodium hydroxide concentration significantly reduce; The Rhizome of Peltate Yam extracting solution is removed sugar and water soluble starch with 0.8～1.5 column volume water elution behind last macroporous resin, use the whole saponin(es of 95% ethanol elution again; 1 ton of fresh Rhizome of Peltate Yam with aforesaid method after, have only 95% ethanol elutant about 500 liters; Directly add hydrochloric acid in the ethanol eluate, with ethanol is that the hydrochloric acid soln that solvent is prepared is hydrolyzed, than directly significantly reduce with the used hydrochloric acid of aqueous hydrochloric acid hydrolysis, thereby the addition amount of sodium hydroxide that plays neutralizing effect obviously reduces, and the solvent concentration process after can saving, produce and can reduce thickening equipment;
(4) having set up with fresh Rhizome of Peltate Yam and dry Rhizome of Peltate Yam simultaneously is the technology of raw material production diosgenin, and except that pre-treatment (section or pulverizing) is different with extraction (poach or extraction using alcohol), the operational path basically identical, enlarged the selection face of producer on the one hand to raw material, make raw material can not be subjected to the restriction that to put into production once gathering in the crops as far as possible, producer also can make full use of equipment many seasons on the other hand, reduces cost better;
(5) technology is simple, is easy to realize industrialization.
Description of drawings
Fig. 1 is the high-efficient liquid phase chromatogram of the diosgenin of the inventive method preparation.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment 1:
The fresh Rhizome of Peltate Yam section of (1) 1kg just having been excavated places the 10L Stainless Steel Kettle, uses the 5L water boiling and extraction, boils and stirs 1 hour, extracts altogether 3 times, and residue is removed in centrifugation; Merge aqueous extract; With macroporous adsorbent resin AB-8 (Φ 35 * 600mm on the aqueous extract, Chemical Plant of Nankai Univ. produces), behind the 500ml water elution, continuing with the 500ml concentration of volume percent is that 95% ethanol elution to thin-layer chromatography point sample detects few saponin constituent in the elutriant, collection ethanol eluate;
(2) add 60ml hydrochloric acid in step (1) gained ethanol eluate, make the 3.0mol/L ethanol solution hydrochloride, stir hydrolysis 12 hours down at 80 ℃, hydrolyzed solution is cooled to room temperature;
(3) add the 25g solid sodium hydroxide and stirred 30 minutes, regulate pH to 7, filter, concentrate, obtain concentrated filtrate 40ml;
(4) add the 40ml sherwood oil to concentrated filtrate, 60 ℃ of reflux extraction 8 hours, cooling concentrates, and gets crystallization, 60 ℃ of vacuum-drying 2 hours, diosgenin finished product 11.87g.Measuring detection diosgenin purity with high performance liquid chromatography (HPLC) is 93.85%.
Embodiment 2:
(1) the dry Rhizome of Peltate Yam of 1kg being pulverized, placed the 10L Stainless Steel Kettle, is 95% alcohol reflux with the 4L concentration of volume percent, and 60 ℃ of stirrings 1 hour are extracted 3 times altogether, and residue is removed in centrifugation; Merge ethanol extract; Concentrate; With macroporous adsorbent resin AB-8 (Φ 35 * 600mm on the concentrated solution, Chemical Plant of Nankai Univ. produces), behind the 500ml water elution, continuing with the 500ml concentration of volume percent is that 95% ethanol elution to thin-layer chromatography point sample detects few saponin constituent in the elutriant, collection ethanol eluate;
(2) add 60ml hydrochloric acid in step (1) gained ethanol eluate, make the 3.0mol/L ethanol solution hydrochloride, stir hydrolysis 16 hours down at 90 ℃, hydrolyzed solution is cooled to room temperature;
(3) add the 25g solid sodium hydroxide and stirred 30 minutes, regulate pH to 7, filter, concentrate, obtain concentrated filtrate 40ml;
(4) add the 40ml sherwood oil to concentrated filtrate, 60 ℃ of reflux extraction 10 hours, cooling concentrates, and gets crystallization, 50 ℃ of vacuum-drying 3 hours, diosgenin finished product 30.23g.Measuring detection diosgenin purity with high performance liquid chromatography (HPLC) is 96.07%.
Embodiment 3:
(1) the dry Rhizome of Peltate Yam of 10kg being pulverized, placed the 100L reactor, is 95% alcohol reflux with the 40L concentration of volume percent, and 60 ℃ of stirrings 2 hours are extracted 2 times altogether, and residue is removed in centrifugation; Merge ethanol extract; Concentrate; With macroporous adsorbent resin X-5 (Φ 50 * 1000mm on the concentrated solution, Chemical Plant of Nankai Univ. produces), behind the 1500ml water elution, continuing with the 4000ml concentration of volume percent is that 95% ethanol elution to thin-layer chromatography point sample detects few saponin constituent in the elutriant, collection ethanol eluate;
(2) add 480ml hydrochloric acid in step (1) gained ethanol eluate, make the 3.5mol/L ethanol solution hydrochloride, stir hydrolysis 10 hours down at 100 ℃, hydrolyzed solution is cooled to room temperature;
(3) adding 196g solid potassium hydroxide stirred 100 minutes, regulated pH to 7, filtered, and utilized distillation method to reclaim ethanol in the filtrate, got concentrated filtrate 333.3ml;
(4) add the 500ml sherwood oil to concentrated filtrate, 50 ℃ of reflux extraction 12 hours, cooling concentrates, and gets crystallization, 60 ℃ of vacuum-drying 2 hours, diosgenin finished product 297.51g.Measure detection diosgenin purity, purity 87.22% with high performance liquid chromatography (HPLC).To this diosgenin once, use high performance liquid chromatography (HPLC) to measure again and detect retention time T with the sherwood oil recrystallization
R=13.582 minutes, purity was 95.42% (color atlas as shown in Figure 1).
Embodiment 4:
(1) the fresh Rhizome of Peltate Yam of 50kg being excavated two days is cut into slices, and places the 500L multi-function extractor, uses the 250L water boiling and extraction, boils and stirs 2 hours, extracts altogether 2 times, and residue is removed in centrifugation; Merge aqueous extract; With macroporous adsorbent resin AB-8 (Φ 120 * 1500mm on the aqueous extract, Chemical Plant of Nankai Univ. produces), behind the 16L water elution, continuing with the 25L concentration of volume percent is that 95% ethanol elution detects in the elutriant to the thin-layer chromatography point sample and do not have saponin constituent, the collection ethanol eluate;
(2) add 2.7L hydrochloric acid in step (1) gained ethanol eluate, make the 3.2mol/L ethanol solution hydrochloride, stir hydrolysis 15 hours down at 85 ℃, hydrolyzed solution is cooled to room temperature;
(3) adding 1.25kg solid sodium hydroxide stirred 100 minutes, regulated pH to 7, filtered, and utilized distillation method to reclaim ethanol in the filtrate, got concentrated filtrate 1666.7ml;
(4) add the 2000ml sherwood oil to concentrated filtrate, 60 ℃ of reflux extraction 10 hours, cooling concentrates and reclaims sherwood oil, obtains the diosgenin crude product; Petroleum ether is used, suction filtration, 60 ℃ of vacuum-dryings of filter cake 2.5 hours in diosgenin crude product cooling back.3 times repeatedly, obtain diosgenin 580.4g.Measuring detection diosgenin purity with high performance liquid chromatography (HPLC) is 96.42%.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. method for preparing diosgenin is characterized in that comprising following operation steps:
(1) with fresh Rhizome of Peltate Yam section, use water boiling and extraction, centrifugal, merge aqueous extract; With resin chromatography column on the aqueous extract, behind the water elution, be 95% ethanol elution with concentration of volume percent, collect ethanol eluate;
Or the exsiccant Rhizome of Peltate Yam pulverized, be 95% alcohol reflux with concentration of volume percent, centrifugal, united extraction liquid, concentrated; With resin chromatography column on the concentrated solution, behind the water elution, be 95% ethanol elution with concentration of volume percent, collect ethanol eluate;
Described resin chromatography column is macroporous adsorbent resin AB-8 or macroporous adsorbent resin X-5;
(2) add hydrochloric acid to step (1) gained ethanol eluate, the ethanol solution hydrochloride of making concentration and be 3～3.5mol/L is hydrolyzed, and the temperature of hydrolysis is 80～100 ℃, and the time of hydrolysis is 10～16 hours, and hydrolyzed solution is cooled to room temperature;
(3) regulate pH to 7, filter, concentrate, get concentrated filtrate;
(4) add sherwood oil to concentrated filtrate, reflux extraction, cooling concentrates, and gets crystallization, and drying gets the diosgenin finished product.
2. a kind of method for preparing diosgenin according to claim 1 is characterized in that: stir in the time of the described water boiling and extraction of step (1); Stir in the time of described alcohol reflux.
3. a kind of method for preparing diosgenin according to claim 1 is characterized in that: the number of times of the described water boiling and extraction of step (1) is 2～3 times, and each time of extracting is 1～2 hour, and the amount of at every turn extracting institute's water is 4～5 liters of/kilogram Chinese yams; The temperature of described alcohol reflux is 55 ℃～65 ℃, and the number of times of extraction is 2～3 times, and each time of extracting is 1～2 hour, and extract used alcoholic acid amount is 4～5 liters of/kilogram Chinese yams at every turn.
4. a kind of method for preparing diosgenin according to claim 1 is characterized in that: the described water elution of step (1) is to carry out water elution with 0.8～1.5 column volume.
5. a kind of method for preparing diosgenin according to claim 1 is characterized in that: the described adjusting of step (3) pH is that adding sodium hydrate solid or potassium hydroxide solid are regulated.
6. a kind of method for preparing diosgenin according to claim 1 is characterized in that: the volume add-on of the described sherwood oil of step (4) is 1～1.5 times of concentrated filtrate volume; The temperature of described reflux extraction is 50～60 ℃, and the time is 8～12 hours; Described drying is vacuum-drying, and drying temperature is 50～60 ℃, and be 2～3 hours time of drying.
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| CN102030813B (en) * | 2010-11-10 | 2013-03-06 | 北京大学 | Preparation method and application of yellow ginger zingiberensis saponin having high-efficiency anti-cancer activity |
| CN104387441A (en) * | 2014-10-24 | 2015-03-04 | 广东工业大学 | Pollution-free new technique for extracting diosgenin from yellow ginger |
| CN108434245A (en) * | 2018-06-20 | 2018-08-24 | 广东工业大学 | A kind of plant button son eggplant extract and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1699399A (en) * | 2004-05-23 | 2005-11-23 | 张万举 | Process for preparing yam saponin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1699399A (en) * | 2004-05-23 | 2005-11-23 | 张万举 | Process for preparing yam saponin |
Non-Patent Citations (1)
| Title |
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| 王凤芝等.薯蓣皂苷元的提取工艺比较.《黑龙江医药科学》.2006,第29卷(第4期),22-23. * |
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