CN101974001A - Process for extracting pure liriodenine from Chinese tuliptree barks - Google Patents
Process for extracting pure liriodenine from Chinese tuliptree barks Download PDFInfo
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- CN101974001A CN101974001A CN2010102357960A CN201010235796A CN101974001A CN 101974001 A CN101974001 A CN 101974001A CN 2010102357960 A CN2010102357960 A CN 2010102357960A CN 201010235796 A CN201010235796 A CN 201010235796A CN 101974001 A CN101974001 A CN 101974001A
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Abstract
The invention relates to a process for extracting pure liriodenine from Chinese tuliptree barks, comprising the following steps: taking the Chinese tuliptree barks as the raw materials, adding certain amount of alkaline water for leaching, then adding an organic solvent for heating and extracting, after cooling filtrate, adding acid to adjust the pH value, carrying out filtration, filtering the filtrate with cation exchange resins, after concentrating lower injecting liquid, using 1-3 times volume of chloroform for extraction, carrying out magnesium oxide medium-pressure column chromatography, carrying out gradient elution with dichloromethane-methanol (50:1-1:1), carrying out detection by HPLC, combining liriodenine eluent, recovering the reagents, carrying out concentration and crystallization and then using methanol or acetone for recrystallization, thus obtaining the pure liriodenine.
Description
Technical field:
The present invention relates to a kind of extraction process of middle pharmaceutically active ingredient, is a kind of technology of extracting the purifying liriodendrin from Cortex Liriodendri Chinensis specifically.
Background technology:
Cortex Liriodendri Chinensis derives from Magnoliaceae Liriodendron plant Liriodendron Liriodendron chinensis (Hemsl.) Sarg. and yellow poplar L.tulipifera L..Be distributed in each province on the south the Changjiang river.Bark is used as medicine, property of medicine suffering, temperature.Have and dispel rheumatism, the cold cough-relieving effect of loosing.Cure mainly rheumatic arthralgia, the cough due to wind and cold.Chinese tuliptree root also can be used as medicine, and has and dispels rheumatism, the effect that strengthens muscles and bones.Cortex Liriodendri Chinensis contains alkaloid, and major part is the aporphine alkaloid, and the former aporphine alkaloid of minority also contains β-Gu Zaichun, daucosterol etc.
Liriodendrin (Liriodenine), molecular formula are C
17H
9NO
3, molecular weight is 275, mp.280-282 ℃; Molecular structural formula is:
Liriodendrin is the luxuriant and rich with fragrance isoquinoline alkaloid of A Piao, is present in a kind of activeconstituents in the Chinese medicinal plant such as Magnoliaceae, Rutaceae.Modern pharmacological research shows, that liriodendrin has is antitumor significantly, antiviral, bacteriostatic activity, antimycotic and antibacterium breeding effect, for discovering of its anticancer and anti-HIV effect: liriodendrin has significant inhibitory effect to the growth of Human Lung Cancer cell A549, can bring out the apoptosis of cancer cells, and its mechanism of action has been carried out the comparatively discussion of system.Employing mtt assay such as Liu Huagang, DNA ladder detect and RT-PCR detects and the immunocytochemical method observation finds that the liriodendrin silver complex can suppress lung carcinoma cell SPC-A-1 cell proliferation and cell death inducing, its mechanism may be the ratio that changes bax/bcl-2, change the set point of apoptosis, make apoptosis strength in cell, account for dominant advantage.
Domestic less to the liriodendrin Study on extraction, existing document only separates each chemical ingredients in the Magnoliacea plant, the extraction process of liriodendrin is not studied as yet.
Summary of the invention:
The purpose of this invention is to provide a kind of from Cortex Liriodendri Chinensis the technology of extraction separation and purifying liriodendrin, this technology specificity is strong, flow process is simple, is easy to preparation, production cost is low, the product purity height.
For achieving the above object, the present invention has taked following technical scheme:
A kind of technology of extracting the purifying liriodendrin from Cortex Liriodendri Chinensis is characterized in that comprising the following steps:
1) extracts: Cortex Liriodendri Chinensis is pulverized, crossed the 20-80 mesh sieve, drop in the extractor, add a certain amount of buck lixiviate 0.5-18 hour; Add 3-15 times of organic solvent heating extraction 0.5-3 hour again, extract 2-4 time, filter, filtrate is cooled to room temperature, adds acid and transfers pH to 4-6, filters, and gets the Cortex Liriodendri Chinensis extracting solution;
2) ion-exchange: extracting solution by Zeo-karb, is collected fluid injection down, be concentrated into density 1.05-1.20, get crude extract;
3) column chromatography: with above-mentioned crude extract with the chloroform extraction of 1-3 times of volume 2-3 time, chloroform extraction liquid is mixed sample with an amount of magnesium oxide, compression leg in the last magnesium oxide, methylene chloride-methanol (50: 1-1: 1) gradient elution, the HPLC monitoring is collected the liriodendrin elutriant, decompression and solvent recovery, concentrate crystallization, get coarse-grain;
4) crystallization: above-mentioned coarse-grain with methyl alcohol or acetone recrystallization 2-6 time, is filtered, and drying promptly gets the pure product of liriodendrin.
The described buck of step 1) is aqueous sodium hydroxide solution, sodium bicarbonate aqueous solution or liming etc., and pH is 8-13, and consumption is with submergence material degree of being, extracting mode can adopt modes such as ultrasonic lixiviate, warm water lixiviate, boiling water bath lixiviate.
In the described organic solvent extraction of step 1): the optional 50-90% aqueous ethanolic solution of organic solvent, methanol aqueous solution or aqueous acetone solution, extracting mode can adopt a kind of in heating and refluxing extraction, Soxhlet extraction, supersound extraction or the microwave extraction.
Used acid can be selected hydrochloric acid, sulfuric acid, tartrate, phosphoric acid for use in the described acid accent of the step 1) pH step, transfers pH to 4-6.
The magnesium oxide order number of magnesium oxide column packed in the described column chromatography of step 3) is the 150-300 order, and the post blade diameter length ratio is 1: 5-10, magnesium oxide and upper prop liquid mass ratio are 4 in the column chromatography: 1-6: 1.
The volume ratio of methylene chloride-methanol is 50 in the described eluent of step 3): 1-1: 1, and volume ratio is 50: 1,20: 1,10: 1,8: 2,2: 1 specifically.
The invention has the advantages that:
(1) present method water-soluble impurity is few, and lipotropy impurity can transfer pH to remove through acid;
(2) the present invention uses organic solvent extraction after adopting alkaline soak again, has reduced consumption of organic solvent, cuts down the consumption of energy, and cost is low, extraction yield is high;
(3) press magnesium oxide post elute effect good in, processing speed is fast.
Embodiment:
The present invention is described further below in conjunction with embodiment.
Embodiment one:
Get dry Cortex Liriodendri Chinensis and pulverized 40 mesh sieves, take by weighing 8kg and drop in the extractor, add pH and be 12 aqueous sodium hydroxide solution, soaked 12 hours under 30 ℃ of conditions until the submergence material, add 6 times of 60% ethanolic soln reflux again, extraction time is 2 hours, extracts 3 times, filters, filtrate is cooled to room temperature, add 0.5mol/L hydrochloric acid and transfer pH to 4, filter, get the Cortex Liriodendri Chinensis extracting solution; The Cortex Liriodendri Chinensis extracting solution is passed through the D72 large hole cation exchanger resin, collect fluid injection down, be concentrated into density 1.15, use the chloroform extraction of 2 times of volumes again, extract 2 times, dry (the pressure 0.8Mpa of compression leg in the last magnesium oxide after extraction liquid and 2 times of amount 200-300 order magnesium oxide are fully mixed thoroughly, blade diameter length ratio 1: 7), use methylene chloride-methanol mixed solution (50: 1 successively, 20: 1,10: 1,8: 2,2: 1) the elutriant wash-out, collect elutriant, under instructing, HPLC merges required activeconstituents, reclaim methylene dichloride, methyl alcohol, obtain the liriodendrin crude product, crude product is made saturated solution with the acetone heating for dissolving, place crystallization, filter, recrystallization 3 times, cryodrying promptly gets the liriodendrin crystal, and crystallization detects through HPLC, with the liriodendrin is reference substance, liriodendrin content 95.7%.
Embodiment two:
Get dry Cortex Liriodendri Chinensis and pulverized 20 mesh sieves, take by weighing 10kg and drop in the extractor, add pH and be 10 lime aqueous solution until the submergence material, at power is 50W, ultrasonic lixiviate is 40 minutes under 40 ℃ of conditions of temperature, adds 4 times of 80% ethanolic soln Soxhlet again and extracts, and extraction time is 4 hours, extract 2 times, filter, filtrate is cooled to room temperature, add 0.5mol/L phosphoric acid and transfer pH to 5, filter, get the Cortex Liriodendri Chinensis extracting solution; The Cortex Liriodendri Chinensis extracting solution is passed through 001 * 7 strongly acidic cation-exchange, collect fluid injection down, be concentrated into density 1.10, use the chloroform extraction of 2 times of volumes again, extract 3 times, dry (the pressure 0.7Mpa of compression leg in the last magnesium oxide after extraction liquid and 3 times of amount 150-250 order magnesium oxide are fully mixed thoroughly, blade diameter length ratio 1: 5), use methylene chloride-methanol mixed solution (50: 1 successively, 20: 1,10: 1,8: 2,2: 1) the elutriant wash-out, collect elutriant, under instructing, HPLC merges required activeconstituents, reclaim methylene dichloride, methyl alcohol, obtain the liriodendrin crude product, crude product is made saturated solution with the methyl alcohol heating for dissolving, place crystallization, filter, recrystallization 4 times, cryodrying promptly gets the liriodendrin crystal, and crystallization detects through HPLC, with the liriodendrin is reference substance, liriodendrin content 92.5%.
Embodiment three:
Get dry Cortex Liriodendri Chinensis and pulverized 50 mesh sieves, take by weighing 10kg and drop in the extractor, add pH and be 13 sodium bicarbonate aqueous solution, in boiling water bath, soaked 8 hours until the submergence material, add 8 times of 75% methanol solution supersound extraction again, extraction time is 1 hour, extracts 3 times, filters, filtrate is cooled to room temperature, add 0.5mol/L tartrate and transfer pH to 5, filter, get the Cortex Liriodendri Chinensis extracting solution; The Cortex Liriodendri Chinensis extracting solution is passed through 004 * 7 strongly acidic cation-exchange, collect fluid injection down, be concentrated into density 1.12, use the chloroform extraction of 3 times of volumes again, extract 2 times, dry (the pressure 0.6Mpa of compression leg in the last magnesium oxide after extraction liquid and 2 times of amount 200-300 order magnesium oxide are fully mixed thoroughly, blade diameter length ratio 1: 10), use methylene chloride-methanol mixed solution (50: 1 successively, 20: 1,10: 1,8: 2,2: 1) the elutriant wash-out, collect elutriant, under instructing, HPLC merges required activeconstituents, reclaim methylene dichloride, methyl alcohol, obtain the liriodendrin crude product, crude product is made saturated solution with the acetone heating for dissolving, place crystallization, filter, recrystallization 5 times, vacuum-drying promptly gets the liriodendrin crystal, and crystallization detects through HPLC, with the liriodendrin is reference substance, liriodendrin content 93.8%.。
Embodiment four:
Get dry Cortex Liriodendri Chinensis and pulverized 30 mesh sieves, take by weighing 13.5kg and drop in the extractor, add pH and be 12 aqueous sodium hydroxide solution, in 40 ℃ of water-baths, soaked 14 hours until the submergence material, add 5 times of 50% acetone soln heating and refluxing extraction again, extraction time is 4 hours, extracts 2 times, filters, filtrate is cooled to room temperature, add 0.5mol/L sulfuric acid and transfer pH to 4, filter, get the Cortex Liriodendri Chinensis extracting solution; The Cortex Liriodendri Chinensis extracting solution is passed through 001 * 7 strongly acidic cation-exchange, collect fluid injection down, be concentrated into density 1.19, use the chloroform extraction of 3 times of volumes again, extract 3 times, dry (the pressure 0.7Mpa of compression leg in the last magnesium oxide after extraction liquid and 3 times of amount 150-250 order magnesium oxide are fully mixed thoroughly, blade diameter length ratio 1: 8), use methylene chloride-methanol mixed solution (50: 1 successively, 20: 1,10: 1,8: 2,2: 1) the elutriant wash-out, collect elutriant, under instructing, HPLC merges required activeconstituents, reclaim methylene dichloride, methyl alcohol, obtain the liriodendrin crude product, crude product is made saturated solution with the acetone heating for dissolving, place crystallization, filter, recrystallization 3 times, cryodrying promptly gets the liriodendrin crystal, and crystallization detects through HPLC, with the liriodendrin is reference substance, liriodendrin content 94.2%.
Embodiment five:
Get dry Cortex Liriodendri Chinensis and pulverized 60 mesh sieves, take by weighing 15kg and drop in the extractor, add pH and be 11 lime aqueous solution until the submergence material, at power 100W, microwave extraction is 1 hour under 45 ℃ of conditions of temperature, adds 7 times of 70% ethanolic soln Soxhlet again and extracts, and extraction time is 3 hours, extract 3 times, filter, filtrate is cooled to room temperature, add 0.5mol/L tartrate and transfer pH to 5, filter, get the Cortex Liriodendri Chinensis extracting solution; The Cortex Liriodendri Chinensis extracting solution is passed through the D72 large hole cation exchanger resin, collect fluid injection down, be concentrated into density 1.14, use the chloroform extraction of 2 times of volumes again, extract 3 times, dry (the pressure 0.6Mpa of compression leg in the last magnesium oxide after extraction liquid and 2 times of amount 200-300 order magnesium oxide are fully mixed thoroughly, blade diameter length ratio 1: 8), use methylene chloride-methanol mixed solution (50: 1 successively, 20: 1,10: 1,8: 2,2: 1) the elutriant wash-out, collect elutriant, under instructing, HPLC merges required activeconstituents, reclaim methylene dichloride, methyl alcohol, obtain the liriodendrin crude product, crude product is made saturated solution with the methyl alcohol heating for dissolving, place crystallization, filter, recrystallization 5 times, vacuum-drying promptly gets the liriodendrin crystal, and crystallization detects through HPLC, with the liriodendrin is reference substance, liriodendrin content 92.8%.
Claims (6)
1. a technology of extracting the purifying liriodendrin from Cortex Liriodendri Chinensis is characterized in that comprising the following steps:
1) extracts: Cortex Liriodendri Chinensis is pulverized, crossed the 20-80 mesh sieve, drop in the extractor, add a certain amount of buck lixiviate 0.5-18 hour; Add 3-15 times of organic solvent heating extraction 0.5-3 hour again, extract 2-4 time, filter, filtrate is cooled to room temperature, adds acid and transfers pH to 4-6, filters, and gets the Cortex Liriodendri Chinensis extracting solution;
2) ion-exchange: extracting solution by Zeo-karb, is collected fluid injection down, be concentrated into density 1.05-1.20, get crude extract;
3) column chromatography: with above-mentioned crude extract with the chloroform extraction of 1-3 times of volume 2-3 time, chloroform extraction liquid is mixed sample with an amount of magnesium oxide, compression leg in the last magnesium oxide, methylene chloride-methanol (50: 1-1: 1) gradient elution, the HPLC monitoring is collected the liriodendrin elutriant, decompression and solvent recovery, concentrate crystallization, get coarse-grain;
4) crystallization: above-mentioned coarse-grain with methyl alcohol or acetone recrystallization 2-6 time, is filtered, and drying promptly gets the pure product of liriodendrin.
2. a kind of technology of from Cortex Liriodendri Chinensis, extracting the purifying liriodendrin according to claim 1, it is characterized in that the described buck of step 1) is aqueous sodium hydroxide solution, sodium bicarbonate aqueous solution or liming etc., pH is 8-13, consumption is with submergence material degree of being, extracting mode can adopt modes such as ultrasonic lixiviate, warm water lixiviate, boiling water bath lixiviate.
3. a kind of technology of from Cortex Liriodendri Chinensis, extracting the purifying liriodendrin according to claim 1, it is characterized in that in the described organic solvent extraction of step 1): the optional 50-90% aqueous ethanolic solution of organic solvent, methanol aqueous solution or aqueous acetone solution, extracting mode can adopt a kind of in heating and refluxing extraction, Soxhlet extraction, supersound extraction or the microwave extraction.
4. a kind of technology of extracting the purifying liriodendrin from Cortex Liriodendri Chinensis according to claim 1 is characterized in that used acid can be selected hydrochloric acid, sulfuric acid, tartrate, phosphoric acid for use in the described acid accent of the step 1) pH step, transfers pH to 4-6.
5. a kind of technology of from Cortex Liriodendri Chinensis, extracting the purifying liriodendrin according to claim 1, it is characterized in that: the magnesium oxide order number of filling in the described column chromatography of step 3) is the 150-300 order, the post blade diameter length ratio is 1: 5-10, magnesium oxide and upper prop liquid mass ratio are 4 in the column chromatography: 1-6: 1.
6. a kind of technology of from Cortex Liriodendri Chinensis, extracting the purifying liriodendrin according to claim 1, it is characterized in that: the volume ratio of methylene chloride-methanol is 50 in the described eluent of step 3): 1-1: 1, and volume ratio is 50: 1,20: 1,10: 1,8: 2,2: 1 specifically.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102357960A CN101974001A (en) | 2010-07-26 | 2010-07-26 | Process for extracting pure liriodenine from Chinese tuliptree barks |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102335234A (en) * | 2011-08-08 | 2012-02-01 | 南京林业大学 | Alkaloid extract of trembling poplar as well as extraction method and application thereof |
| CN103333174A (en) * | 2013-07-04 | 2013-10-02 | 天津市南开医院 | Preparation method of Liriodendrin |
| CN110721188A (en) * | 2019-11-18 | 2020-01-24 | 牡丹江医学院 | Pharmaceutical composition for treating leukemia |
-
2010
- 2010-07-26 CN CN2010102357960A patent/CN101974001A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102335234A (en) * | 2011-08-08 | 2012-02-01 | 南京林业大学 | Alkaloid extract of trembling poplar as well as extraction method and application thereof |
| CN102335234B (en) * | 2011-08-08 | 2013-11-13 | 南京林业大学 | Alkaloid extract of trembling poplar as well as extraction method and application thereof |
| CN103333174A (en) * | 2013-07-04 | 2013-10-02 | 天津市南开医院 | Preparation method of Liriodendrin |
| CN103333174B (en) * | 2013-07-04 | 2015-04-15 | 天津市南开医院 | Preparation method of Liriodendrin |
| CN110721188A (en) * | 2019-11-18 | 2020-01-24 | 牡丹江医学院 | Pharmaceutical composition for treating leukemia |
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Application publication date: 20110216 |