CN106957346B - Method for preparing salicin by using populus euphratica leaves - Google Patents
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- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
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Abstract
The invention belongs to the technical field of extracting salicin from plants, and particularly relates to a method for preparing salicin by using populus euphratica leaves. The invention takes naturally dried poplar leaves as raw materials, after the processes of methanol extraction, decoloration, flocculation, filtration, petroleum ether and chloroform impurity removal, ethanol crystallization is added to obtain the salicin crystal with the content of up to 95 wt%. Can realize the resource development and utilization of the poplar leaves and provide reference for the production of salicin by enterprises. The method is simple in process, is designed according to the physicochemical characteristics of the poplar leaves, can efficiently extract high-purity salicin from the poplar leaves, enlarges the range of raw materials for preparing the salicin, and is beneficial to expanding the production scale and market application of the salicin.
Description
Technical Field
The invention belongs to the technical field of extracting salicin from plants, and particularly relates to a method for preparing salicin by using populus euphratica leaves.
Background
Salicin (a), (b), (c), (dSalicin，salicoside) Also called saligenin and saligenin, the molecular formula is C13H18O7The molecule has free phenolic hydroxyl, belonging to phenolic glycoside compounds. Is white crystal, soluble in water, soluble in boiling water, insoluble in ethanol, insoluble in ether or chloroform, and soluble in alkali solution, pyridine or glacial acetic acid. Most of the existing salicin production processes adopt a quick lime method, acid extraction and hydrous ethanol to extract willow bark, willow branches and willow leaves, and a crude product is obtained by combining a crystallization method. Further purifying by multiknot enzymolysis, resin adsorption, supercritical carbon dioxide extraction, etc. The various methods have respective advantages and disadvantages, for example, the quicklime method is not beneficial to powder control in a production workshop, but the process is simple, the cost performance is high, and mainly alkaline conditions are utilized to remove tannin substances; the carbon dioxide supercritical extraction method has high extraction efficiency but high cost; in the compound extraction methodThe product obtained by adopting a water extraction method has more impurities, which brings difficulty to separation and purification; the alcohol extraction method or the n-butanol extraction method is simple, but the solubility of the salicin in the ethanol and the n-butanol is low, so the alcohol extraction method has extremely low efficiency; the membrane filtration method is difficult to remove organic acid with molecular weight less than 5000, monosaccharide and part of pigment substances, and only polysaccharide and macromolecular particles can be removed. In summary, the method is more suitable for extracting salicin from willow leaves, branches and barks because the content of tannin substances and macromolecular particles is higher.
In the existing salicin production process, no technical scheme that populus euphratica leaves are used as raw materials is available, because the populus euphratica leaves belong to a blank area of directional selection of salicin preparation raw materials, the quantity of macromolecular particles containing tannin and polysaccharide in the populus euphratica leaves is small, and the process in the prior art is not suitable for extracting salicin in the populus euphratica leaves.
Disclosure of Invention
The invention aims to provide a method for preparing salicin by using populus euphratica leaves. The method is simple in process, is designed according to the physicochemical characteristics of the poplar leaves, can efficiently extract high-purity salicin from the poplar leaves, enlarges the range of raw materials for preparing the salicin, and is beneficial to expanding the production scale and market application of the salicin.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the method for preparing salicin by using populus euphratica leaves comprises the following steps:
1) leaching: adding methanol into dried populus diversifolia leaf powder according to the material-liquid ratio of 1:10-20, and leaching to obtain a sample solution;
2) and (3) filtering and removing impurities: removing alcohol from the sample liquid obtained in the step 1), decoloring, flocculating and filtering, taking filtrate, and sequentially removing impurities from petroleum ether and concentrating to obtain concentrated sample liquid;
3) primary crystallization: adding ethanol into the concentrated sample liquid obtained in the step 2), freezing and crystallizing, and filtering to obtain crystals with the salicin content of 60-70 wt%;
4) and (3) recrystallization: dissolving the crystal obtained in the step 3) in water, adding chloroform for removing impurities, adding ethanol again, freezing for crystallization, and filtering to obtain the crystal with the salicin content of more than 95 wt%.
Preferably, the leaching step is as follows:
pulverizing naturally dried folium populi Davidianae, adding 50% methanol solution at a material-to-liquid ratio of 1:15, extracting at 60 deg.C for 90min, cooling, filtering, and collecting filtrate to obtain sample solution.
Preferably, the filtration and impurity removal steps are as follows:
removing alcohol from the sample liquid obtained in the step 1), adding activated carbon accounting for 3wt% of the total amount of the sample liquid for decoloring for 1h, adding polyaluminium sulfate solution accounting for 1% of the total amount of the sample liquid in volume and activated clay accounting for 1wt% of the total amount of the sample liquid for flocculation, and filtering to obtain filtrate; adding petroleum ether with the same volume into the filtrate for extraction, standing for phase separation, taking the lower phase and concentrating to 1/2 volumes to obtain a concentrated sample solution. Extracting the weak polar impurities in the filtrate by using petroleum ether.
Preferably, the primary crystallization step is as follows:
adding an ethanol solution with the volume concentration of 95% into the concentrated sample liquid obtained in the step 2) according to the volume ratio of 1:5, crystallizing for 24 hours under a freezing condition, and filtering to obtain crystals with the salicin content of 60-70 wt%.
Preferably, the recrystallization step is as follows:
dissolving the crystal obtained in the step 2) in water, adding chloroform with the same volume of the water solution for extraction, standing for phase splitting, taking the upper phase, adding ethanol solution with the volume concentration of 95% according to the volume ratio of 1:5, crystallizing for 24 hours under the freezing condition, and filtering to obtain the crystal with the salicin content of not less than 95 wt%. And extracting the medium-polarity impurities in the crystal water solution by using triple filtration methane.
Preferably, the sample solution is separated and the methanol is recovered under the conditions of 0.1Mp and 60 ℃; and (3) taking the upper phase to recover the petroleum ether when the petroleum ether is extracted, kept stand and subjected to phase separation.
Preferably, when the chloroform is extracted, kept standing and separated, the chloroform is recovered by taking down the phase.
Preferably, the polyaluminium sulfate solution has a concentration of 7 wt%.
The process for extracting the raw material by taking the poplar leaves as the salicin for the first time is characterized in that an extraction solvent and relevant process parameters need to be creatively tested and selected according to the physicochemical characteristics of the poplar leaves:
1. selection of extraction solvent
Because the content of tannin substances in populus euphratica leaves is low, the inventor determines a solvent with the highest effect of dissolving salicin from different types of conventional organic extraction solvents according to the principle of similar compatibility: accurately weighing 0.1 g salicin standard, adding 1 mL frozen organic solvent (including methanol, ethanol, ethyl acetate, chloroform, n-butanol, n-hexane and petroleum ether), and shaking for 5 min. If no, 1 mL of the solution was added to 5 mL, and if no, the solution was heated in a 50 ℃ water bath. If the solution is dissolved, the solution is placed in a refrigerator at the temperature of minus 25 ℃ to see whether the dissolved substance is separated out or not. If not, the organic solvent was added to 10 mL and the phenomenon was observed. The results demonstrate that aqueous methanol dissolves best.
2. Determination of optimal extraction parameters
And after the extract is determined to be methanol aqueous solution, determining the volume concentration of the methanol aqueous solution, the ratio of the methanol aqueous solution to the populus euphratica leaves and the extraction time.
Weighing nine parts of populus diversifolia leaf powder 5g in an erlenmeyer flask, adding methanol with different concentrations according to different material-liquid ratios, extracting in a 60 ℃ water bath kettle for different times, taking out, filtering, concentrating the filtrate, evaporating to dryness, dissolving with 10 times of water, and centrifuging to remove water insoluble substances. Removing impurities from the supernatant with petroleum ether of the same volume, standing for phase separation, concentrating the water phase, evaporating to dryness, weighing, and detecting the purity.
TABLE 1 purified L of salicin from Populus euphratica leaves9（34) Results of methanol Quadrature test
| Numbering | A (volume concentration of extractant) | B (extraction time) | C (feed liquid ratio) | Empty column | Purity wt% |
| 1 | 1 (methanol anhydrous) | 1（1h） | 1(1:15) | 1 | 26.34 |
| 2 | 1 | 2（1.5h） | 2(1:20) | 2 | 46.45 |
| 3 | 1 | 3（2h） | 3(1:25) | 3 | 36.34 |
| 4 | 2 (75% methanol) | 1 | 2 | 3 | 40.45 |
| 5 | 2 | 2 | 3 | 1 | 30.53 |
| 6 | 2 | 3 | 1 | 2 | 46.48 |
| 7 | 3 (50% methanol) | 1 | 3 | 2 | 45.76 |
| 8 | 3 | 2 | 1 | 3 | 43.56 |
| 9 | 3 | 3 | 2 | 1 | 38.78 |
As can be seen from Table 1, the three factors of extractant concentration, extraction time and feed-liquid ratio have no significant effect on the purification of salicin in populus euphratica leaves through anoanalysis of variance. Therefore, A is analyzed according to the range difference3C2B3. Although the analysis of variance is not significant,however, the A-C-B is very poor and excellent, so that the A should be at the optimum level, namely A3And others may be at any level. In summary, the best combination is A3B1C1Namely, methanol with the volume concentration of 50 percent is extracted for 1h at the temperature of 60 ℃ at the feed-liquid ratio of 1: 15.
3. Determination of organic solvent impurity removing agent
And (3) analyzing the extract liquid after alcohol removal, decoloration and flocculation impurity removal, wherein the impurities are mostly weak-polarity impurities and medium-polarity impurities, and extracting the impurities by respectively adopting ethyl acetate, n-butyl alcohol, trichloroethylene, trichloroethane, n-hexane and petroleum ether.
Compared with the prior art, the invention has the following advantages:
1) the method has simple process, can efficiently extract high-purity salicin from populus euphratica leaves, expands the range of raw materials for preparing salicin, and is beneficial to expanding the production scale and market application of salicin.
2) The method is designed aiming at the physicochemical characteristic that the poplar leaves contain less tannin and polysaccharide large-particle substances, abandons the guiding of the misdistinguishing technology of removing tannin by a lime method and removing impurities such as polysaccharide and the like by membrane treatment in the prior art, adopts methanol aqueous solution to directly extract salicin, and prepares high-purity salicin by matching with petroleum ether to remove weak-polarity impurities and trichloroethane to remove medium-polarity impurities and finally crystallizing.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
1) Pulverizing naturally dried folium populi Davidianae, adding 50% methanol solution at a material-to-liquid ratio of 1:15, extracting at 60 deg.C for 90min, cooling, filtering, and collecting filtrate to obtain sample solution.
2) Separating the obtained sample liquid at 0.1Mp and 60 ℃, recovering methanol, adding activated carbon accounting for 3wt% of the total amount of the sample liquid for decoloring for 1h, adding a polyaluminium sulfate solution accounting for 1% of the total amount of the sample liquid in volume and activated clay accounting for 1wt% of the total amount of the sample liquid for flocculation, and filtering to obtain a filtrate; adding petroleum ether with the same volume to the filtrate to extract the low-polarity impurities, standing for phase splitting, taking the lower phase and concentrating to 1/2 volumes to obtain a concentrated sample solution; taking the upper phase and recovering petroleum ether.
3) Adding an ethanol solution with the volume concentration of 95% into the concentrated sample liquid obtained in the step 2) according to the volume ratio of 1:5, crystallizing for 24 hours under a freezing condition, and filtering to obtain crystals with the salicin content of 60-70 wt%.
4) Dissolving the crystal obtained in the step 2) in water, adding chloroform with the same volume of the water solution to extract medium-polarity impurities, standing for phase splitting, taking the upper phase, adding ethanol solution with the volume concentration of 95% according to the volume ratio of 1:5, crystallizing for 24 hours under the freezing condition, and filtering to obtain the crystal with the salicin content of not less than 95 wt%; taking the lower phase to recover the trichloromethane.
Example 2
1) Putting 100g of dried and crushed populus diversifolia leaves into a three-necked bottle, adding 1500 mL of methanol aqueous solution with the volume concentration of 50%, stirring and leaching in a water bath kettle at 60 ℃ for 90min, cooling, filtering, and taking filtrate to obtain sample liquid.
2) Separating the obtained sample liquid at 0.1Mp and 60 ℃ and recovering methanol to obtain a crude salicin extract (about 700 mL, the salicin purity in the crude extract is 23.5 wt%), adding 21g of activated carbon into the crude salicin extract, decoloring at 60 ℃ for 1 hour, adding 7 mL of 7wt% polyaluminum solution and 7g of activated clay, and filtering to remove impurities to obtain a refined salicin extract (about 670mL, the salicin purity in the refined extract is 41.7 wt%); adding 670mL of petroleum ether into the salicin extract to extract the low-polarity impurities, standing for phase separation, separating out a petroleum ether phase, concentrating and recovering the petroleum ether, and separating out a water phase and concentrating to 1/2 volumes (about 350 mL).
3) And adding a 95% ethanol solution with volume concentration of 5 times of the volume of the obtained concentrated water phase, stirring, dissolving thoroughly, and crystallizing for 24 hours under a freezing condition to obtain a primary crystal, wherein the content of salicin in the primary crystal is 65.6 wt%.
4) Dissolving the primary crystal in water, adding chloroform with the same volume of the water solution to extract impurities with medium polarity, standing for phase splitting, and recovering a chloroform phase; simultaneously adding 5 times volume of 95% ethanol into the water phase, and crystallizing for 24 hours under a freezing condition to obtain the salicin crystal with the content of 95.8 wt%.
Example 3
1) Putting 100g of dried and crushed populus diversifolia leaves into a three-necked bottle, adding 1500 mL of methanol aqueous solution with the volume concentration of 50%, stirring and leaching in a water bath kettle at 60 ℃ for 90min, cooling, filtering, and taking filtrate to obtain sample liquid.
2) Separating the obtained sample liquid at 0.1Mp and 60 ℃ and recovering methanol to obtain a crude salicin extract (about 650 mL, the salicin purity in the crude extract is 19.8 wt%), adding 20g of activated carbon into the crude salicin extract, decoloring at 60 ℃ for 1 hour, adding 6.5 mL of 7wt% polyaluminum solution and 6.5g of activated clay, and filtering to remove impurities to obtain a refined salicin extract (about 600mL, the salicin purity in the refined extract is 45.2 wt%); then 600mL of petroleum ether is added into the salicin extract to extract the weak polar impurities, after standing and phase splitting, the petroleum ether phase is separated out, the petroleum ether is recovered by concentration, the water phase is separated out and concentrated to 1/2 volume (about 300 mL).
3) And adding a 95% ethanol solution with volume concentration of 5 times of the volume of the obtained concentrated water phase, stirring and dissolving thoroughly, and crystallizing for 24 hours under a freezing condition to obtain a primary crystal, wherein the content of the salicin in the primary crystal is 68.4 wt%.
4) Dissolving the primary crystal in water, adding chloroform with the same volume of the water solution to extract impurities with medium polarity, standing for phase splitting, and recovering a chloroform phase; simultaneously adding 5 times volume of 95% ethanol into the water phase, and crystallizing for 24 hours under a freezing condition to obtain a salicin crystal with the content of 96.1 wt%.
Claims (1)
1. The method for preparing salicin by using populus euphratica leaves is characterized by comprising the following steps:
1) leaching: pulverizing naturally dried folium populi Davidianae, adding 50 vol% methanol solution into dried folium populi Davidianae powder at a material-to-liquid ratio of 1:15, extracting at 60 deg.C for 90min, cooling, filtering, and collecting filtrate to obtain sample solution;
2) and (3) filtering and removing impurities:
removing alcohol from the sample liquid obtained in the step 1), adding activated carbon accounting for 3wt% of the total amount of the sample liquid for decoloring for 1h, adding polyaluminium sulfate solution accounting for 1% of the total amount of the sample liquid in volume and activated clay accounting for 1wt% of the total amount of the sample liquid for flocculation, wherein the concentration of the polyaluminium sulfate solution is 7wt%, and filtering to obtain filtrate; adding petroleum ether with the same volume into the filtrate for extraction, standing for phase separation, taking the lower phase and concentrating to 1/2 volumes to obtain a concentrated sample solution; dealcoholizing the sample liquid at 0.1Mp and 60 ℃ and recovering methanol; extracting petroleum ether, standing and separating the phases, and taking the upper phase to recover the petroleum ether;
3) primary crystallization: adding an ethanol solution with the volume concentration of 95% into the concentrated sample liquid obtained in the step 2) according to the volume ratio of 1:5, crystallizing for 24 hours under a freezing condition, and filtering to obtain crystals with the salicin content of 60-70 wt%;
4) and (3) recrystallization: dissolving the crystal obtained in the step 3) in water, adding chloroform with the same volume of the water solution for extraction, standing for phase splitting, taking the lower phase for recovering the chloroform, taking the upper phase, adding an ethanol solution with the volume concentration of 95% according to the volume ratio of 1:5, crystallizing for 24 hours under the freezing condition, and filtering to obtain the crystal with the salicin content of not less than 95 wt%.
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| CN1261443C (en) * | 2003-10-30 | 2006-06-28 | 西安皓天生物工程技术有限责任公司 | Process for preparing salicin |
| CN1554663A (en) * | 2003-12-29 | 2004-12-15 | 西安三江生物工程有限公司 | Process for extracting and separating salicin from fresh hranch of red willow |
| CN102079764B (en) * | 2009-12-01 | 2013-04-17 | 汉中秦赢生物科技有限责任公司 | Method for preparing medicinal raw material salicin from white willow branch bark |
| CN104262421B (en) * | 2014-08-08 | 2017-03-08 | 图木舒克市昆神植物提取有限责任公司 | The technique extracting salicoside from Populus euphratica fallen leaves |
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