CN1978422B - Method for separating and purifying shikimic acid - Google Patents
Method for separating and purifying shikimic acid Download PDFInfo
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- CN1978422B CN1978422B CN2005101113031A CN200510111303A CN1978422B CN 1978422 B CN1978422 B CN 1978422B CN 2005101113031 A CN2005101113031 A CN 2005101113031A CN 200510111303 A CN200510111303 A CN 200510111303A CN 1978422 B CN1978422 B CN 1978422B
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- shikimic acid
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- essential oil
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- JXOHGGNKMLTUBP-JKUQZMGJSA-N shikimic acid Natural products O[C@@H]1CC(C(O)=O)=C[C@H](O)[C@@H]1O JXOHGGNKMLTUBP-JKUQZMGJSA-N 0.000 title claims abstract description 70
- JXOHGGNKMLTUBP-HSUXUTPPSA-N shikimic acid Chemical compound O[C@@H]1CC(C(O)=O)=C[C@@H](O)[C@H]1O JXOHGGNKMLTUBP-HSUXUTPPSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000341 volatile oil Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000605 extraction Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 7
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000011347 resin Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- 150000003440 styrenes Chemical class 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 239000002585 base Substances 0.000 claims 2
- 125000000129 anionic group Chemical group 0.000 claims 1
- 239000012141 concentrate Substances 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 claims 1
- 150000003364 shikimic acids Chemical class 0.000 claims 1
- 240000007232 Illicium verum Species 0.000 abstract description 8
- 235000008227 Illicium verum Nutrition 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 239000000284 extract Substances 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000001757 shikimic acid group Chemical group 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010008132 Cerebral thrombosis Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 201000001429 Intracranial Thrombosis Diseases 0.000 description 1
- 240000009023 Myrrhis odorata Species 0.000 description 1
- 235000007265 Myrrhis odorata Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000012550 Pimpinella anisum Nutrition 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 241000218315 Winteraceae Species 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011275 oncology therapy Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- PGZUMBJQJWIWGJ-ONAKXNSWSA-N oseltamivir phosphate Chemical compound OP(O)(O)=O.CCOC(=O)C1=C[C@@H](OC(CC)CC)[C@H](NC(C)=O)[C@@H](N)C1 PGZUMBJQJWIWGJ-ONAKXNSWSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
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- 229940061367 tamiflu Drugs 0.000 description 1
- 241000712461 unidentified influenza virus Species 0.000 description 1
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- 239000003643 water by type Substances 0.000 description 1
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Abstract
本发明公开了一种八角叶精油提取后残渣的再利用。含有莽草酸的八角叶精油提取后残渣用水溶解后经强碱性阴离子交换树脂和强酸性阳离子交换树脂处理后得到的洗脱液浓缩后在低温下结晶得到高纯度的莽草酸。本发明利用八角叶生产挥发油后的剩余残渣生产莽草酸，工艺简单，其工艺过程不需要特殊设备，即可生产高纯度莽草酸，具高回收率，可达80％以上，高纯度，可达98％以上，大大的降低了莽草酸的生产成本，而且节省能源，生产周期短，消耗溶剂少，基本不使用有机溶媒对环境污染小等优点。适于一般药厂生产。The invention discloses the reutilization of residue after extraction of star anise leaf essential oil. The residue after extraction of star anise leaf essential oil containing shikimic acid is dissolved in water, and the eluate obtained after being treated with strong basic anion exchange resin and strong acid cation exchange resin is concentrated and then crystallized at low temperature to obtain high purity shikimic acid. The present invention utilizes the remaining residue after producing volatile oil from star anise leaves to produce shikimic acid, the process is simple, and the process does not require special equipment to produce high-purity shikimic acid with a high recovery rate of more than 80% and a high purity of up to More than 98%, which greatly reduces the production cost of shikimic acid, and has the advantages of energy saving, short production cycle, less solvent consumption, basically no use of organic solvents, and little environmental pollution. Suitable for general pharmaceutical production.
Description
Technical field
The present invention relates to natural product chemistry, after more specifically referring to extract essential oil in the anistree leaf, the method for extraction from residue, separation, purifying shikimic acid.
Background technology
Shikimic acid (shikimic acid), chemistry is called 3,4,5-trihydroxy--1-cyclohexyl-1-carboxylic acid, molecular formula is C
7H
10O
5Molecular weight is 174.16.Soluble in water, be insoluble in chloroform, benzene and sherwood oil.185 ℃～187 ℃ of fusing points.Being a kind of monomeric compound that extracts from the fruit star anise of Winteraceae plant anise, anti-inflammatory, analgesic activity are arranged, is the cancer therapy drug intermediate.The unique of World Health Organization's affirmation at present is the raw material synthetic with the shikimic acid to the effective medicine Tamiflu of H5N1 avian influenza virus exactly; Beijing University of Chinese Medicine's Pharmacology Lab early-stage Study finds that first shikimic acid has obvious anti-thrombosis function, can suppress artery and vein thrombus and cerebral thrombosis.Shikimic acid belongs to high value added product, and its market price is 400 dollars/kilogram at present, and its price is also in rising.
All the time, shikimic acid all makes with synthesis method, and high-purity shikimic acid process for purification report also seldom.With the separating substances of shikimic acid and similar also is the thing of comparison difficulty always.
Nineteen sixty Simonart and Wiaux had once reported the method (Nature, 186,78-79,1960) with anion exchange process shikimic acid fermented liquid.But they well do not separate by products such as shikimic acid and dehydroshikimis acid.The Japanese is studying the separation method of shikimic acid always recently, and some patents have been applied for, comprising two pieces of world patents (international publication PCT/IB03/00131 and PCT/JP01/02086), but these methods all are methods of extracting from shikimic acid fermented liquid or anistree fruit star anise.
Star anise belongs to integration of drinking and medicinal herbs, both can be used for eating at home, also be used in the traditional Chinese medical science prescription, very big at consumption among the people, and at present most in the world shikimic acid all extracts from star anise and obtains, though extracting method is very ripe, the resource-constrained of star anise can not satisfy the demand of present All Around The World for shikimic acid at all; And the resource of anistree leaf is very sufficient, shikimic acid content wherein is probably about 5% after testing, but present anistree leaf mainly is to be used for industrialization to extract its essential oil, and remaining waste residue (tankage) goes out of use, well do not utilized, very unfortunate, after testing, the content of shikimic acid is about 10～20% in the tankage.
Present method can extract shikimic acid (tankage) from the waste residue of anistree leaf essential oil extraction back efficiently, has reduced the production cost of shikimic acid greatly.Be a kind of good shikimic acid process for purification, and can be, accomplish the largest optimization configuration of resource, thereby provide an economical and practical industrialized producing technology for the extraction separation of shikimic acid the waste liquid utilization of waste material.
Summary of the invention
The purpose of this invention is to provide a kind of from anistree leaf, extract essential oil after, from this residue, extract the method for shikimic acid.
The present invention adopts negatively charged ion and cationic exchange resin adsorption to replace wash-out, removes impurity, extracts the method for shikimic acid.
The present invention is meant that anistree leaf is through fat-soluble solvent, as the residue that obtains behind the essential oil in the anistree leaf of extractions such as normal hexane, with this residue with water dissolution after, adopt anionite-exchange resin, anionite-exchange resin is advisable with basic resin, eluent is advisable with strong alkali solution, and is best with NaOH and KOH liquid especially.
This method is finished by utilizing OH type resin, make the alkalinisation treatment process that contains shikimic acid solution and anionite-exchange resin adsorption process to merge into a step.
The anionite-exchange resin that present method is used is the best with this quasi-alkali resin of 717 strong-basicity styrene series (Shanghai remittance fat).Resin demand will carry out equivalent conversion according to total ionic weight in the shikimic acid stock liquid, that is to say that the loading capacity of resin will surpass the molar weight of the whole ions (comprising amino acid, organic acid, chloride ion) in the stock liquid.
Various stock liquids after the alkalinisation treatment utilize plastic resin treatment in order to following method.
Absorption: stock liquid is flow through anionite-exchange resin shikimic acid is adsorbed on the resin, temperature is controlled at below 90 ℃ when crossing post, crosses post liquid PH and is controlled at neutrality or alkalescence, flow velocity SV=1～5 (being advisable with SV=1～3).After the absorption,, remove impurity such as carbohydrate with the pure water rinsing resin of 1～5 times of column volume (being advisable) with 3 times of amounts.
Wash-out: shikimic acid is eluted from resin, can utilize strong alkaline aqueous solution.Solution passes through resin with 3 ~ 5 times of amount column volumes with flow velocity SV=1～5 (being advisable with SV=1～3), shikimic acid can be eluted.When it should be noted that to some impurity beyond the removal dehydroshikimis acid or class edge thing, eluent is good with aqueous alkali, and concentration is 1%～10%NaOH or KOH, and the best is the 1%～5%NaOH or the KOH aqueous solution.Can be referring to the HPLC analysis chart of Fig. 2.
Remove sodium ion: in the NaOH aqueous solution or KOH aqueous solution wash-out, elutriant can be removed sodium ion with strong acidic ion resin.The Zeo-karb that present method is used is the best with 732 strongly acidic styrenes system (Shanghai remittance fat) this class highly acidic resin.
The shikimic acid solution of gained can utilize the method for concentrating under reduced pressure cooling crystallization to obtain the crystallization of shikimic acid, and recrystallization solvent is water or C
1-C
4Alcohol or rare alcohol, recrystallization carries out at-15～15 ℃.
Beneficial effect:
Invention utilizes the residual residue production shikimic acid after anistree leaf is produced volatile oil, and technology is simple, and its technological process does not need specific installation, can produce high-pure shikimic acid, the tool high-recovery can reach more than 80% high purity, can reach more than 98%, reduce the production cost of shikimic acid greatly, and saved the energy, with short production cycle, the consumption solvent is few, does not use advantages such as the organic solvent environmental pollution is little substantially.Being suitable for general pharmaceutical factory produces.
Description of drawings
Fig. 1 is the operational path of extraction separation shikimic acid from anistree leaf essential oil extraction back is residual.
Fig. 2 is the analysis chart of the isolating HPLC of shikimic acid.
Embodiment
Embodiment 1
Anistree leaf essential oil extraction back residue 100g (shikimic acid content is 12% after testing) with the dissolving of 200ml pure water, adds the gac (Haiyang Chemical Plant, Qingdao) of 5g, and room temperature～45 ℃ stirring 30min filters and obtains destainer.500ml adorns post with 717 strong-basicity styrene series (Shanghai remittance fat), and the NaOH solution with 3% is treated to OH type resin column with it.Above-mentioned destainer is crossed the OH type anion-exchange resin column of handling, the absorption shikimic acid.The 1000ml pure water cleans, and uses the NaOH wash-out of 1500ml3% afterwards, obtains containing the position of shikimic acid.Sodium ion is removed by H type storng-acid cation exchange resin (732 strongly acidic styrenes system, fat converges in Shanghai) 500ml in this position.The solution concentration of gained.Leave standstill crystallization in the time of 0～4 ℃, get shikimic acid (9.7g, 98.5%).
Purity check chromatographic condition: instrument: high performance liquid chromatograph is that U.S. Waters company produces Waters2690,2487 UV-detector; Chromatographic column is diol post (4.6 * 250mm, 5 μ m); Detect wavelength: 210nm; Column temperature: 25 ℃; Moving phase: 98% acetonitrile: 2%0.1% phosphate aqueous solution; Flow velocity: 0.8ml/min; The retention time of shikimic acid is 11min.
Embodiment 2
Anistree leaf essential oil extraction back residue 1000g (shikimic acid content is 10% after testing) with the dissolving of 2000ml pure water, adds the gac (with the pure medicine of light) of 50g, and room temperature～45 ℃ stirring 30min filters and obtains destainer.5000ml adorns post with 717 strong-basicity styrene series (Shanghai remittance fat), and the NaOH solution with 5% is treated to OH type resin column with it.Above-mentioned destainer is crossed the OH type anion-exchange resin column of handling, the absorption shikimic acid.The 10000ml pure water cleans, and uses the NaOH wash-out of 15000ml5% afterwards, obtains containing the position of shikimic acid.Sodium ion is removed by H type storng-acid cation exchange resin (732 strongly acidic styrenes system, fat converges in Shanghai) 5000ml in this position.The solution concentration of gained.Leave standstill crystallization in the time of 0～4 ℃, get shikimic acid (88.5g, 98.2%).
Embodiment 3
Anistree leaf essential oil extraction back residue 1000g (shikimic acid content is 10% after testing) with the dissolving of 2000ml pure water, adds the gac (with the pure medicine of light) of 50g, and room temperature～45 ℃ stirring 30min filters and obtains destainer.5000ml adorns post with 717 strong-basicity styrene series (Shanghai remittance fat), and the NaOH solution with 10% is treated to OH type resin column with it.Above-mentioned destainer is crossed the OH type anion-exchange resin column of handling, the absorption shikimic acid.The 10000ml pure water cleans, and uses the NaOH wash-out of 15000ml10% afterwards, obtains containing the position of shikimic acid.Sodium ion is removed by H type storng-acid cation exchange resin (732 strongly acidic styrenes system, fat converges in Shanghai) 5000ml in this position.The solution concentration of gained.Leave standstill crystallization in the time of 0～4 ℃, get shikimic acid.
Embodiment 4
Anistree leaf essential oil extraction back residue 1000g (shikimic acid content is 10% after testing) with the dissolving of 2000ml pure water, adds the gac (with the pure medicine of light) of 50g, and room temperature～45 ℃ stirring 30min filters and obtains destainer.5000ml adorns post with 717 strong-basicity styrene series (Shanghai remittance fat), and the NaOH solution with 1% is treated to OH type resin column with it.Above-mentioned destainer is crossed the OH type anion-exchange resin column of handling, the absorption shikimic acid.The 10000ml pure water cleans, and uses the NaOH wash-out of 15000ml1% afterwards, obtains containing the position of shikimic acid.Sodium ion is removed by H type storng-acid cation exchange resin (732 strongly acidic styrenes system, fat converges in Shanghai) 5000ml in this position.The solution concentration of gained.Leave standstill crystallization in the time of 0～4 ℃, get shikimic acid.
Claims (5)
1. a method of separating shikimic acid is characterized in that:, specifically comprise the steps: as raw material with the residue behind the extraction essential oil in the anistree leaf
A. the residue of removing in the anistree leaf behind the essential oil is soluble in water, and activated carbon decolorizing filters to such an extent that destainer is stand-by;
B. adorn post with strongly basic anion exchange resin, with the 1-10% strong base solution handle OH type resin column;
C. with above-mentioned OH type resin column absorption shikimic acid on the above-mentioned stand-by residue destainer, pure water is washed the 1-10% strong base solution and is washed to such an extent that contain the elutriant of shikimic acid;
D. this shikimic acid elutriant is removed the metal ion in the aqueous alkali by H type storng-acid cation exchange resin, concentrate shikimic acid, recrystallization gets pure shikimic acid.
2. the method for separation shikimic acid according to claim 1 is characterized in that: described strongly basic anionic resin is 717 strong-basicity styrene series.
3. the method for separation shikimic acid according to claim 1 is characterized in that: the highly basic elutriant is 1-10%NaOH or KOH solution.
4. the method for separation shikimic acid according to claim 1 is characterized in that: storng-acid cation exchange resin is 732 strongly acidic styrenes systems.
5. the method for separation shikimic acid according to claim 1 is characterized in that: the shikimic acid recrystallization solvent is water or C
1-C
4Alcohol, temperature is-15～15 ℃ during recrystallization.
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| CN2005101113031A CN1978422B (en) | 2005-12-08 | 2005-12-08 | Method for separating and purifying shikimic acid |
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| CN1978422B true CN1978422B (en) | 2011-07-20 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102584571A (en) * | 2011-11-21 | 2012-07-18 | 河南孟成生物药业股份有限公司 | Extraction process for shikimic acid in fermentation liquor |
| CN102826994A (en) * | 2012-09-17 | 2012-12-19 | 广西中医药大学 | Preparation method of shikimic acid |
| JP6893356B2 (en) * | 2017-08-24 | 2021-06-23 | 一般社団法人八角平和計画研究所 | How to make shikimic acid |
| CN109721487B (en) * | 2019-01-15 | 2021-11-30 | 浙江海正药业股份有限公司 | Process for efficiently purifying shikimic acid by using continuous ion exchange technology |
| CN111056941B (en) * | 2019-12-26 | 2022-07-05 | 浙江康恩贝制药股份有限公司 | Method for preparing high-purity shikimic acid by utilizing ginkgo leaf extract chromatography waste liquid |
| CN113582835A (en) * | 2021-08-05 | 2021-11-02 | 湖北金日生态能源股份有限公司 | Method for extracting shikimic acid from ginkgo leaf waste residue and application |
| CN114436816B (en) * | 2021-12-25 | 2024-05-28 | 新疆阜丰生物科技有限公司 | Method for efficiently extracting shikimic acid by ion exchange technology |
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| JP特开2001-258583A 2001.09.25 |
| JP特开2001-26567A 2001.01.30 |
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