CN101318893B - Process for extracting shikimic acid and ethereal oil from octagonal - Google Patents
Process for extracting shikimic acid and ethereal oil from octagonal Download PDFInfo
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- CN101318893B CN101318893B CN2006101264182A CN200610126418A CN101318893B CN 101318893 B CN101318893 B CN 101318893B CN 2006101264182 A CN2006101264182 A CN 2006101264182A CN 200610126418 A CN200610126418 A CN 200610126418A CN 101318893 B CN101318893 B CN 101318893B
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- shikimic acid
- anise
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- volatile oil
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Abstract
The present invention discloses a process route for synchronous extraction of shikimic acid and essential oil from star aniseseen, belonging to the natural product separating and extracting technical field. The process route combines the separation and extraction process of the shikimic acid from the star aniseseen and the separation and extraction process of the essential oil from the star anisessen and realizes the synchronous extraction of the shikimic acid and the essential oil from the star aniseseen. A 3 percent shikimic acid and an 8 percent essential oil can be obtained by operating according to the process route. The shikimic acid is recognized as a starting material for synthesizing Tamiflu which is specific medicine against the H5N1 type Avian influenza virus, while the essential oil of the star aniseseen is recognized as a natural essence and a flavouring substance which has wide applications in food, drink, spice, wine, tobacco, etc. fields at home and abroad. Synchronous extraction of the two products of high additional value has a great importance to the comprehensive use of the star aniseseen in China.
Description
Technical field
This patent relates to a kind of separation-extraction technology that obtains shikimic acid and volatile oil from anise simultaneously, belongs to the separation and extraction technology field of natural product.
Background technology
Anise is the dry mature fruit of Magnoliacea plant anise (Illicium verum Hook.f.), is distinctive special product spice of China and Chinese medicine class economic plants resource, and its producing region mainly is distributed in provinces such as China Guangxi, Guizhou, Yunnan.Wherein contain unique fragrance ingredient, traditionally, it is the main raw material of traditional Chinese food flavourings such as the spice mixture that abounds with of China, fricassee material, SHISANXIANG, the then common wherein contained volatile oil of the steam distilled method separation and Extraction of water in the essence and flavoring agent industry, be used for single from suitable-methyl allylphenol, the preparation aubepine as the daily essence of allotment perfumed soap, oral-cavity article etc., also is used for the product essence such as candy, beverage, cigarette, wine with medicine fragrance.Simultaneously, anistree have the cough-relieving of being good for the stomach effect as traditional herbal medicine, pharmaceutically is used for the treatment of diseases such as neurasthenia, maldigestion, Jie Xian.
The Star Anise Fruit essential oil is colourless to weak yellow liquid, has the special aroma of anistree sample, and it is sweet to distinguish the flavor of, and is frozen into white cured shape solid during low temperature, and zero pour is 21-22 ℃, and boiling range is 231-237 ℃, proportion d
4 15Be 0.980-0.994, refractive index n
20Be 1.553-1.558, can be dissolved in 95% ethanol of 2-3 times of volume and 80% ethanol of about 8 times of volumes, almost insoluble with water, main component is suitable-methyl allylphenol of about 87%, with about 8% limonene, and qualitative significant aubepine (1%), phantol (0.8%) and methyl chavicol compositions such as (0.5%).
Shikimic acid is natural 3,4 in the anise that be present in, 5-dihydroxyl-1-tetrahydrobenzene-1-carboxylic acid, and molecular formula is C
7H
10O
5, molar mass is 174.15gmol
-1, its English name is Shikimic acid, and CAS is numbered 138-59-0, and EINECS is numbered 205-334-2.These product are white powder, proportion 1.64, and fusing point 185-187 ℃, soluble in water, the solubleness in water is 180gl
-1, its topmost plant origin is the dry mature fruit of Magnoliacea plant anise (Illicium verum Hook.f.).
Research about shikimic acid, external research mainly concentrates on the utilization biotechnology and transforms microorganism, by shikimic acid related in the shikimic acid pathway being produced and metabolism two big enzyme groups' gene recombination and regulation and control, construct the genetic engineering bacterium that can in fermented liquid, accumulate shikimic acid, thereby realize on the fermentative Production of shikimic acid
[1,2]Meanwhile, also by the research of the measuring method of relevant shikimic acid
[3]Domestic research is less relatively, only limits to the measuring method aspect of shikimic acid
[4]
About the research of separation and Extraction useful component from anise, the steam distillation technology belongs to traditional sophisticated volatile oil separation and extraction technology, in many relevant engineering professional books introduction is arranged all
[5]In addition, there are a lot of relevant utilization new technologies to carry out the research of the separation and Extraction of Star Anise Fruit essential oil at present
[6,7], but the research report that relates to the separation and extraction technology of shikimic acid in the anise does not have substantially.Especially, do not see any bibliographical information both at home and abroad about while separation and Extraction shikimic acid and Star Anise Fruit essential oil from anise.
Reference:
[1]US?Patent6472169.
[2]US?Patent6613552.
[3]US?Patent6482654.
[4] Wang Xiaoqiang, Guo Yajian, Yang Chunshu. high-efficient liquid phase technique is measured the content [J] of shikimic acid in the Illicium part fruit. CHINA JOURNAL OF CHINESE MATERIA MEDICA, 2001,26 (7): 447-449.
[5] Philip R.Ashurst work Tang Luhong translates. the chemistry of food flavor(ing) and technology
[6] Wang Qin, Jiang Lin, Wen Qibiao. anistree progress [J]. grain and grease, 2005,5:42-44.
[7] Gong Lifen, Hu Donghong, Pan Xiaofang etc. the research [J] of extraction using alcohol Fructus Anisi Stellati oil technology. Quanzhou Normal University's journal, 2002,20 (2): 66-69.
Summary of the invention
This patent has been invented an operational path that extracts shikimic acid and volatile oil from anise simultaneously.Comparatively unique is, it organically has been integrated into the separation-extraction technology of shikimic acid in the anise and traditional in the water vapour distillation technology of separation and Extraction volatile oil, has realized obtaining simultaneously from anise the purpose of shikimic acid and Star Anise Fruit essential oil from anise.Operate according to this patent, compare, can not reduce wherein arbitrary product with traditional method before this, shikimic acid or volatile oil, the prerequisite of productive rate under, the another kind of product of the acquisition of high yield.This improvement is vital for the comprehensive utilization of anistree this Chinese peculiar integration of drinking and medicinal herbs natural perfume plant resource, and effective utilization rate of resource is greatly increased, and improves the degree of utilizing of natural resource greatly, increases utility value.
Shikimic acid is known as the starting raw material of synthetic anti-H5N1 type avian influenza virus specifics Tamiflu (Tamiflu), and the Star Anise Fruit essential oil is known to can be used as natural essence and food flavouring extensively applies to fields such as food both domestic and external, beverage, spices, drinks, tobacco.
Specifically, at first, we find that it is stable that shikimic acid contained in the anise is handled steam distillation, under the steam distillation processing condition that we taked, neither can be extracted in the overhead product, also can not be degraded in the high temperature hygrothermal environment of steam distillation, adopt the steam distillation technology to extract the operation of contained volatile oil in the anise thereby can wherein contained shikimic acid not impacted, the raffinate and the residue that promptly extract behind the volatile oil still can be used as the raw material that extracts shikimic acid.Established the basis of from anise, extracting shikimic acid and volatile oil simultaneously thus.
Secondly, after various extractions commonly used such as ethanol, acetone are compared with solvent, we find as solvent residue to be carried out cold soaking with the water under the certain pH, can effectively shikimic acid separation and Extraction contained in the residue be come out, and contained impurity are minimum in the extract.And find that the aqueous extract that obtains thus can obtain the pure product of shikimic acid after following step process: the aqueous extract that (1) will contain shikimic acid is handled through (or without) column chromatography, is concentrated into driedly, obtains a syrup; (2) be that solvent carries out refluxing extraction to resulting syrup with acetone, obtain containing the acetone extract of shikimic acid; (3) acetone extract that will contain shikimic acid is concentrated into driedly, obtains the shikimic acid crude product; (4) after the shikimic acid crude product is dissolution with solvents with methyl alcohol, be that sorbent material carries out column chromatography with silica gel, eluent is the mixed solvent of methyl alcohol: chloroform=1:4 (v/v); (5) collect the part that turns out to be the shikimic acid one-component through thin-layer chromatography, concentrate, leave standstill, collect the white crystals of separating out.
We find that in extracting extraction process parameters such as solvent, extraction time, extraction temperature and solid-liquid ratio, lixiviate number of times, the pH value of water and soaking temperature are of paramount importance for extraction yield.Wherein, the pH value should be within the 2-12 scope, preferably in the scope of 2-7; Soaking temperature should be in 0-90 ℃ of scope, preferably in the scope of room temperature ± 20 ℃.Other parameters, lixiviate can only be carried out once, also can carry out 2-5 time, wherein the volume of water be anistree weight 3-30 doubly, extraction time is 0.5-12hr/ time.
As a result along band, we have set up the fast and convenient shikimic acid method for qualitative and quantitative detection of a cover.The qualitative detection of shikimic acid can be carried out with thin layer chromatography: the extracting solution point sample on the silica gel G thin plate that contains shikimic acid, with benzene: butanone: methyl alcohol=3:1:1 is first developping agent, methyl alcohol: chloroform: formic acid=2:7.5:0.5 is that second developping agent carries out two-way thin-layer chromatography, then according to following step colour developing: the Periodic acid solution or the periodate solution that on thin plate, spray 0.5% (w/v), dry up, and then on thin plate, spray 1moll
-1Sodium hydroxide and 0.05moll
-1The mixing solutions of S-WAT (pressing the mixed of 3:2) dries up once more.Spray Periodic acid solution and also dry up the back nondiscoloration, spray the person that is the yellow spotting behind sodium hydroxide-S-WAT mixing solutions, be shikimic acid.The Rf value of shikimic acid in first development system is 0.24, and the Rf value in second development system is 0.38, and observing under 254nm and 365nm ultraviolet lamp does not all have fluorescence.The limit of detection of this method is 30ng.The then available colorimetry of the detection by quantitative of shikimic acid is carried out: get the solution to be measured that 400ul contains shikimic acid, add 0.5% (w/v) Periodic acid solution of 200ul, constant temperature took out the 1moll that adds 400ul after 10 minutes in 40 ℃ of water-baths
-1Sodium hydroxide and 0.05moll
-1The mixing solutions of S-WAT (pressing the mixed of 3:2).Under 382nm, measure absorbancy with ultraviolet spectrophotometer, compare with the typical curve that records under the identical conditions then, can draw the content of shikimic acid.
Embodiment
Following example will specify working method of the present invention, but can not be as limitation of the invention.
Get the 100g anise, pulverize to Powdered, place the steam distillation device then, feed water vapor, being distilled to anistree powder does not have (being generally 3-5hr) till the hot smell of anistree distinctive perfume (or spice).The oil-water mixture that obtains obtains about 8g Fructus Anisi Stellati oil behind separatory; The anistree residue that obtains behind the steam distillation adds deionized water that pH transfers to 2-7 according to the ratio of 1:8 (w/v) and extracts shikimic acid and spend the night (about 12hr) in soaking under the room temperature, filters then.Resulting water extract is at 60 ℃, is concentrated into driedly under the 0.005MPa, obtains a syrup.Ratio according to 1:3 (w/v) is added solvent acetone and reflux 30min in syrup, filter, and collects acetone extract, and at 60 ℃, is concentrated into driedly under the 0.005MPa, obtains the shikimic acid crude product; Shikimic acid crude product dissolve with methanol, last silicagel column, use methyl alcohol: the developping agent wash-out of chloroform=1:4, just having begun the darker elutriant of effusive color will not collect, repeat upper prop, after treating that the elutriant color and luster is thin out gradually, begin to collect the part that turns out to be the shikimic acid one-component through thin-layer chromatography, in elutriant, can not detect till the shikimic acid; Elutriant is concentrated, leave standstill, collect the white crystals of separating out, obtain 3g purity and reach shikimic acid solid more than 98%.
Claims (4)
1. method of from anise, extracting shikimic acid and volatile oil simultaneously.This method is made up of the following step:
Anise is carried out steam distillation, and overhead product reclaims behind standing demix and obtains volatile oil, heats up in a steamer excess and obtain shikimic acid after following step process:
(1) heating up in a steamer excess and be cooled to room temperature, is that solvent soaks extraction with water, obtains containing the aqueous extract of shikimic acid;
(2) aqueous extract that will contain shikimic acid through or handle without column chromatography, be concentrated into driedly, obtain a syrup;
(3) be that solvent carries out refluxing extraction to resulting syrup with acetone, obtain containing the acetone extract of shikimic acid;
(4) acetone extract that will contain shikimic acid is concentrated into driedly, obtains the shikimic acid crude product;
(5) after the shikimic acid crude product is dissolution with solvents with methyl alcohol, be that sorbent material carries out column chromatography with silica gel, eluent is that volume ratio is a methyl alcohol: the mixed solvent of chloroform=1: 4;
(6) collect the part that turns out to be the shikimic acid one-component through thin-layer chromatography, concentrate, leave standstill, the adularescent crystallization is separated out, and both has been shikimic acid;
The anise of being declared is dry mature fruit or its powder through pulverizing of Magnoliacea plant anise (Illicium verum Hook..f.);
The steam distillation of being declared means and allows water vapor pass the anistree bed of material, collects the water vapor of condensation and the operating process of volatile oil;
The overhead product of being declared means anistree condensation product collected behind steam distillation; The volatile oil of being declared means overhead product resulting oil phase part after oily water separation;
The excess of being declared that heats up in a steamer means anistree through resulting remainder except that overhead product behind the steam distillation;
The shikimic acid of being declared is natural 3,4 in the anise that be present in, 5-trihydroxy--1-tetrahydrobenzene-1-carboxylic acid, and molecular formula is C
7H
10O
5, molar mass is 174.15gmol
-1, its English name is Shikimic acid, and CAS is numbered 138-59-0, and EINECS is numbered 205-334-2.
2. the method for extracting shikimic acid and volatile oil from anise simultaneously according to claim 1 is characterized in that used water system refers to that pH regulator is the deionized water of certain certain value, and its pH value is within the 2-12 scope.
3. the method for from anise, extracting shikimic acid and volatile oil simultaneously according to claim 1, it is characterized in that soaking and extract, can only carry out once, also can carry out 2-5 time, wherein the volume of water be anistree weight 3-30 doubly, soaking temperature is in 0-90 ℃ of scope, and soak time is 0.5-12hr/ time.
4. the method for from anise, extracting shikimic acid and volatile oil simultaneously according to claim 1, it is characterized in that the shikimic acid one-component analyses finger on the silica GF254 thin plate, with benzene: butanone: methyl alcohol=3: 1: 1 is first developping agent, methyl alcohol: chloroform: formic acid=2: 7.5: 0.5 is that second developping agent carries out after two-way thin-layer chromatography launches, 254nm only observes down at Rf1=0.24, there is single blackening at the Rf2=0.38 place, and 365nm observes the elutriant part without any the fluorescence spot down; Further confirmation method is: spray w/v concentration and be 0.5% Periodic acid solution or periodate solution on thin plate, dry up, and then spray the 1moll of the mixed of pressing 3: 2 on the thin plate
-1Sodium hydroxide and 0.05moll
-1The mixing solutions of S-WAT dries up once more; Spray Periodic acid solution and also dry up the back nondiscoloration, spray the person that is the yellow spotting behind sodium hydroxide-S-WAT mixing solutions, be shikimic acid.
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| CN2006101264182A CN101318893B (en) | 2006-08-25 | 2006-08-25 | Process for extracting shikimic acid and ethereal oil from octagonal |
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| CN2006101264182A CN101318893B (en) | 2006-08-25 | 2006-08-25 | Process for extracting shikimic acid and ethereal oil from octagonal |
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| CN101318893B true CN101318893B (en) | 2011-07-20 |
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| CN103145550A (en) * | 2013-03-27 | 2013-06-12 | 张达燕 | Method of extracting shikimic acid from star anise |
| 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 |
| CN108977272A (en) * | 2018-07-27 | 2018-12-11 | 广东工业大学 | A method of extracting the volatile oil fat microballoon of water soluble ingredient from fragrant plant |
| CN112094184B (en) * | 2019-06-17 | 2021-07-13 | 江苏得乐康生物科技有限公司 | Method for extracting shikimic acid from ginkgo leaf extract chromatographic wastewater |
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