CN104909999B - A kind of isolated and purified anthraquinone analog compound and method of styrene acid from Radix Et Rhizoma Rhei - Google Patents
A kind of isolated and purified anthraquinone analog compound and method of styrene acid from Radix Et Rhizoma Rhei Download PDFInfo
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- CN104909999B CN104909999B CN201510179428.1A CN201510179428A CN104909999B CN 104909999 B CN104909999 B CN 104909999B CN 201510179428 A CN201510179428 A CN 201510179428A CN 104909999 B CN104909999 B CN 104909999B
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- methanol
- carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/10—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention provides a kind of isolated and purified anthraquinone analog compound and method of styrene acid from Radix Et Rhizoma Rhei extract.Rhubarb medicinal material is pulverized, and adds phenyl-hydrogen-sulfate mixed liquor heating and refluxing extraction, and extracting solution filtration, concentrating under reduced pressure are obtained extractum rhei；Being dissolved by extractum rhei methanol, after filtering, carry out supercritical fluid chromatography separation, chromatographic column is glycol-based chromatographic column, and flowing is supercritical fluid mutually, and modifier is methanol.The present invention does not use the organic solvent having harm to environment, production process environmental protection, and products obtained therefrom unharmful substance remains；Carbon dioxide recovery utilizes easily, and energy consumption is low, and production cost is low.
Description
Technical field
The invention belongs to chemical industry and pharmaceutical field, be specifically related to a kind of isolated and purified Anthraquinones from Radix Et Rhizoma Rhei extract
Compound and the method for styrene acid.
Background technology
Radix Et Rhizoma Rhei is conventional Chinese medicine, have under rushing down, antibacterial, antiviral, intestinal stasis relieving relieving constipation, relieving stranguria by diuresis, 'Shugan Lidan ', stagnant abdomen
Bitterly, antitumor, antiinflammatory, hemostasis, emesis, the multiple effect such as pain relieving, be widely used in chronic renal failure, upper digestion clinically
The multiple diseases such as gastrointestinal hemorrhage, acute pancreatitis, acute ileus, hepatitis gravis, uremia, dysentery, pulmonary carcinoma, leukemia and diabetes
Sick treatment.Its main active is anthraquinone derivative, including chrysophanic acid, rheum emodin, chrysophanol, aloe-emodin and Radix Et Rhizoma Rhei
Element methyl ether.
The tradition of Active Constituents in Rhubarb separates pure method, uses organic solvent extraction-thin layer chromatography, efficient liquid phase more
Chromatography etc..Although thin layer chromatography has the features such as easy to operate, equipment is simple, but its separating degree is the highest, and separating degree is held
Easily affected by relative humidity and temperature.High performance liquid chromatography separating degree is high, applied range, but its separation costs is high.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that one is easy and simple to handle, fractional dose big, integrated cost
Fast purifying from Radix Et Rhizoma Rhei low, environmental protection prepares anthraquinone analog compound and the method for styrene acid, separates pure by a step
Change can obtain high-purity anthraquinone analog compound and styrene acid monomers compound from Radix Et Rhizoma Rhei extract.
The solution of the present invention is as follows:
A kind of isolated and purified anthraquinone analog compound and method of styrene acid from Radix Et Rhizoma Rhei extract, step is:
Step 1: rhubarb medicinal material pulverize, add benzene-sulfuric acid mixture liquid, heating and refluxing extraction, by extracting solution filter, reduce pressure dense
Contract to obtain extractum rhei.
Step 2: being dissolved by extractum rhei methanol, after filtering, carry out supercritical fluid chromatography separation, chromatographic column is two
Alcohol radical chromatographic column, flowing is supercritical fluid mutually, and modifier is methanol.Separation process is detected by UV-detector, according to detection
Signal collection target components fraction.
Foregoing method, preferred scheme is, the sulfuric acid concentration in step 1 is 10-40%, and optimum is 20%；Benzene with
The volume ratio of sulphuric acid is 10:1～2:1, and optimum is 5:1；Benzene-sulfuric acid mixture liquid is 3:1～10:1 with the ratio of medical material, optimum
For 6:1；The number of times extracted is 3 times, and each return time is 0.5-5 hour, and optimum is 1.5 hours.
Foregoing method, preferred scheme is, filtering filter membrane used in step 2 is 0.45 μm filter membrane.
Foregoing method, preferred scheme is, in step 2, supercritical fluid is supercritical carbon dioxide, supercritical
The pressure of carbon dioxide is 9 ~ 20MPa, and optimum is 13 MPa；The flow velocity of supercritical carbon dioxide be 1-10 times of column volume/minute,
Optimum be 4 times of column volumes/minute.
Foregoing method, preferred scheme is, in step 2, chromatogram column temperature is 35 ~ 55 ° of C, and optimum is 45 ° of C.
Foregoing method, preferred scheme is, in step 2, the ratio of modifier methanol is 0% ~ 10%, and optimum is 4%.
A kind of isolated and purified anthraquinone analog compound and method of styrene acid from Radix Et Rhizoma Rhei of the present invention, has the advantage that
(1) in the Radix Et Rhizoma Rhei extract obtained by, active constituent content is high (as can be seen from Figure 1).
(2) need not, as prior art, sample is carried out separating for several times purification, it is only necessary to a separating step
Obtain high-purity anthraquinone analog compound and styrene acid, through a step isolated and purified can be obtained by 5 kinds of anthraquinone analog compounds and
Styrene acid.
(3) purge process uses supercritical carbon dioxide, do not use the organic solvent that environment is had harm, production process
Environmental protection, products obtained therefrom unharmful substance remains.
(4) carbon dioxide recovery utilizes easily, and energy consumption is low, and production cost is low.
(5) method is simple to operate, it is easy to Automated condtrol, and efficiency is high, and process cycle is short.
Accompanying drawing explanation
Fig. 1 is embodiment 1 supercritical fluid chromatography figure.
Detailed description of the invention
Describe technical scheme in detail below in conjunction with embodiment and accompanying drawing, but protection domain is not limited by this.Real
Execute device therefor or raw material in example all to obtain from market.Agents useful for same is analytical pure, purchased from Tianjin reagent four factory, used
Carbon dioxide is high-purity carbon dioxide.
Embodiment 1
Weigh Radix Et Rhizoma Rhei 100 g, pulverize with pulverizer, put in glass container, add 600 ml benzene-20% sulphuric acid (5:1, V/
V) mixed liquor, heating and refluxing extraction 3 times, each 1.5 hours, united extraction liquid, filtration, concentrating under reduced pressure obtained extractum rhei.
Extractum rhei methanol is dissolved, after filtering (filter membrane used is 0.45 μm filter membrane), carries out shooting flow body colour
Spectrum separates, and chromatographic column is glycol-based chromatographic column, and chromatogram column temperature is 45 ° of C.Flowing is supercritical carbon dioxide mutually, and flow velocity is 4
Times column volume/minute, pressure is 13 MPa.Modifier is methanol, and its ratio is 4%.Separation process is detected by UV-detector,
Detection wavelength is 254 nm, according to detection signal collection target components fraction, respectively obtains 5 kinds of anthraquinone analog compounds and styrene
Acid.
Fig. 1 is embodiment 1 supercritical fluid chromatography figure.The purity of each component of gained is the highest, all more than 98%.
Embodiment 2
Weigh Radix Et Rhizoma Rhei 100 g, pulverize with pulverizer, put in glass container, add 800 ml benzene-15% sulphuric acid (5:1, V/
V) mixed liquor, heating and refluxing extraction 3 times, each 1 hour, united extraction liquid, filtration, concentrating under reduced pressure obtained extractum rhei.
Being dissolved by extractum rhei methanol, after filtering, carry out supercritical fluid chromatography separation, chromatographic column is glycol primary colours
Spectrum post, chromatogram column temperature is 40 ° of C.Flowing be supercritical carbon dioxide mutually, flow velocity be 3.5 times of column volumes/minute, pressure is 12
MPa.Modifier is methanol, and its ratio is 3%.Separation process is detected by UV-detector, and detection wavelength is 254 nm, according to inspection
Survey signal collection target components fraction, respectively obtain 5 kinds of anthraquinone analog compounds and styrene acid.
Embodiment 3
Weigh Radix Et Rhizoma Rhei 100 g, pulverize with pulverizer, put in glass container, add 500 ml benzene-25% sulphuric acid (6:1, V/
V) mixed liquor, heating and refluxing extraction 3 times, each 2 hours, united extraction liquid, filtration, concentrating under reduced pressure obtained extractum rhei.
Being dissolved by extractum rhei methanol, after filtering, carry out supercritical fluid chromatography separation, chromatographic column is glycol primary colours
Spectrum post, chromatogram column temperature is 35 ° of C.Flowing be supercritical carbon dioxide mutually, flow velocity be 3 times of column volumes/minute, pressure is 11
MPa.Modifier is methanol, and its ratio is 2%.Separation process is detected by UV-detector, and detection wavelength is 254 nm, according to inspection
Survey signal collection target components fraction, respectively obtain 5 kinds of anthraquinone analog compounds and styrene acid.
Testing through HPLC area normalization method analysis, the purity of each component obtained by embodiment 1-3 is the highest, all exists
More than 98%.
Identifying through NMR, MS, in Fig. 1, A, B, C, D, E, F represent chrysophanol, physcione, styrene acid, Radix Et Rhizoma Rhei respectively
Element, aloe-emodin, chrysophanic acid, its chemical constitution is as follows:
Claims (10)
1. isolated and purified anthraquinone analog compound and a method for styrene acid from Radix Et Rhizoma Rhei extract, is characterized in that, step is:
Step 1: rhubarb medicinal material is pulverized, adds benzene-sulfuric acid mixture liquid, heating and refluxing extraction, extracting solution filtration, concentrating under reduced pressure is obtained
Extractum rhei；Sulfuric acid concentration is 10-40%；Benzene is 10:1～2:1 with the volume ratio of sulphuric acid；Benzene-sulfuric acid mixture liquid and medical material
Ratio is 3:1～10:1；Extraction time is 3 times, and each return time is 0.5-5 hour；
Step 2: being dissolved by extractum rhei methanol, after filtering, carry out supercritical fluid chromatography separation, chromatographic column is glycol-based
Chromatographic column, flowing is supercritical fluid mutually, and modifier is methanol, and separation process is detected by UV-detector, according to detection signal
Collect target components fraction；Supercritical fluid is supercritical carbon dioxide, and the pressure of supercritical carbon dioxide is 9 ~ 20MPa；Super
The flow velocity of critical carbon dioxide be 1-10 times of column volume/minute；Chromatogram column temperature is 35 ~ 55 DEG C；The ratio of methanol is 0% ~ 10%.
Method the most according to claim 1, is characterized in that, the sulfuric acid concentration in step 1 is 20%.
Method the most according to claim 1, is characterized in that, in step 1, benzene is 5:1 with the volume ratio of sulphuric acid.
Method the most according to claim 1, is characterized in that, in step 1, benzene-sulfuric acid mixture liquid is 6:1 with the ratio of medical material.
Method the most according to claim 1, is characterized in that, in step 1, each return time is 1.5 hours.
Method the most according to claim 1, is characterized in that, filtering filter membrane used in step 2 is 0.45 μm filter membrane.
Method the most according to claim 1, is characterized in that, in step 2, the pressure of supercritical carbon dioxide is 13 MPa.
Method the most according to claim 7, is characterized in that, the flow velocity of supercritical carbon dioxide be 4 times of column volumes/minute.
Method the most according to claim 1, is characterized in that, in step 2, chromatogram column temperature is 45 DEG C.
Method the most according to claim 1, is characterized in that, in step 2, the ratio of methanol is 4%.
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| CN201510179428.1A CN104909999B (en) | 2015-04-16 | 2015-04-16 | A kind of isolated and purified anthraquinone analog compound and method of styrene acid from Radix Et Rhizoma Rhei |
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| CN201510179428.1A CN104909999B (en) | 2015-04-16 | 2015-04-16 | A kind of isolated and purified anthraquinone analog compound and method of styrene acid from Radix Et Rhizoma Rhei |
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| CN104909999B true CN104909999B (en) | 2016-07-20 |
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| CN105859715A (en) * | 2016-04-27 | 2016-08-17 | 聊城大学 | Critical fluid chromatographic method for separating and purifying evodiamine and rutaecarpine from fructus evodiae |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1349966A (en) * | 2001-11-09 | 2002-05-22 | 南京中山制药厂 | Extraction and purification process of general rhubarb anthraquinone and its application in preparing kidney hypofuction-treating medicine |
| CN101053596A (en) * | 2007-05-23 | 2007-10-17 | 浙江大学 | Supercritical carbon dioxide method for extracting high purity rhubarb free anthraquinones |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1349966A (en) * | 2001-11-09 | 2002-05-22 | 南京中山制药厂 | Extraction and purification process of general rhubarb anthraquinone and its application in preparing kidney hypofuction-treating medicine |
| CN101053596A (en) * | 2007-05-23 | 2007-10-17 | 浙江大学 | Supercritical carbon dioxide method for extracting high purity rhubarb free anthraquinones |
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