CN101585837A - Method for separating matrine and oxymatrine from total matrines - Google Patents
Method for separating matrine and oxymatrine from total matrines Download PDFInfo
- Publication number
- CN101585837A CN101585837A CNA2009100994393A CN200910099439A CN101585837A CN 101585837 A CN101585837 A CN 101585837A CN A2009100994393 A CNA2009100994393 A CN A2009100994393A CN 200910099439 A CN200910099439 A CN 200910099439A CN 101585837 A CN101585837 A CN 101585837A
- Authority
- CN
- China
- Prior art keywords
- matrine
- sophocarpidine
- oxymatyine
- separating
- filtrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a method for separating matrine and oxymatrine from total matrines. The method comprises the steps of firstly detecting the content of the matrine in the total matrines; dissolving the total matrines in water, adding metal halide MYz and halogen acid HN solution, wherein M is trivalent Fe, Cu, Zn, Al or Mn, z is the valency of M, Y and N are respectively independently Cl, Br or I; agitating and reacting at 60-100 DEG C, cooling the reaction liquid to 0-30 DEG C after the reaction is completed, putting aside, separating out crystal, and finally filtering to obtain filter cake A and filtrate A; the oxymatrine is remained in the filtrate A and the filter cake A is the matrine crystal rough product. The invention has the advantages that the resolving efficiency is relatively high, crystallization is carried out for one time only, the yields of the separated matrine and oxymatrine monomer are between 90% and 95%, and the purities thereof are between 95% and 99%. The invention has simple operation, good repeatability, low implementation cost and favorable industrial expansion.
Description
(1) technical field
The present invention relates to a kind of from sophocarpidine the method for separating matrine and Oxymatyine.
(2) background technology
That the dry root of the root of leguminous plants kuh-seng, leguminous plants sophora tonkinensis Gapnep and rhizome (Radix Sophorae Tonkinensis), cassia leguminous plant Herba Sophorae alopecuroidis all have is clearing heat and detoxicating, the effect of wind dispelling insecticide, relieving sore throat and diminishing swelling.This three kind of plant all contain quinolines such as in various degree matrine, Oxymatyine, sophocarpine, Sophocarpidin in western pyridine Alkaloid,, secondly be matrine wherein with oxymatrine concentration the highest (account for Radix Sophorae Flavescentis total alkaloids 70%).At present, on the angle of scientific research, Radix Sophorae Flavescentis alkaloid has reached comparatively meticulous degree in breadboard separation, can isolate the very high composition of purity.But on the production angle, how efficiently, extraction and separating matrine, Oxymatyine apace, satisfy its ever-increasing heavy demand at aspects such as medicine, sterilant, plant-growth regulator, the research of this respect is also few, mostly product is the mixture of total alkali or Oxymatyine and matrine, has influenced the performance of matrine and Oxymatyine pharmacologically active.So, from this three kind of plant, separate single creature alkali, its meaning is apparent.
The molecular formula of matrine and Oxymatyine is respectively shown in following formula (I) and formula (II):
Formula (I) matrine formula (II) Oxymatyine
By the molecular structure of above-mentioned matrine, Oxymatyine as can be seen, both structural formulas are quite similar, are difficult to both are separated with conventional means.Though in the laboratory, utilize methods such as chromatography, ion-exchange, high performance countercurrent chromatography can from above three kinds of medicinal plants, isolate single creature alkali, there are drawbacks such as technology is loaded down with trivial details, small scale, cost height, can't be applied to scale operation.
Molecular recognition is meant under non covalent bond effects such as hydrogen bond, Van der Waals force, the interaction that intermolecular height is selected.The identification phenomenon had both existed in the solid, also was present among the solution, was presented on widely especially in the life system, often was described to inclusion, affinity, combination, condenses, adhered to, fusion etc.Molecular recognition is multi-disciplinary centers such as chemistry, pharmacy and biology, manifests unique glamour in separation especially.
How the molecular recognition technology being applied to matrine, the monomeric separation of Oxymatyine, is the problem of a very worth research.
(3) summary of the invention
The technical problem to be solved in the present invention is to provide a kind of molecular recognition principle separating matrine and Oxymatyine monomer methods from sophocarpidine utilized simply, efficiently.
Research thinking of the present invention is: be connected with a Sauerstoffatom on the nitrogen-atoms in the Oxymatyine molecule, and not connecting Sauerstoffatom in the matrine molecule on the nitrogen-atoms of this position, this difference has caused different recognition capability between distinctive main body guest molecule.Develop separation method efficiently by this molecular recognition phenomenon.
For solving the technology of the present invention problem, the present invention adopts following technical scheme:
A kind of from sophocarpidine the method for separating matrine and Oxymatyine, described method may further comprise the steps: (1) detects content of matrine in the sophocarpidine earlier, usually record with liquid chromatography, obtain the amount of matrine in the sophocarpidine, then that sophocarpidine is soluble in water, add metal halide MY
zWith haloid acid HN solution, described M is trivalent Fe, Cu, Zn, Al or Mn, z is the valency of M, and Y, N independently are Cl, Br or I separately, stirring reaction under 60-100 ℃ of temperature, after reaction finishes, reaction solution is cooled to 0-30 ℃, leaves standstill to separate out crystal, filters and obtains filter cake A and filtrate A, Oxymatyine is stayed among the filtrate A, and filter cake A is a matrine crystal crude product; Described metal halide MY
zWith the amount of substance ratio of matrine in the sophocarpidine be 1～2: 1; HN is 1～2: 1 with the ratio of the amount of substance of metal halide in the described halogen acid solution; (2) behind the filter cake A usefulness recrystallization solvent recrystallization that step (1) obtains, add the less water dissolving, " on a small quantity " water here is meant the whole dissolved amounts of crystallization is got final product, regulating the pH value with alkali lye again is more than or equal to 7, add the organic solvent A extraction then, standing demix is got the organic layer distillation except that desolvating, surplus materials is the monomer matrine, and it is one of following that described recrystallization solvent is selected from: methyl alcohol, ethanol, acetone or water; Described organic solvent A is methylene dichloride, chloroform or benzene.
The filtrate A that described step (1) obtains adds the organic solvent B extraction, and standing demix is got the organic layer distillation except that desolvating, and surplus materials is the monomer Oxymatyine; Described organic solvent B is methylene dichloride, chloroform or benzene.
Sophocarpidine of the present invention can be in advance with liquid chromatographic detection matrine and oxymatrine concentration wherein.
Metal halide MY of the present invention
zIn, M is trivalent Fe, Cu, Zn, Al or Mn, is preferably Fe or Cu, Y is Cl, Br or I, is preferably Cl; That is to say metal halide MY
zBe preferably FeCl
3Or CuCl
2
The concentration of described haloid acid is 5～12mol/L, and being preferably 8～10mol/L haloid acid HN is HCl, HBr or HI, is preferably HCl.
The consumption of water is counted 20～30ml/g with the quality of matrine in the sophocarpidine in the described step (1), is preferably 25ml/g.
The stirring reaction time is generally 1～2 minute in the described step (1).
It is 6-10 days that leaving standstill in the described step (1) separated out the crystalline time.
It is one of following that recrystallization solvent in the step of the present invention (2) is selected from: methyl alcohol, ethanol, acetone or water; Be preferably methyl alcohol or acetone.
Alkali lye in the described step (2) is saturated sodium bicarbonate solution or saturated sodium carbonate solution.
Described organic solvent A is preferably methylene dichloride or chloroform; Organic solvent B is preferably methylene dichloride or chloroform.
Comparatively concrete, recommend of the present invention from sophocarpidine the method for separating matrine and Oxymatyine carry out according to following steps:
(1) with content of matrine in the liquid chromatographic detection sophocarpidine, obtain the amount of matrine in the sophocarpidine, then that sophocarpidine is soluble in water, add metal halide MY
zAnd hydrochloric acid, described MY
zBe FeCl
3Or CuCl
2, stirring reaction is 1～2 minute under 60-100 ℃ of temperature, and reaction finishes, and reaction solution is cooled to 0-30 ℃, leaves standstill 6-10 days, separates out crystal, filters and obtains filter cake A and filtrate A, and Oxymatyine is stayed among the filtrate A, and filter cake A is a matrine crystal crude product; Described metal halide MY
zWith the amount of substance ratio of matrine in the sophocarpidine be 1～2: 1; HCl is 1～2: 1 with the ratio of the amount of substance of metal halide in the described hydrochloric acid; The concentration of described hydrochloric acid is 5～12mol/; The consumption of described water is counted 20～30ml/g with the quality of matrine in the sophocarpidine; (2) behind the filter cake A usefulness recrystallization solvent recrystallization that step (1) obtains, add the less water dissolving, regulating the pH value with alkali lye again is more than or equal to 7, add the organic solvent A extraction then, standing demix is got the organic layer distillation except that desolvating, and surplus materials is the monomer matrine; It is one of following that described recrystallization solvent is selected from: methyl alcohol, ethanol, acetone or water; Described alkali lye is saturated sodium bicarbonate solution or saturated sodium carbonate solution; Described organic solvent A is methylene dichloride, chloroform or benzene; (3) the filtrate A that obtains of step (1) adds the organic solvent B extraction, and standing demix is got the organic layer distillation and removed and desolvate, and surplus materials is the monomer Oxymatyine; Described organic solvent B is methylene dichloride, chloroform or benzene.
Compared with prior art, present method is based on the ultimate principle of supramolecule assembling, utilize being complementary on the topology between host molecule and the guest molecule, make matrine in halogen acid solution, optionally form stable molecular crystal with metal halide, thereby realize centrifugation efficiently and rapidly, its advantage mainly is:
A) efficiency ratio of Chai Fening is higher.Because the high selectivity of molecular recognition only needs primary crystallization, the monomeric yield of matrine and Oxymatyine can be between 90%-95%, and its purity is between 95%-99%.
B) simple to operate, good reproducibility, implementation cost is low, helps industry and amplifies.
(4) embodiment
Further specify technical scheme of the present invention with specific embodiment below, but protection scope of the present invention is not limited thereto.
Embodiment 1:
In the 500ml beaker, 15 gram sophocarpidine powder (through liquid chromatographic detection, matrine content is 23%, and the content of Oxymatyine is 67%) are dissolved in the 105ml water, the hydrochloric acid 6ml that adds 4.8 gram iron trichlorides and 36% then, under agitation be heated to 100 ℃, insulation reaction 2min obtains settled solution, is cooled to room temperature, placed seven days under the room temperature, there are yellowish brown, crystalline transparent to separate out, filter and obtain matrine crystal crude product, keep filtrate; Matrine crystal crude product is dissolved in the water after recrystallizing methanol, and being adjusted to the pH value with saturated sodium bicarbonate solution again is 7, adds chloroform extraction then, standing demix obtains water layer and organic layer, and organic layer removes through distillation and desolvates, surplus materials is matrine monomer 3.26 grams, yield 94.7%.The filtrate that keeps is added chloroform extract, leave standstill and obtain layering solution, separate obtaining water layer and organic layer, organic layer removes through distillation and desolvates, and surplus materials is Oxymatyine monomer 9.25 grams, yield 92.0%.Matrine purity: 98.1%, Oxymatyine purity: 97.2%, detection method is a liquid chromatography.
Embodiment 2:
In the 500ml beaker, 20 gram sophocarpidine powder (through liquid chromatographic detection, matrine content is 23%, and the content of Oxymatyine is 67%) are dissolved in the 92ml water, the hydrochloric acid 3ml that adds 4.0 gram zinc chloride and 36% then, under agitation be heated to 80 ℃, insulation reaction 2min obtains settled solution, is cooled to room temperature, place the Ninth Heaven under the room temperature, there is colourless, crystalline transparent to separate out, filters and obtain matrine crystal crude product, keep filtrate; Matrine crystal crude product is dissolved in the water behind ethyl alcohol recrystallization, and being adjusted to the pH value with saturated sodium bicarbonate solution again is 7, adds chloroform extraction then, separate and obtain water layer and organic layer, organic layer removes through distillation and desolvates, and residuum is matrine monomer 4.15 grams, yield 90.2%.The filtrate that keeps is added chloroform extract, obtain layering solution, separate obtaining water layer and organic layer, organic layer removes through distillation and desolvates, and residuum is Oxymatyine monomer 11.88 grams, yield 88.7%.Matrine purity: 96.5%, Oxymatyine purity: 95.8%, detection method is a liquid chromatography.
Embodiment 3:
In the 500ml beaker, 15 gram sophocarpidine powder (through liquid chromatographic detection, matrine content is 23%, and the content of Oxymatyine is 67%) are dissolved in the 105ml water, the hydrochloric acid 3ml that adds 2.55 gram Copper dichloride dihydrates and 36% then, under agitation be heated to 100 ℃, insulation reaction 2min obtains settled solution, is cooled to room temperature, placed six days under the room temperature, there are yellowish brown, crystalline transparent to separate out, filter and obtain matrine crystal crude product, keep filtrate; Matrine crystal crude product is dissolved in the water behind acetone recrystallization, and being adjusted to the pH value with saturated sodium bicarbonate solution again is 7, adds dichloromethane extraction then, separate and obtain water layer and organic layer, organic layer removes through distillation and desolvates, and promptly gets matrine monomer 3.22 grams, yield 93.3%.The filtrate that keeps is added methylene dichloride extract, obtain layering solution, separate obtaining water layer and organic layer, organic layer removes to desolvate through distillation and promptly gets Oxymatyine monomer 9.20 grams, yield 91.5%.Matrine purity: 98.6%, Oxymatyine purity: 97.4%, detection method is a liquid chromatography.
Embodiment 4:
In the 500ml beaker, 15 gram sophocarpidine powder (through liquid chromatographic detection, matrine content is 23%, and the content of Oxymatyine is 67%) are dissolved in the 105ml water, the Hydrogen bromide 4.3ml that adds 5.9 gram four hydration Manganous chloride tetrahydrates and 40% then, under agitation be heated to 100 ℃, insulation reaction 2min obtains settled solution, is cooled to room temperature, placed seven days under the room temperature, there is colourless, crystalline transparent to separate out, filters and obtain matrine crystal crude product, keep filtrate; Matrine crystal crude product is dissolved in the water behind the water recrystallization, being adjusted to the pH value with saturated sodium bicarbonate solution again is 7, adds chloroform extraction then, separates to obtain water layer and organic layer, organic layer removes to desolvate through distillation and promptly gets matrine monomer 3.15 grams, yield 91.2%.The filtrate that keeps is added chloroform extract, obtain layering solution, separate obtaining water layer and organic layer, organic layer removes to desolvate through distillation and promptly gets Oxymatyine monomer 8.79 grams, yield 87.5%.Matrine purity: 96.7%, Oxymatyine purity: 95.8%, detection method is a liquid chromatography.
Embodiment 5:
In the 500ml beaker, 15 gram sophocarpidine powder (through liquid chromatographic detection, matrine content is 23%, and the content of Oxymatyine is 67%) are dissolved in the 105ml water, the Hydrogen bromide 4.3ml that adds 4.8 gram iron trichlorides and 40% then, under agitation be heated to 100 ℃, insulation reaction 2min obtains settled solution, is cooled to room temperature, placed eight days under the room temperature, there are yellowish brown, crystalline transparent to separate out, filter and obtain matrine crystal crude product, keep filtrate; Matrine crystal crude product is dissolved in the water behind ethyl alcohol recrystallization, being adjusted to the pH value with saturated sodium bicarbonate solution again is 7, adds chloroform extraction then, separates to obtain water layer and organic layer, organic layer removes to desolvate through distillation and promptly gets matrine monomer 3.20 grams, yield 92.7%.The filtrate that keeps is added chloroform extract, obtain layering solution, separate obtaining water layer and organic layer, organic layer removes to desolvate through distillation and promptly gets Oxymatyine monomer 9.08 grams, yield 90.3%.Matrine purity: 97.4%, Oxymatyine purity: 95.2%, detection method is a liquid chromatography.
Embodiment 6:
In the 500ml beaker, 15 gram sophocarpidine powder (through liquid chromatographic detection, matrine content is 23%, and the content of Oxymatyine is 67%) are dissolved in the 105ml water, the Hydrogen bromide 4.3ml that adds 5.2 gram Copper dichloride dihydrates and 40% then, under agitation be heated to 60 ℃, insulation reaction 2min obtains settled solution, is cooled to room temperature, placed six days under the room temperature, there are yellowish brown, crystalline transparent to separate out, filter and obtain matrine crystal crude product, keep filtrate; Matrine crystal crude product is dissolved in the water after recrystallizing methanol, being adjusted to the pH value with saturated sodium bicarbonate solution again is 7, adds the benzene extraction then, separates obtaining water layer and organic layer, organic layer removes to desolvate through distillation and promptly gets matrine monomer 3.16 grams, yield 91.6%.The filtrate that keeps is added benzene extract, obtain layering solution, separate obtaining water layer and organic layer, organic layer removes to desolvate through distillation and promptly gets Oxymatyine monomer 8.74 grams, yield 87%.Matrine purity: 97.5%, Oxymatyine purity: 96.7%, detection method is a liquid chromatography.
Embodiment 7:
In the 500ml beaker, 15 gram sophocarpidine powder (through liquid chromatographic detection, matrine content is 23%, and the content of Oxymatyine is 67%) are dissolved in the 105ml water, the hydrochloric acid 6ml that adds 7.23 gram Aluminium chloride hexahydrates and 36% then, under agitation be heated to 100 ℃, insulation reaction 2min obtains settled solution, is cooled to room temperature, placed seven days under the room temperature, there is colourless, crystalline transparent to separate out, filters and obtain the crystal crude product, keep filtrate; The crystal crude product is dissolved in the water behind the water recrystallization, and being adjusted to the pH value with saturated sodium bicarbonate solution again is 7, adds chloroform extraction then, separates to obtain water layer and organic layer, and organic layer removes to desolvate through distillation and promptly gets matrine monomer 3.20 grams, yield 92.7%.The filtrate that keeps is added chloroform extract, obtain layering solution, separate obtaining water layer and organic layer, organic layer removes to desolvate through distillation and promptly gets Oxymatyine monomer 9.26 grams, yield 90.1%.Matrine purity: 96.1%, Oxymatyine purity: 94.8%, detection method is a liquid chromatography.
Claims (10)
1, a kind of from sophocarpidine the method for separating matrine and Oxymatyine, it is characterized in that described method may further comprise the steps: (1) detects content of matrine in the sophocarpidine earlier, and sophocarpidine is soluble in water, adds metal halide MY
zWith haloid acid HN solution, described M is trivalent Fe, Cu, Zn, Al or Mn, z is the valency of M, and Y, N independently are Cl, Br or I separately, stirring reaction under 60-100 ℃ of temperature, after reaction finishes, reaction solution is cooled to 0-30 ℃, leaves standstill to separate out crystal, filters and obtains filter cake A and filtrate A, Oxymatyine is stayed among the filtrate A, and filter cake A is a matrine crystal crude product; Described metal halide MY
zWith the amount of substance ratio of matrine in the sophocarpidine be 1～2: 1; HN is 1～2: 1 with the ratio of the amount of substance of metal halide in the described halogen acid solution; (2) behind the filter cake A usefulness recrystallization solvent recrystallization that step (1) obtains, add the less water dissolving, regulating the pH value with alkali lye again is more than or equal to 7, add the organic solvent A extraction then, standing demix, get organic layer distillation and remove and desolvate, surplus materials is the monomer matrine, and it is one of following that described recrystallization solvent is selected from: methyl alcohol, ethanol, acetone or water; Described organic solvent A is methylene dichloride, chloroform or benzene.
2, as claimed in claim 1 from sophocarpidine the method for separating matrine and Oxymatyine, it is characterized in that the filtrate A that described step (1) obtains adds the organic solvent B extraction, standing demix is got the organic layer distillation except that desolvating, and surplus materials is the monomer Oxymatyine; Described organic solvent B is methylene dichloride, chloroform or benzene.
3, as claimed in claim 1 from sophocarpidine the method for separating matrine and Oxymatyine, it is characterized in that described metal halide MY
zBe FeCl
3Or CuCl
2
4, as claimed in claim 1 from sophocarpidine the method for separating matrine and Oxymatyine, it is characterized in that described haloid acid HN is HCl.
5, as claimed in claim 1 from sophocarpidine the method for separating matrine and Oxymatyine, the concentration that it is characterized in that the haloid acid in the described step (1) is 5～12mol/L.
6, as claimed in claim 1 from sophocarpidine the method for separating matrine and Oxymatyine, it is characterized in that the consumption of water in the described step (1) is counted 20～30ml/g with the quality of matrine in the sophocarpidine.
7, as claimed in claim 1 from sophocarpidine the method for separating matrine and Oxymatyine, it is one of following to it is characterized in that recrystallization solvent in the described step (2) is selected from: methyl alcohol or acetone.
8, as claimed in claim 1 from sophocarpidine the method for separating matrine and Oxymatyine, it is characterized in that the alkali lye in the described step (2) is saturated sodium bicarbonate solution or saturated sodium carbonate solution.
9, as claimed in claim 1 from sophocarpidine the method for separating matrine and Oxymatyine, it is characterized in that it is 6-10 days that leaving standstill in the described step (1) separated out the crystalline time.
10, as claimed in claim 1 from sophocarpidine the method for separating matrine and Oxymatyine, it is characterized in that described method may further comprise the steps: (1) detects content of matrine in the sophocarpidine earlier, sophocarpidine is soluble in water, add metal halide MY
zAnd hydrochloric acid, described MY
zBe FeCl
3Or CuCl
2, stirring reaction is 1～2 minute under 60-100 ℃ of temperature, and after reaction finished, reaction solution was cooled to 0-30 ℃, leaves standstill 6-10 days, separates out crystal, filtered and obtained filter cake A and filtrate A, and Oxymatyine is stayed among the filtrate A, and filter cake A is a matrine crystal crude product; Described metal halide MY
zWith the amount of substance ratio of matrine in the sophocarpidine be 1～2: 1; HCl is 1～2: 1 with the ratio of the amount of substance of metal halide in the described hydrochloric acid; The concentration of described hydrochloric acid is 5～12mol/L; The consumption of described water is counted 20～30ml/g with the quality of matrine in the sophocarpidine; (2) behind the filter cake A usefulness recrystallization solvent recrystallization that step (1) obtains, add the less water dissolving, regulating the pH value with alkali lye again is more than or equal to 7, add the organic solvent A extraction then, standing demix is got the organic layer distillation except that desolvating, and surplus materials is the monomer matrine; It is one of following that described recrystallization solvent is selected from: methyl alcohol, ethanol, acetone or water; Described alkali lye is saturated sodium bicarbonate solution or saturated sodium carbonate solution; Described organic solvent A is methylene dichloride, chloroform or benzene; (3) the filtrate A that obtains of step (1) adds the organic solvent B extraction, and standing demix is got the organic layer distillation and removed and desolvate, and surplus materials is the monomer Oxymatyine; Described organic solvent B is methylene dichloride, chloroform or benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100994393A CN101585837B (en) | 2009-06-05 | 2009-06-05 | Method for separating matrine and oxymatrine from total matrines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100994393A CN101585837B (en) | 2009-06-05 | 2009-06-05 | Method for separating matrine and oxymatrine from total matrines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101585837A true CN101585837A (en) | 2009-11-25 |
| CN101585837B CN101585837B (en) | 2011-05-25 |
Family
ID=41370289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100994393A Expired - Fee Related CN101585837B (en) | 2009-06-05 | 2009-06-05 | Method for separating matrine and oxymatrine from total matrines |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101585837B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591329A (en) * | 2022-03-03 | 2022-06-07 | 北京岳达生物科技有限公司 | Mutual transformation method of sophora flavescens effective components |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130541B (en) * | 2007-09-11 | 2010-09-29 | 重庆大学 | Method for extracting and separating matrine and oxymatrine from trialkyl phosphine oxide inverse micellar solution |
-
2009
- 2009-06-05 CN CN2009100994393A patent/CN101585837B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591329A (en) * | 2022-03-03 | 2022-06-07 | 北京岳达生物科技有限公司 | Mutual transformation method of sophora flavescens effective components |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101585837B (en) | 2011-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102002082B (en) | Method for preparing baicalin | |
| CN102395591B (en) | Method for preparing prasugrel | |
| CN103087059A (en) | Preparation method for high-purity olprinone hydrochloride | |
| CN101585837B (en) | Method for separating matrine and oxymatrine from total matrines | |
| CN101747210A (en) | Method for preparing alpha-(di-n-butylaminomethyl)-2,7-dichloro-4-fluorenemethanol and the hydrochloride thereof | |
| CN102417506B (en) | A kind of preparation method of antiviral drug of Entecavir | |
| CN105820145A (en) | Method for preparing 5-nitro-2-furaldehyde and nifuratel | |
| CN101786963A (en) | Synthesis method of Azasetron intermediate | |
| CN109096347B (en) | Method for purifying high-purity 3,2 ', 6' -tri-N-acetyl gentamicin C1a alkali (P1) | |
| CN103788010A (en) | Febuxostat intermediate and preparation method thereof | |
| CN102432516A (en) | Method for refining oxiracetam | |
| CN102464661A (en) | Preparation method of 5,6,7,8-tetrahydro-imidazo[1,5-a]pyrazine-1-carboxylic acid ethyl ester | |
| CN103570619B (en) | A kind of preparation method of montelukast sodium derivative | |
| CN105085524A (en) | Preparation method of high purity valganciclovir hydrochloride | |
| CN102924473A (en) | Preparation method of 2-chlorine-7-iodothieno[3,2-D] pyrimidine | |
| CN102070644B (en) | Method for preparing camptothecin derivatives and intermediates thereof | |
| CN102786527B (en) | Tailed porphyrin compound modified by N1-substituted 3, 4-dihydropyrimidine-2-ketone and preparation method thereof | |
| CN101671333B (en) | Method for separating emtricitabine | |
| CN101805339A (en) | Entecavir compound prepared in novel method | |
| CN101781175A (en) | Method for separating 2,4-Dichlorophenol and 2,6-Dichlorophenol | |
| CN103408439A (en) | Chemical synthetic method of norbelladine | |
| CN113004272B (en) | Quinoline [4,3-b ] carbazole derivative and application thereof in preparation of antitumor drugs | |
| CN111320588B (en) | Method for purifying Lesinurad | |
| CN101891767B (en) | Preparation method of adefovir dipivoxil | |
| CN101570564A (en) | Method for refining tanshinone II A acrylic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110525 Termination date: 20180605 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |