CN107089965B - Method for preparing oligomeric proanthocyanidins based on catalytic transfer hydrogenation technology - Google Patents
Method for preparing oligomeric proanthocyanidins based on catalytic transfer hydrogenation technology Download PDFInfo
- Publication number
- CN107089965B CN107089965B CN201710297478.9A CN201710297478A CN107089965B CN 107089965 B CN107089965 B CN 107089965B CN 201710297478 A CN201710297478 A CN 201710297478A CN 107089965 B CN107089965 B CN 107089965B
- Authority
- CN
- China
- Prior art keywords
- ethanol
- oligomeric
- proanthocyanidins
- reaction
- ammonium formate
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/60—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with aryl radicals attached in position 2
- C07D311/62—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with aryl radicals attached in position 2 with oxygen atoms directly attached in position 3, e.g. anthocyanidins
Abstract
The invention provides a method for preparing oligomeric proanthocyanidins based on a catalytic transfer hydrogenation technology, which takes high polymeric proanthocyanidins as a substrate raw material, ammonium formate as a hydrogen source, Pd/C as a catalyst, ethanol-water as a solvent, and ammonium formate as a hydrogen donor, and has the advantages of low price, easy obtaining, good reduction performance and the like, and the residual ammonium formate after the reaction can be rapidly decomposed into hydrogen, carbon dioxide and ammonia under the action of Pd/C, so that the residual ammonium formate is easy to remove from a reaction system, and the environmental pollution can not be caused; the Pd/C catalytic hydrogen addition enables the reaction to be carried out under mild conditions, simplifies the operation, reduces the requirements on equipment, reduces the danger of the reaction, and only needs to filter the palladium-carbon catalyst after the reaction is finished.
Description
Technical Field
The invention relates to a method for preparing oligomeric proanthocyanidins based on a catalytic transfer hydrogenation technology, and belongs to the technical field of medicine synthesis.
Background
Procyanidin has multiple biological activities of antioxidation, anti-inflammation, anticancer, cardiovascular and cerebrovascular protection, neuroprotection and brain health care, etc., procyanidin with different polymerization degrees has different biological activities, and poly procyanidin has lower biological activity because the activity of phenolic hydroxyl is influenced by the larger molecular weight and steric effect; the biological activity of monomer and oligomeric proanthocyanidin in the proanthocyanidins is superior to that of polymeric proanthocyanidins, and research shows that the oligomeric proanthocyanidin polymer (especially di-trimer and trimer) is superior to that of monomer and high polymer in reducing serum cholesterol, resisting oxidation activity, enzyme inhibiting activity, resisting mutation activity and intestinal absorption capacity, and the oligomeric proanthocyanidin has good water solubility and can be used in food, medicine and cosmetic industries with high requirement on water solubility. On the contrary, the high polymeric proanthocyanidin has low bioavailability and its development of antioxidant activity is greatly restricted, so that most of the high polymeric proanthocyanidin separated as a by-product in the process of refining oligomeric proanthocyanidin from the extract can be used only as a low value-added product such as natural pigment.
However, most procyanidins in plants exist in a high polymer form, so in order to improve the bioavailability and water solubility of active substances in plant extracts, high polymeric procyanidins are degraded into oligomeric procyanidins to exert potential antioxidant activity, and the method has a far-reaching significance in improving the utilization rate of natural resources and the added value of procyanidin products.
At present, the methods for degrading high polymeric proanthocyanidins into oligomeric proanthocyanidins mainly include acid and base degradation methods, oxidative degradation methods and hydrogenation degradation methods. For example, chinese patent document CN101012216A discloses a process for preparing oligomeric procyanidins by an acidic degradation method, wherein an acidic solution used in the acidic degradation method causes corrosion to equipment and pollutes the environment; chinese patent document CN1654463 discloses a method for preparing oligomeric procyanidin by oxidative degradation, which adopts hydrogen peroxide with higher concentration as an oxidant, and is unstable and easy to decompose in the using and storing processes, thereby resulting in low catalyst efficiency, high consumption and potential safety hazard; the catalytic hydrogenation method can effectively degrade high polymeric proanthocyanidins into oligomeric proanthocyanidins with stronger biological activity, but the conventional catalytic hydrogenation degradation method uses hydrogen as a hydrogen source, needs high-temperature and high-pressure conditions, has high requirements on reaction equipment, and has a plurality of unsafe factors. Therefore, in order to overcome the defects and shortcomings of the prior art, the method for degrading the high polymeric proanthocyanidins into the oligomeric proanthocyanidins has the advantages of mild reaction conditions, simple post-treatment, high safety and low equipment requirement and is of great significance.
Disclosure of Invention
The invention aims to solve the technical problems that the method for degrading the high polymeric proanthocyanidins into the oligomeric proanthocyanidins in the prior art has the defects of complex reaction conditions, high equipment requirement and low safety, so that the method for degrading the high polymeric proanthocyanidins into the oligomeric proanthocyanidins is mild in reaction conditions, simple in post-treatment, high in safety and low in equipment requirement.
Therefore, the technical scheme for realizing the purpose is as follows:
a method for preparing oligomeric proanthocyanidins based on a catalytic transfer hydrogenation technology comprises the following steps:
(1) dissolving high polymer procyanidine and ammonium formate in an ethanol water solution, adding a palladium-carbon catalyst, controlling the temperature to be 20-60 ℃, filtering after the reaction is finished, and concentrating the filtrate to obtain the crude product of the oligomeric procyanidine; (2) and (3) loading the crude oligomeric proanthocyanidins product into a macroporous resin column, eluting with distilled water and an ethanol water solution in sequence, collecting an eluent, concentrating under reduced pressure, and drying to obtain the oligomeric proanthocyanidins.
In the step (1), the mass ratio of the high polymer procyanidin to the ammonium formate to the palladium-carbon catalyst is 1: (2-4): (0.05-0.2).
In the step (1), the volume ratio of ethanol to water in the ethanol water solution is (6-9): 1.
in the step (2), the macroporous resin column is an AB-8 type macroporous resin column or an LSA-21 type macroporous resin column.
In the step (2), the volume concentration of ethanol in the ethanol water solution is 30-70%.
In the step (2), the volume ratio of the macroporous resin column to the distilled water is 1: (2-5);
the volume ratio of the macroporous resin column to the ethanol aqueous solution is 1: (2-4).
In the step (2), the average polymerization degree of the oligomeric proanthocyanidins is 2-3.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the method for preparing the oligomeric proanthocyanidins based on the catalytic transfer hydrogenation technology comprises the steps of dissolving high polymer proanthocyanidins and ammonium formate in an ethanol water solution, adding a palladium-carbon catalyst, controlling the temperature to be 20-60 ℃, filtering after the reaction is finished, and concentrating the filtrate to obtain an oligomeric proanthocyanidins crude product; then loading the crude product of the oligomeric proanthocyanidins into a macroporous resin column, eluting with distilled water and an ethanol aqueous solution in sequence, collecting eluent, concentrating under reduced pressure, and drying to obtain the oligomeric proanthocyanidins, wherein the method takes high polymeric proanthocyanidins as a substrate raw material, ammonium formate as a hydrogen source, Pd/C as a catalyst, and ethanol-water as a solvent, and performs catalytic transfer hydrogenation reaction on the high polymeric proanthocyanidins to prepare the oligomeric proanthocyanidins, the ammonium formate as a hydrogen donor has the advantages of low price, easy obtainment, good reduction performance and the like, and the residual ammonium formate after the reaction can be rapidly decomposed into hydrogen, carbon dioxide and ammonia under the action of Pd/C, so that the oligomeric proanthocyanidins can be easily removed from a reaction system, and the environmental pollution can not be caused; the Pd/C catalytic hydrogen addition enables the reaction to be carried out under mild conditions, avoids the reduction by hydrogen pressurization in a closed system, simplifies the operation, reduces the requirement on equipment, reduces the danger of the reaction, and only needs to filter the palladium-carbon catalyst after the reaction is finished.
2. The method for preparing the oligomeric proanthocyanidins based on the catalytic transfer hydrogenation technology can reduce the proanthocyanidins with the polymerization degree of 6-8 into the proanthocyanidins with the polymerization degree of 2-3, so that the water solubility of the product can be improved, and the product can be further applied to the industries of foods, medicines and cosmetics with higher requirements on water solubility, and the application range of the product is expanded; in addition, the content of the oligomeric proanthocyanidins prepared by the method is more than 82%, so that the preparation method is simple and the content of the oligomeric proanthocyanidins is high.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The method for preparing oligomeric proanthocyanidins based on the catalytic transfer hydrogenation technology provided by the embodiment comprises the following steps:
(1) preparing a high polymer procyanidin extract: weighing 10kg of grape seeds, crushing, sieving with a 20-mesh sieve, placing in a 100L extraction tank, adding 60L of petroleum ether, soaking and degreasing twice, and filtering to obtain degreased grape seed powder; extracting defatted grape seed powder with 60% ethanol water solution 50L at 50 deg.C twice for 60min, washing the residue with distilled water twice, collecting extractive solution and washing solution, and concentrating at 50 deg.C under reduced pressure until the specific gravity of the solution is 1.15 to obtain 4.5L concentrated solution; adding 3L ethanol into the concentrated solution to precipitate to remove impurities such as protein and polysaccharide, filtering, and concentrating the filtrate under reduced pressure to obtain 4.5L concentrated solution with specific gravity of 1.02; adding 3L ethyl acetate at room temperature to extract the concentrated solution twice, collecting the extractive solution, concentrating under reduced pressure to obtain high polymer procyanidin extract, and drying the high polymer procyanidin extract in vacuum oven to obtain 1.2kg dry high polymer procyanidin for use.
The procyanidin content is determined by Folin-Ciocalteau and HPLC combined method, and the procyanidin content is 84% and the average polymerization degree is 8.76 by detection and analysis.
(2) Placing 5g of the high polymeric proanthocyanidin prepared in the step (1) into a reaction bottle, adding 100mL of ethanol aqueous solution, wherein the volume ratio of ethanol to water in the ethanol aqueous solution is 9:1, adding 20g of ammonium formate into the ethanol aqueous solution, stirring to completely dissolve the ammonium formate, then adding 1g of 5 mass percent Pd/C catalyst, stirring for 4 hours at 25 ℃, filtering the Pd/C catalyst, and concentrating the filtrate to obtain a crude oligomeric proanthocyanidin product;
(3) and (2) loading the crude product of the oligomeric proanthocyanidins on an AB-8 macroporous resin column, sequentially eluting with 3 times of column volume of distilled water and 3 times of column volume of 50% ethanol aqueous solution, collecting eluent, concentrating under reduced pressure, and drying to obtain 2.5g of grape seed oligomeric proanthocyanidins.
The procyanidin content is determined by Folin-Ciocalteau and HPLC combined method, and the procyanidin content is 82% and the average polymerization degree is 2.31 by detection and analysis.
Example 2
The method for preparing oligomeric proanthocyanidins based on the catalytic transfer hydrogenation technology provided by the embodiment comprises the following steps:
(1) preparing a high polymer procyanidin extract: weighing 10kg of grape seeds, crushing, sieving with a 20-mesh sieve, placing in a 100L extraction tank, adding 60L of petroleum ether, soaking and degreasing twice, and filtering to obtain degreased grape seed powder; extracting defatted grape seed powder with 50 vol% ethanol water solution 50L twice at 50 deg.C for 60min, washing the residue with distilled water twice, collecting extractive solution and washing solution, and concentrating at 50 deg.C under reduced pressure until the specific gravity of the solution is 1.2 to obtain 4.5L concentrated solution; adding 3L ethanol into the concentrated solution to precipitate to remove impurities such as protein and polysaccharide, filtering, and concentrating the filtrate under reduced pressure to obtain 4.5L concentrated solution with specific gravity of 1.0; adding 3L ethyl acetate at room temperature to extract the concentrated solution twice, collecting the extractive solution, concentrating under reduced pressure to obtain high polymer procyanidin extract, and drying the high polymer procyanidin extract in vacuum oven to obtain 1.2kg dry high polymer procyanidin for use.
The procyanidin content is determined by Folin-Ciocalteau and HPLC combined method, and the procyanidin content is 80% and the average polymerization degree is 12 by detection and analysis.
(2) Putting 5g of the high polymeric proanthocyanidin prepared in the step (1) into a reaction bottle, adding 100mL of ethanol aqueous solution, wherein the volume ratio of ethanol to water in the ethanol aqueous solution is 6:1, adding 10g of ammonium formate into the ethanol aqueous solution, stirring to completely dissolve the ammonium formate, then adding 0.25g of 5% Pd/C catalyst by mass fraction, stirring for 2 hours at 60 ℃, filtering the Pd/C catalyst, and concentrating the filtrate to obtain a crude oligomeric proanthocyanidin product;
(3) and (2) loading the crude product of the oligomeric proanthocyanidins on an AB-8 macroporous resin column, sequentially eluting with 2 times of column volume of distilled water and 4 times of column volume of 30% ethanol aqueous solution, collecting eluent, concentrating under reduced pressure, and drying to obtain 2.5g of grape seed oligomeric proanthocyanidins.
The procyanidin content is determined by Folin-Ciocalteau and HPLC combined method, and the procyanidin content is 85% and the average polymerization degree is 3 by detection and analysis.
Example 3
The method for preparing oligomeric proanthocyanidins based on the catalytic transfer hydrogenation technology provided by the embodiment comprises the following steps:
(1) preparing a high polymer procyanidin extract: weighing 10kg of grape seeds, crushing, sieving with a 20-mesh sieve, placing in a 100L extraction tank, adding 60L of petroleum ether, soaking and degreasing twice, and filtering to obtain degreased grape seed powder; extracting defatted grape seed powder with 70% ethanol water solution 50L at 50 deg.C twice for 60min, washing the residue with distilled water twice, collecting extractive solution and washing solution, and concentrating at 50 deg.C under reduced pressure until the specific gravity of the solution is 1.1 to obtain 4.5L concentrated solution; adding 3L ethanol into the concentrated solution to precipitate to remove impurities such as protein and polysaccharide, filtering, and concentrating the filtrate under reduced pressure to obtain 4.5L concentrated solution with specific gravity of 1.05; adding 3L ethyl acetate at room temperature to extract the concentrated solution twice, collecting the extractive solution, concentrating under reduced pressure to obtain high polymer procyanidin extract, and drying the high polymer procyanidin extract in vacuum oven to obtain 1.2kg dry high polymer procyanidin for use.
The procyanidin content is determined by Folin-Ciocalteau and HPLC combined method, and the procyanidin content is 95% and the average polymerization degree is 8 by detection and analysis.
(2) Putting 5g of the high polymeric proanthocyanidin prepared in the step (1) into a reaction bottle, adding 100mL of ethanol aqueous solution, wherein the volume ratio of ethanol to water in the ethanol aqueous solution is 7:1, adding 15g of ammonium formate into the ethanol aqueous solution, stirring to completely dissolve the ammonium formate, then adding 0.5g of 5% Pd/C catalyst by mass fraction, stirring for 5 hours at the temperature of 20 ℃, filtering the Pd/C catalyst, and concentrating the filtrate to obtain a crude oligomeric proanthocyanidin product;
(3) loading the crude product of the oligomeric proanthocyanidins on an LSA-21 type macroporous resin column, sequentially eluting with 5 times of column volume of distilled water and 2 times of column volume of 70% ethanol aqueous solution, collecting eluate, concentrating under reduced pressure, and drying to obtain 2.5g of grape seed oligomeric proanthocyanidins.
The procyanidin content is determined by Folin-Ciocalteau and HPLC combined method, and the procyanidin content is 89% and the average polymerization degree is 2 by detection and analysis.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (4)
1. A method for preparing oligomeric proanthocyanidins based on a catalytic transfer hydrogenation technology is characterized by comprising the following steps:
(1) dissolving high polymer procyanidine and ammonium formate in an ethanol water solution, adding a palladium-carbon catalyst, controlling the temperature to be 20-60 ℃, filtering after the reaction is finished, and concentrating the filtrate to obtain the crude product of the oligomeric procyanidine;
(2) loading the crude product of the oligomeric proanthocyanidins into a macroporous resin column, sequentially eluting with distilled water and an ethanol water solution, collecting an eluent, concentrating under reduced pressure, and drying to obtain the oligomeric proanthocyanidins;
in the step (1), the mass ratio of the high polymer procyanidin to the ammonium formate to the palladium-carbon catalyst is 1: (2-4): (0.05-0.2); the volume ratio of ethanol to water in the ethanol water solution is (6-9): 1;
in the step (2), the average polymerization degree of the oligomeric proanthocyanidins is 2-2.31.
2. The method for preparing oligomeric proanthocyanidin based on catalytic transfer hydrogenation technology as claimed in claim 1, wherein, in the step (2),
the macroporous resin column is AB-8 type macroporous resin column or LSA-21 type macroporous resin column.
3. The method for preparing oligomeric procyanidins based on catalytic transfer hydrogenation as claimed in claim 2, wherein in the step (2), the volume concentration of ethanol in the ethanol aqueous solution is 30-70%.
4. The method for preparing oligomeric proanthocyanidin based on catalytic transfer hydrogenation technology as claimed in claim 1,
in the step (2), the volume ratio of the macroporous resin column to the distilled water is 1: (2-5);
the volume ratio of the macroporous resin column to the ethanol aqueous solution is 1: (2-4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710297478.9A CN107089965B (en) | 2017-04-28 | 2017-04-28 | Method for preparing oligomeric proanthocyanidins based on catalytic transfer hydrogenation technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710297478.9A CN107089965B (en) | 2017-04-28 | 2017-04-28 | Method for preparing oligomeric proanthocyanidins based on catalytic transfer hydrogenation technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107089965A CN107089965A (en) | 2017-08-25 |
| CN107089965B true CN107089965B (en) | 2019-12-24 |
Family
ID=59637483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710297478.9A Active CN107089965B (en) | 2017-04-28 | 2017-04-28 | Method for preparing oligomeric proanthocyanidins based on catalytic transfer hydrogenation technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107089965B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239963A (en) * | 2008-03-18 | 2008-08-13 | 上海大学 | Method for catalytic hydrogenolysis of cinnamon proanthocyanidins high polymer to oligomer |
-
2017
- 2017-04-28 CN CN201710297478.9A patent/CN107089965B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239963A (en) * | 2008-03-18 | 2008-08-13 | 上海大学 | Method for catalytic hydrogenolysis of cinnamon proanthocyanidins high polymer to oligomer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107089965A (en) | 2017-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106381319B (en) | Efficient extraction and separation method for grape seed procyanidin oligomers | |
| CN103265520B (en) | Method for preparing oligomeric proanthocyanidins and tannin pigment from grape seeds after winemaking | |
| Ahmad et al. | Recent trends in extraction, purification, and antioxidant activity evaluation of plant leaf‐extract polysaccharides | |
| CN103992359A (en) | Preparation process for extracting green tea polyphenols from tea | |
| CN103263514A (en) | Method for extracting flavones, low-molecule pectin and cellulose from orange peels in combined way | |
| CN106632205A (en) | Method for extracting proanthocyanidins from Yunnan pine bark | |
| CN104523836A (en) | Method for comprehensively extracting protein, polysaccharide and polyphenol from avocado kernels | |
| CN108690099A (en) | A method of the extraction separation procyanidine from black fruit fructus lycii | |
| CN113647623B (en) | Method for improving anthocyanin stability | |
| CN1749253A (en) | Process for extracting proanthocyanidin from grape seed by super critical carbon dioxide | |
| CN107089965B (en) | Method for preparing oligomeric proanthocyanidins based on catalytic transfer hydrogenation technology | |
| CN104000935B (en) | A kind of method that anti-oxidant phenolic acid is extracted in the slag from jacket | |
| CN103483302A (en) | Method for separating and purifying oligomeric proanthocyanidins | |
| CN110818547B (en) | A method for extracting curcumin and gingerol from rhizoma Zingiberis recens | |
| CN101390975A (en) | Extraction method of citrus active ingredient | |
| CN102643261A (en) | Method for extracting cyanidin from blueberry wine residues | |
| CN111943827B (en) | Method for purifying coenzyme Q10 | |
| CN101099752B (en) | Method for extracting pollen essential from Chinese pine pollen | |
| CN109096076B (en) | Chalcone compound and preparation method thereof | |
| CN102851327A (en) | Method for extracting resveratrol in Rhizoma Polygoni Cuspidati through biological process | |
| KR20140002315A (en) | Method for converting and producing functional saponin from ginseng extract using subcritical water and composition using the same | |
| CN103432205A (en) | Novel method for extracting high-purity lotus leaf flavone | |
| CN110054704B (en) | Method for refining mesona chinensis benth polysaccharide by combining ammonium sulfate and CTAB (cetyl trimethyl ammonium bromide) precipitation with macroporous resin | |
| CN107349430B (en) | Phyllanthus emblica polysaccharide-EGCG compound and preparation method thereof | |
| CN107935980B (en) | Production process of D-alpha-tocopherol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |