CN105294630B - A kind of preparation method of myricetin - Google Patents
A kind of preparation method of myricetin Download PDFInfo
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- CN105294630B CN105294630B CN201510810054.9A CN201510810054A CN105294630B CN 105294630 B CN105294630 B CN 105294630B CN 201510810054 A CN201510810054 A CN 201510810054A CN 105294630 B CN105294630 B CN 105294630B
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- myricetin
- dihydromyricetin
- preparation
- alcohols
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- 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
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
- C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
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- 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
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/40—Separation, e.g. from natural material; Purification
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention provides a kind of preparation method of myricetin, comprises the following steps：Dihydromyricetin is mixed with alcohols, liquor natrii hypochloritis and catalyst is added, continuously adds liquor natrii hypochloritis after question response is complete, obtain myricetin；Alcohols is methanol or ethanol；Catalyst is aluminum trichloride (anhydrous) or anhydrous ferric trichloride.The present invention prepares product myricetin using dihydromyricetin as initiation material by semi-synthetic；Obtained because dihydromyricetin extracts from plant vine tea, content more than 98%, cost is low, simple to operate, and product yield is high, and product is without refined, content more than 98%, suitable for industrialized production.
Description
Technical field
The present invention relates to chemosynthesis technical field, and in particular to the semisynthesis of natural products myricetin.
Background technology
Myricetin, also known as myricetin, the flavonol of chemical name 3,3,4,5,5,7-6, sterling is yellow needle-like crystals.Poplar
Syphilis is widely present in the leaf, root and limb of red bayberry, has vasoconstriction, rise blood pressure, excited heart, cholagogic, anti-inflammatory, cause prominent
The effect such as change, it is also used as treating diabetes and cataract, therefore the developmental research for myricetin is significant.Poplar
The structural formula of syphilis is as follows：
Myricetin content in natural plants is seldom, and document report shows tooth in natural vine tea and Vitaceae ampelopsis
2% or so content is there are about in the leaf of porcelain ampelopsis, but is up in plant vine tea containing abundant dihydromyricetin, content
To 30%, many documents and materials are reported extracting dihydromyricetin from vine tea.Patent CN101973976 report from
A kind of method that dihydromyricetin is extracted from vine tea；Patent CN03138054 report from vine tea extract dihydromyricetin and
The method of the composition of myricetin；Patent CN1887881 is reported using vine tea as raw material water extraction, concentration, weak base is added, by dihydro
Myricetin converts to obtain myricetin, and yield is only 8%.
The content of the invention
Problem to be solved by this invention be to provide it is a kind of it is simple to operate, product yield is high and is used in industrialized production poplar
The preparation method of syphilis.
The technical scheme to solve the above problems：The preparation method of the myricetin provided, comprises the following steps：
Dihydromyricetin is mixed with alcohols, adds liquor natrii hypochloritis and catalyst, continues to add after question response is complete
Enter liquor natrii hypochloritis, obtain myricetin；The alcohols is methanol or ethanol；The catalyst is aluminum trichloride (anhydrous) or anhydrous three
Iron chloride.
Comprise the following steps that：Dihydromyricetin and alcohols are mixed evenly, it is 10% then to add mass concentration
Liquor natrii hypochloritis and catalyst, temperature rising reflux, mass concentration are continuously added as 10% liquor natrii hypochloritis, temperature rising reflux,
After question response is complete, room temperature is down to, is stood, is filtered, dries, obtains yellow needles solid, i.e. myricetin；The alcohols is methanol
Or ethanol；The catalyst is aluminum trichloride (anhydrous) or anhydrous ferric trichloride；
Above-mentioned alcohols is methanol or ethanol；The catalyst is aluminum trichloride (anhydrous) or anhydrous ferric trichloride；
The mass ratio of above-mentioned dihydromyricetin and alcohols is 1：5-10；The dihydromyricetin and the hypochlorous acid added twice
The mass ratio of sodium solution is 1：0.5-0.8；The mass ratio of the dihydromyricetin and catalyst is 1：0.05.Above-mentioned sodium hypochlorite
Solution is industrial rank, and specification is mass concentration 10%, takes the mode added, and dosage is to ensure the PH of reaction solution controls in 7-
8。
The mass concentration of above-mentioned ethanol or methanol is 85%-95%.
The above-mentioned temperature rising reflux time is 1-3h.
It is complete using TLC detection raw material reactions.
Advantages of the present invention：
The present invention prepares product myricetin using dihydromyricetin as initiation material by semi-synthetic；Due to dihydromyricetin
Extract and obtain from plant vine tea, content more than 98%, cost is low, simple to operate, and product yield is high, and product contains without refining
Amount more than 98%, suitable for industrialized production.
Embodiment
The semisynthesis of myricetin of the present invention includes following synthetic route：
Embodiment 1
In four mouthfuls of reaction bulbs, feed intake dihydromyricetin 20g, and mass concentration is 85% ethanol 200ml, is stirred,
The liquor natrii hypochloritis 13ml that mass concentration is 10% is added dropwise, anhydrous ferric trichloride 1g, temperature rising reflux, after 2h, it is dense to add quality
The liquor natrii hypochloritis 2ml for 10% is spent, continues to flow back, after 2h, TLC detections, raw material reaction finishes, and stops reaction, is down to room
Temperature, stand overnight, filter, 60 DEG C of dryings, obtain yellow needles solid 17g.Content 98% (HPLC), yield 85.5%.
Embodiment 2
In four mouthfuls of reaction bulbs, feed intake dihydromyricetin 20g, and mass concentration is 90% ethanol 260ml, is stirred,
The liquor natrii hypochloritis 12ml that mass concentration is 10% is added dropwise, anhydrous ferric trichloride 1g, temperature rising reflux, after 1h, it is dense to add quality
The liquor natrii hypochloritis 2.5ml for 10% is spent, continues to flow back, after 2.5h, TLC detections, raw material reaction finishes, and stops reaction, drop
To room temperature, stand overnight, filter, 60 DEG C of dryings, obtain yellow needles solid 17.4g.Content 98% (HPLC), yield
87.6%.
Embodiment 3
In four mouthfuls of reaction bulbs, feed intake dihydromyricetin 20g, and mass concentration is 92% ethanol 150ml, is stirred,
The liquor natrii hypochloritis 11ml that mass concentration is 10% is added dropwise, aluminum trichloride (anhydrous) 1g, temperature rising reflux, after 1h, it is dense to add quality
The liquor natrii hypochloritis 2ml for 10% is spent, continues to flow back, after 3h, TLC detections, raw material reaction finishes, and stops reaction, is down to room
Temperature, stand overnight, filter, 60 DEG C of dryings, obtain yellow needles solid 17.9g.Content 98% (HPLC), yield 90.1%.
Embodiment 4
In four mouthfuls of reaction bulbs, feed intake dihydromyricetin 20g, and mass concentration is 95% methanol 140ml, is stirred,
The liquor natrii hypochloritis 12ml that mass concentration is 10% is added dropwise, aluminum trichloride (anhydrous) 1g, temperature rising reflux, after 2h, it is dense to add quality
The liquor natrii hypochloritis 2ml for 10% is spent, continues to flow back, after 2h, TLC detections, raw material reaction finishes, and stops reaction, is down to room
Temperature, stand overnight, filter, 60 DEG C of dryings, obtain yellow needles solid 18.1g.Content 98% (HPLC), yield 91.2%.
Embodiment 5
In four mouthfuls of reaction bulbs, feed intake dihydromyricetin 20g, and mass concentration is 90% methanol 160ml, is stirred,
The liquor natrii hypochloritis 12ml that mass concentration is 10% is added dropwise, anhydrous ferric trichloride aluminium 1g, temperature rising reflux, after 2h, adds quality
Concentration is 10% liquor natrii hypochloritis 2ml, continues to flow back, and after 2.5h, TLC detections, raw material reaction finishes, and stops reaction, drop
To room temperature, stand overnight, filter, 60 DEG C of dryings, obtain yellow needles solid 16.9g.Content 98% (HPLC), yield
85.2%.
Claims (4)
1. a kind of preparation method of myricetin, it is characterised in that comprise the following steps：Dihydromyricetin and alcohols are mixed
Uniformly, the liquor natrii hypochloritis and catalyst, temperature rising reflux that mass concentration is 10% are then added, continuously adding mass concentration is
10% liquor natrii hypochloritis, temperature rising reflux, after question response is complete, room temperature is down to, stood, filtered, dried, obtain yellow needles
Solid, i.e. myricetin；The alcohols is methanol or ethanol；The catalyst is aluminum trichloride (anhydrous) or anhydrous ferric trichloride；
The mass ratio of the dihydromyricetin and alcohols is 1：5-10；The dihydromyricetin and the sodium hypochlorite added twice are molten
The mass ratio of liquid is 1：0.5-0.8；The mass ratio of the dihydromyricetin and catalyst is 1：0.05.
2. the preparation method of myricetin according to claim 1, it is characterised in that：The mass concentration of the ethanol or methanol
For 85%-95%.
3. the preparation method of myricetin according to claim 2, it is characterised in that：The temperature rising reflux time is 1-3h.
4. the preparation method of myricetin according to claim 3, it is characterised in that：It is complete using TLC detection raw material reactions.
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| CN201510810054.9A CN105294630B (en) | 2015-11-20 | 2015-11-20 | A kind of preparation method of myricetin |
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| CN105294630B true CN105294630B (en) | 2018-01-02 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108586409A (en) * | 2018-04-12 | 2018-09-28 | 铜仁学院 | A kind of preparation method being converted into myricetin with efficient dihydromyricetin |
| CN109020938A (en) * | 2018-08-17 | 2018-12-18 | 昆明龙津药业股份有限公司 | A kind of preparation method of myricetin |
| CN109267088A (en) * | 2018-09-05 | 2019-01-25 | 湖南中茂生物科技有限公司 | A kind of method of dihydromyricetin dehydrogenation |
| CN110627761A (en) | 2019-10-12 | 2019-12-31 | 上海尹胜咨询管理合伙企业(有限合伙) | Method for synthesizing myricetin |
| CN112851614A (en) * | 2020-12-28 | 2021-05-28 | 江苏天晟药业股份有限公司 | Preparation method of myricetin |
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| CN103819442A (en) * | 2014-03-01 | 2014-05-28 | 张家港威胜生物医药有限公司 | Synthesis technology of active natural product dihydromyricetin |
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