CN106008437A - Preparation method of tetraacetylscutellarein - Google Patents
Preparation method of tetraacetylscutellarein Download PDFInfo
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- CN106008437A CN106008437A CN201610511264.2A CN201610511264A CN106008437A CN 106008437 A CN106008437 A CN 106008437A CN 201610511264 A CN201610511264 A CN 201610511264A CN 106008437 A CN106008437 A CN 106008437A
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- scutellarin
- genin
- acetyl
- pyridine
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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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- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a preparation method of tetraacetylscutellarein. The tetraacetylscutellarein is obtained by taking scutellarin as a starting raw material, refluxing the scutellarin with acetic anhydride and pyridine, cooling reaction liquid after a reaction is finished and carrying out silica-gel column chromatography; 4-dimethylamino-pyridine is also added into the reaction liquid. The tetraacetylscutellarein is prepared from the scutellarin in one step and synthesis steps and processes are reduced, so that the working efficiency is improved; the dosage of acid is reduced so hat the cost is saved and the environmental pollution is reduced; the yield is greatly improved.
Description
Technical field
The invention belongs to organic chemical synthesis field, be specifically related to the preparation method of a kind of four acetyl scutellarin genin.
Background technology
Herba Erigerontis is one of distinctive natural drug in Yunnan Province, has another name called Herba Erigerontis, Erigeron breviscapus (Vant.) Hand.-Mazz., flies for Compositae Radix Asteris race
Fluffy platymiscium Erigeron breviscapus (Vant.) Hand.-Mazz. [Erigeron breviscapus(Vant.) Hand.-mazz] dry herb, its
Cold in nature, mildly bitter flavor, Gan Wenxin, there is the effects such as wind dispelling cold expelling, blood circulation promoting and blood stasis dispelling, dredge the meridian passage, anti-inflammatory analgetic.Scutellarin is lamp
The principle active component of small cup flower, has another name called scutellarin, and the glucuronic acid sloughing 7 after hydrolysis generates scutellarin genin.Grind
Study carefully discovery, scutellarin and aglycon thereof to there is antioxidation, protection brain trauma, prevent pulmonary fibrosis, anti-cerebral anoxia, protection brain to lack
Blood, protection brain trauma, protection diabetes and hypertension kidney injury, anti-apoptotic, protection cardiovascular and cerebrovascular vessel, AntiHIV1 RT activity, anti-swollen
The effects such as tumor, suppression liver drug enzyme activity.
In terms of pharmaceutical chemistry research, scutellarin and aglycon thereof have been carried out series structure as lead compound by people
Transformation, has obtained a series of scutellarin derivant with potential using value.Building-up process in scutellarin derivant
In, four acetyl scutellarin genin are important intermediate.At present, synthesize the method for four acetyl scutellarin genin be with
Scutellarin is raw material, first obtains scutellarin genin after acid-catalyzed hydrolysis；Tetrem is obtained through acetylation after separating-purifying
Acyl scutellarin genin, needs through two steps.Inventor is at education department of Yunnan Province scientific research fund project " scutellarin
The synthesis of aglycon-L-arginine derivant " (bullets: 2015Y314) support under, in research process by scutellarin with
Acetic anhydride, pyridine reflux together, have unexpectedly obtained just having been obtained four acetyl scutellarin genin by scutellarin one step.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of four acetyl scutellarin genin.
The object of the present invention is achieved like this:
With scutellarin as initiation material, reflux together with acetic anhydride, pyridine, wherein scutellarin: the mol ratio of acetic anhydride is
1:5 ~ 1:20, acetic anhydride: the volume ratio of pyridine is 1.2:1 ~ 2:1；Reaction obtains through silica gel column chromatography after terminating the cooling of rear reactant liquor
To four acetyl scutellarin genin.
Reactant liquor is also added into DMAP, wherein DMAP: the mol ratio of scutellarin is
0.02:1~0.2:1。
Feeding intake of scutellarin is 5 grams, acetic anhydride 15 milliliters, pyridine 10 milliliters.
Return time is 4 hours.
The invention have the advantages that
1, the present invention has just been obtained four acetyl scutellarin genin by scutellarin one step, decreases synthesis step process, increases
Work efficiency.
2, in building-up process before, owing to the intermediate scutellarin genin generated is the most oxidized, cause productivity relatively low.
The present invention is directly synthesized four acetyl scutellarin genin by scutellarin one step, and productivity is greatly promoted.
3, the present invention need not, through acid-catalyzed hydrolysis step, decrease the consumption of acid, cost-effective, reduces environmental pollution.
Detailed description of the invention
The present invention is further illustrated below, but is any limitation as the present invention never in any form, based on the present invention
Any conversion made, belongs to protection scope of the present invention.
Embodiment 1:
By scutellarin 5.0 grams (10.8mmol), backflow 4 is little together with acetic anhydride 15 milliliters (158.7mmol), pyridine 10 milliliters
Time, obtain four acetyl scutellarin genin 4.01 grams (productivity 81.6%) through silica gel column chromatography after cooling.
Embodiment 2:
By scutellarin 5.9 grams (12.7mmol), reflux 4 hours together with acetic anhydride 6 milliliters (63.5mmol), pyridine 6 milliliters,
Four acetyl scutellarin genin 3.42 grams (productivity 59.0%) is obtained through silica gel column chromatography after cooling.
Embodiment 3:
By scutellarin 5.9 grams (12.7mmol), backflow 4 is little together with acetic anhydride 24 milliliters (254mmol), pyridine 12 milliliters
Time, obtain four acetyl scutellarin genin 4.63 grams (productivity 80.2%) through silica gel column chromatography after cooling.
Embodiment 4:
By scutellarin 5.0 grams (10.8mmol), with acetic anhydride 15 milliliters (158.7mmol), DMAP 26.4 milli
Gram (0.216mmol), pyridine 10 milliliters reflux 4 hours together, obtain four acetyl scutellarin glycosides through silica gel column chromatography after cooling
4.08 grams (productivity 83.1%) of unit.
Embodiment 5:
By scutellarin 5.0 grams (10.8mmol), with acetic anhydride 15 milliliters (158.7mmol), DMAP 264.0 milli
Gram (2.16mmol), pyridine 10 milliliters reflux 4 hours together, obtain four acetyl scutellarin genin through silica gel column chromatography after cooling
4.19 grams (productivity 85.4%).
Comparative example 1:
Scutellarin 5.0 grams (10.8mmol), 5 milliliters of water, 60 milliliters of ethanol, 60 milliliters of concentrated hydrochloric acid are refluxed under nitrogen protection
Overnight, after being cooled to room temperature, reactant liquor is poured into water, filters, wash filter cake with water the most neutral, collect filter cake, be dried, i.e. oil lamp
B prime aglycon.By dry scutellarin genin and acetic anhydride 15 milliliters (158.7mmol), DMAP 264.0 milli
Gram (2.16mmol), pyridine 10 milliliters reflux 4 hours together, obtain four acetyl scutellarin genin through silica gel column chromatography after cooling
1.15 grams (two step productivity 23.4%).
Claims (4)
1. the preparation method of an acetyl scutellarin genin, it is characterised in that with scutellarin as initiation material, with acetic acid
Acid anhydride, pyridine reflux together, wherein scutellarin: the mol ratio of acetic anhydride is 1:5 ~ 1:20, acetic anhydride: the volume ratio of pyridine is
1.2:1~2:1；Reaction obtains four acetyl scutellarin genin through silica gel column chromatography after terminating the cooling of rear reactant liquor.
The preparation method of four acetyl scutellarin genin the most according to claim 1, it is characterised in that also add in reactant liquor
Enter DMAP, wherein DMAP: the mol ratio of scutellarin is 0.02:1 ~ 0.2:1.
The preparation method of four acetyl scutellarin genin the most according to claim 1 and 2, is characterized in that: described oil lamp
Feeding intake of B prime is 5 grams, acetic anhydride 15 milliliters, pyridine 10 milliliters.
The preparation method of four acetyl scutellarin genin the most according to claim 1 and 2, is characterized in that: described backflow
Time is 4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610511264.2A CN106008437B (en) | 2016-07-04 | 2016-07-04 | A kind of preparation method of four acetyl Scutellarein |
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| CN201610511264.2A CN106008437B (en) | 2016-07-04 | 2016-07-04 | A kind of preparation method of four acetyl Scutellarein |
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| CN106008437A true CN106008437A (en) | 2016-10-12 |
| CN106008437B CN106008437B (en) | 2018-08-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358879A (en) * | 2017-09-04 | 2018-08-03 | 云南中医学院 | Scutellarein ether derivative and the preparation method and application thereof |
-
2016
- 2016-07-04 CN CN201610511264.2A patent/CN106008437B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| YANG PING等: "Synthesis and biological evaluation of 8-substituted and deglucuronidated scutellarin and baicalin analogues as antioxidant responsive element activators", 《SCIENCE CHINA CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358879A (en) * | 2017-09-04 | 2018-08-03 | 云南中医学院 | Scutellarein ether derivative and the preparation method and application thereof |
| CN108358879B (en) * | 2017-09-04 | 2021-07-23 | 云南中医学院 | Scutellarin aglycone ether derivative and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN106008437B (en) | 2018-08-03 |
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Address after: 650500, 1076, Yuhua District, Xincheng Town, Yunnan, Kunming, Chenggong Patentee after: Yunnan University of Traditional Chinese Medicine Address before: 650500, 1076, Yuhua District, Xincheng Town, Yunnan, Kunming, Chenggong Patentee before: YUNNAN University OF TRADITIONAL CHINESE MEDICINE |
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Effective date of registration: 20191205 Address after: 652199 Kuangyuan town damuxing village, Yiliang County, Kunming City, Yunnan Province Patentee after: Yunnan HaoChen Pharmaceutical Co.,Ltd. Address before: 650500, 1076, Yuhua District, Xincheng Town, Yunnan, Kunming, Chenggong Patentee before: Yunnan University of Traditional Chinese Medicine |
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