CN111233806A - Preparation method of 3,5, 4' -triacetoxy-7-hydroxyflavone - Google Patents
Preparation method of 3,5, 4' -triacetoxy-7-hydroxyflavone Download PDFInfo
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- CN111233806A CN111233806A CN202010201463.XA CN202010201463A CN111233806A CN 111233806 A CN111233806 A CN 111233806A CN 202010201463 A CN202010201463 A CN 202010201463A CN 111233806 A CN111233806 A CN 111233806A
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- 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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Abstract
The invention discloses a preparation method of 3,5, 4' -triacetoxy-7-hydroxyflavone, which comprises the following steps: mixing 3,5,7, 4' -tetraacetoxyflavone, pyridine hydrochloride and silica gel in the presence of a solvent; then, after removing the solvent, reacting at a first temperature to obtain the 3,5, 4' -triacetoxy-7-hydroxyflavone. The preparation method of the invention utilizes the synergistic interaction of silica gel and pyridine hydrochloride to carry out deacetylation reaction on 7-position of 3,5,7, 4' -tetraacetoxyflavone with high selectivity, does not use a reagent with larger toxicity, and has high safety and simple operation.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of 3,5, 4' -triacetoxy-7-hydroxyflavone.
Background
Kaempferol (Kaempferol), the chemical name is 3,5,7, 4' -tetrahydroxyflavone, present in plant root, leaf and fruit extensively, Kaempferol distributes in many vegetables and fruits such as Chinese chive, onion, mung bean, pumpkin, potato, tomato, strawberry, etc., and fructus forsythiae, herba Rosmarini officinalis, Acacia, folium Ginkgo, herba Mimosae Pudicae, Chinese cinnamon, etc. traditional Chinese herbal medicine extensively, the modern pharmacological research finds that Kaempferol has many pharmacological activities such as antioxidation, anti-inflammatory, anticancer and prevention cardiovascular disease, because its 7 position is inactivated after being esterified by glucoside or sulfuric acid easily, the bioavailability is low, therefore, it is especially important to modify its 7 position; wherein, 3,5, 4' -triacetoxy-7-hydroxyflavone is an important intermediate for synthesizing derivatives at the 7 th position of kaempferol, and the synthesis route is shown as follows: is generally obtained by selective deacetylation of 3,5,7, 4' -tetraacetoxyflavone under the conditions of thiophenol and imidazole; however, thiophenol is a liquid with strong toxicity and foul smell, is difficult to be amplified for preparation, and has great potential safety hazard; the selectivity of directly using imidazole is very low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of 3,5,4 '-triacetoxy-7-hydroxyflavone, which utilizes the synergistic cooperation of silica gel and pyridine hydrochloride to carry out deacetylation reaction on 7-position of 3,5,7, 4' -tetraacetoxyflavone with high selectivity, does not use a reagent with high toxicity, and has high safety and simple operation.
In order to achieve the above objects, the present invention provides a method for preparing 3,5, 4' -triacetoxy-7-hydroxyflavone, comprising: mixing 3,5,7, 4' -tetraacetoxyflavone, pyridine hydrochloride and silica gel in the presence of a solvent; then, after removing the solvent, reacting at a first temperature to obtain the 3,5, 4' -triacetoxy-7-hydroxyflavone.
The technical scheme of the invention has the following beneficial effects:
(1) the preparation method of the invention utilizes the synergistic interaction of silica gel and pyridine hydrochloride to carry out deacetylation reaction on 7-position of 3,5,7, 4' -tetraacetoxyflavone with high selectivity, does not use a reagent with larger toxicity, and has high safety and simple operation.
(2) The preparation method of the invention has high selectivity and high yield.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
Figure 1 shows a reaction product mass spectrum according to one embodiment of the present invention.
FIG. 2 shows a liquid chromatogram of the reaction product according to example 1 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The invention provides a preparation method of 3,5, 4' -triacetoxy-7-hydroxyflavone, which comprises the following steps: mixing 3,5,7, 4' -tetraacetoxyflavone, pyridine hydrochloride and silica gel in the presence of a solvent; then, after removing the solvent, reacting at a first temperature to obtain the 3,5, 4' -triacetoxy-7-hydroxyflavone.
In the invention, the silica gel is preferably column chromatography silica gel, and the average particle size is 100-200 meshes or 200-300 meshes.
According to the present invention, preferably, the preparation method further comprises the following steps after the reaction at the first temperature: adding an elution solvent for extraction, filtering and removing the elution solvent to obtain the 3,5, 4' -triacetoxy-7-hydroxy flavone.
According to the present invention, preferably, the elution solvent is at least one of ethyl acetate, acetone, butanone, methanol and ethanol.
According to the present invention, it is preferable that the first temperature is 70 to 80 ℃ and the reaction is carried out at the first temperature for 1 hour or more.
According to the present invention, preferably, the solvent is at least one of DMF, ethyl acetate, ethanol, methanol, n-butanol, acetone, and butanone.
According to the invention, the temperature at which the solvent is removed is preferably from 40 to 80 ℃.
According to the present invention, preferably, the molar ratio of the pyridine hydrochloride to the 3,5,7, 4' -tetraacetoxyflavone is not less than 2; the weight ratio of the silica gel to the 3,5,7, 4' -tetraacetoxyflavone is not less than 3.
The invention is further illustrated by the following examples:
the structural formula of 3,5,7,4 '-tetraacetoxyflavone used in the following examples and comparative examples is shown in formula I, and the structural formula of yellow solid 3,5, 4' -triacetoxy-7-hydroxyflavone prepared in the following examples is shown in formula II;
the silica gel used in the following examples and comparative examples was column chromatography silica gel having an average particle size of 100-200 mesh and purchased from Qingdao ocean corporation.
Example 1
This example provides a method for preparing 3,5, 4' -triacetoxy-7-hydroxyflavone, which includes the following steps:
adding 45.4 g of 3,5,7, 4' -tetraacetoxyflavone, 150 g of silica gel, 22.2 g of pyridine hydrochloride and DMF500ml into a single-mouth bottle, evaporating the solvent to dryness at 70 ℃ under reduced pressure, keeping the temperature at 70 ℃ for 2 hours, heating and refluxing 1500ml of ethyl acetate for extraction, filtering, and recovering the ethyl acetate to obtain 31 g of yellow solid with the yield of 75% and the purity of 99.2%.1HNMR(DMSO-d 6500 Hz). delta.2.59 (9H, s),6.18(1H, s),6.44(1H, s)6.92(2H, d),8.04(2H, d),10.74(1H, s, 7-OH) MS-ESI, 411. The mass spectrum is shown in figure 1. The liquid chromatogram is shown in FIG. 2.
Example 2
This example provides a method for preparing 3,5, 4' -triacetoxy-7-hydroxyflavone, which includes the following steps:
adding 45.4 g of 3,5,7, 4' -tetraacetoxyflavone, 200 g of silica gel, 40 g of pyridine hydrochloride and 800ml of ethyl acetate into a single port, evaporating the solvent to dryness at 60 ℃ on a rotary evaporator, keeping the temperature at 70 ℃ for 3 hours, heating and refluxing 1000ml of ethanol for extraction, filtering, and recovering ethanol to obtain 29.2 g of yellow solid, wherein the yield is 71 percent, and the purity is 99.3 percent.1HNMR(DMSO-d 6500 Hz). delta.2.59 (9H, s),6.18(1H, s),6.44(1H, s)6.92(2H, d),8.04(2H, d),10.74(1H, s, 7-OH) MS-ESI, 411. The mass spectrum is shown in figure 1.
Example 3
This example provides a method for preparing 3,5, 4' -triacetoxy-7-hydroxyflavone, which includes the following steps:
adding 45.4 g of 3,5,7, 4' -tetraacetoxyflavone, 200 g of silica gel, 30 g of pyridine hydrochloride and 1000ml of butanone into a single port, evaporating the solvent on a rotary evaporator at 50 ℃ until the solvent is dried, keeping the temperature at 80 ℃ for 3 hours, heating and refluxing 1000ml of ethyl acetate for extraction, filtering, and recovering ethyl acetate to obtain 30.1 g of yellow solid, wherein the yield is 73% and the purity is 99.3%.1HNMR(DMSO-d 6500 Hz). delta.2.59 (9H, s),6.18(1H, s),6.44(1H, s)6.92(2H, d),8.04(2H, d),10.74(1H, s, 7-OH) MS-ESI, 411. The mass spectrum is shown in figure 1.
Example 4
This example provides a method for preparing 3,5, 4' -triacetoxy-7-hydroxyflavone, which includes the following steps:
adding 45.4 g of 3,5,7, 4' -tetraacetoxyflavone, 200 g of silica gel, 350 g of pyridine hydrochloride and 1500ml of n-butyl alcohol into a single port, evaporating the solvent to dryness at 60 ℃ on a rotary evaporator, keeping the temperature at 70 ℃ for 2 hours, heating and refluxing 800ml of methanol for extraction, filtering, and recovering the methanol to obtain 31 g of yellow solid, wherein the yield is 75 percent, and the purity is 99.1 percent.1HNMR(DMSO-d 6500 Hz). delta.2.59 (9H, s),6.18(1H, s),6.44(1H, s)6.92(2H, d),8.04(2H, d),10.74(1H, s, 7-OH) MS-ESI, 411. The mass spectrum is shown in figure 1.
Comparative example 1
Adding 45.4 g of 3,5,7,4 '-tetraacetoxyflavone, 22.2 g of pyridine hydrochloride and DMF500ml into a single-neck flask, evaporating the solvent to dryness at 70 ℃ under reduced pressure, keeping the temperature at 70 ℃ for 2 hours, heating and refluxing 1500ml of ethyl acetate for extraction, filtering, and recovering the ethyl acetate to obtain no yellow solid, namely, the reaction can not prepare the 3,5, 4' -triacetoxy-7-hydroxyflavone. This indicates that deacetylation of the 7-position of 3,5,7, 4' -tetraacetoxyflavone cannot occur without addition of silica gel.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (7)
1. A preparation method of 3,5, 4' -triacetoxy-7-hydroxyflavone is characterized in that the preparation method comprises the following steps: mixing 3,5,7, 4' -tetraacetoxyflavone, pyridine hydrochloride and silica gel in the presence of a solvent; then, after removing the solvent, reacting at a first temperature to obtain the 3,5, 4' -triacetoxy-7-hydroxyflavone.
2. The method of claim 1, further comprising, after reacting at the first temperature, the steps of: adding an elution solvent for extraction, filtering and removing the elution solvent to obtain the 3,5, 4' -triacetoxy-7-hydroxy flavone.
3. The production method according to claim 2, wherein the eluting solvent is at least one of ethyl acetate, acetone, methyl ethyl ketone, methanol, and ethanol.
4. The method according to claim 1, wherein the first temperature is 70 to 80 ℃ and the reaction is carried out at the first temperature for 1 hour or more.
5. The method according to claim 1, wherein the solvent is at least one of DMF, ethyl acetate, ethanol, methanol, n-butanol, acetone and butanone.
6. The production method according to claim 1, wherein the temperature at which the solvent is removed is 40 to 80 ℃.
7. The production method according to claim 1, wherein the molar ratio of the pyridine hydrochloride to the 3,5,7, 4' -tetraacetoxyflavone is not less than 2; the weight ratio of the silica gel to the 3,5,7, 4' -tetraacetoxyflavone is not less than 3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114478457A (en) * | 2022-02-25 | 2022-05-13 | 中南大学 | Activatable aggregation-inducible luminescent probe and application thereof in sensitive detection of carbaryl |
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| CN108752409A (en) * | 2018-07-10 | 2018-11-06 | 武汉工程大学 | The method for preparing epiandrosterone as raw material using androstenedione |
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Patent Citations (4)
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| WO2014056038A1 (en) * | 2012-10-11 | 2014-04-17 | Neuprotect Pty Ltd | Novel flavonoid compounds and uses thereof |
| CN104557891A (en) * | 2013-10-22 | 2015-04-29 | 南京惠特莱医药科技有限公司 | Quercetin derivative and preparation method and application thereof |
| CN107759551A (en) * | 2016-08-22 | 2018-03-06 | 昆明龙津药业股份有限公司 | A kind of synthetic method of breviscapine B aglycone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114478457A (en) * | 2022-02-25 | 2022-05-13 | 中南大学 | Activatable aggregation-inducible luminescent probe and application thereof in sensitive detection of carbaryl |
| CN114478457B (en) * | 2022-02-25 | 2023-09-22 | 中南大学 | Activated aggregation-induced emission probe and application thereof in sensitive detection of carbaryl |
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