CN110590727A - Preparation method of equol - Google Patents
Preparation method of equol Download PDFInfo
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- CN110590727A CN110590727A CN201910868788.0A CN201910868788A CN110590727A CN 110590727 A CN110590727 A CN 110590727A CN 201910868788 A CN201910868788 A CN 201910868788A CN 110590727 A CN110590727 A CN 110590727A
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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
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Abstract
The invention relates to a preparation method of equol, which comprises the following steps: s1: synthesis of the Benzochroman: weighing daidzein raw material, dissolving in DMF, adding palladium carbon in a hydrogenation kettle, and reacting at the same speed at constant temperature and constant pressure; filtering the catalyst, adding ice water into the filtrate, stirring to separate out a white solid, filtering, washing with water, and drying to obtain an intermediate a; s2: and (3) synthesis of a condensation compound: adding the intermediate a, dichloroethane and polyphosphoric acid into a three-mouth bottle, performing reflux reaction, cooling, and adding into ice water; taking organic phase by layers, drying the organic phase by sodium sulfate, concentrating dichloroethane to obtain yellow oily matter, and recrystallizing the yellow oily matter by 90% ethanol water to obtain an intermediate b; s3: and (3) synthesizing equol: and adding the intermediate b, DMF and a catalyst into a hydrogenation kettle, reacting at constant temperature and constant pressure, filtering out the catalyst, adding the filtrate into ice water, stirring to separate out a gray solid, filtering, and recrystallizing a filter cake with 70% methanol water to obtain the equol. The method has the advantages of simple steps, high total yield, environmental protection and easy operation.
Description
Technical Field
The invention relates to a preparation method of equol.
Background
Equol, english name, chemical name 3- (4-hydroxyphenyl) -7 chromanol, cas number 94105-90-5. Equol is the final metabolite of soybean isoflavone, is more beneficial to the absorption of human body, has oxidation resistance, has the effects of preventing and treating breast cancer and prostatic cancer, and has the effect of regulating estrogen. At present, the main production place is in Japan, the main application is also in Japan, and many advanced Japanese health care cosmetic products contain the effective component. In China, either production, manufacture or use is essentially a blank. I judge that the product has further expanded application range and market. And therefore efforts are being made to develop and produce equol. Two preparation methods are known and reported at present. Firstly, m-oxyphenol and p-hydroxyphenylacetic acid are used as raw materials, and the reaction is carried out by 5 steps of Friedel-crafts reaction, catalytic hydrogenation, demethylation and the like, the total yield is 20 percent, and the reaction is obtained by resolution, so the reaction steps are complicated and are not suitable for large-scale production. Secondly, the equol is obtained by 6 steps of reaction by using resorcinol as a raw material, the total yield is 30%, the production period is long, and the cost is high.
Disclosure of Invention
The invention aims to solve the problems and provide the preparation method of the equol, which has the advantages of simple steps, high total yield, environmental protection and easy operation.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of equol comprises the following steps:
s1: synthesis of the Benzochroman:
weighing a plurality of daidzein raw materials, dissolving the daidzein raw materials in DMF (dimethyl formamide), adding palladium carbon into a dry and clean hydrogenation kettle, and reacting for a plurality of hours at constant temperature and constant pressure according to the same rotating speed; filtering the catalyst, adding the filtrate into ice water, stirring to separate out a white solid, filtering, washing with water, and drying to obtain an intermediate a;
s2: and (3) synthesis of a condensation compound:
adding a plurality of intermediates a, dichloroethane and polyphosphoric acid into a three-necked bottle, performing reflux reaction, cooling and cooling; adding into ice water; taking an organic phase by layers, drying the organic phase by sodium sulfate, concentrating dichloroethane to obtain a yellow oily substance, and recrystallizing the yellow oily substance by using 90% ethanol water to obtain a white-like solid which is an intermediate b;
s3: and (3) synthesizing equol:
adding the intermediate b, DMF and a catalyst into a hydrogenation kettle, and reacting for several hours at constant temperature and constant pressure at the same rotating speed; after the reaction is finished, filtering out the catalyst, adding the filtrate into ice water, stirring to separate out a gray solid, filtering, and recrystallizing the filter cake by using 70% methanol water to obtain the product equol.
Further, the palladium carbon is 5% palladium carbon, and the daidzein raw material, the intermediate a and the intermediate b weighed in the steps S1, S2 and S3 are all 0.1 mol.
Further, in S1, intermediate a was obtained in 24g with a yield of 93%.
Further, in S2, intermediate b was obtained in 18g with a yield of 75%.
Further, in the S1, 20-30 g of daidzein raw material, 80-100 g of DMF and 5-15 g of palladium carbon are weighed; the temperature is 20-30 ℃, the hydrogen pressure is 0.08Mpa, the rotating speed is 500-800 r, and the reaction time is 3-5 hours.
Preferably, in the step S1, 25.4g of daidzein raw material, 100g of DMF and 10g of palladium on carbon are weighed; the temperature is 25 ℃, the hydrogen pressure is 0.08Mpa, the rotating speed is 500 r, and the reaction time is 3 hours.
Further, in the S2, adding 20-30 g of the intermediate a, 300-500 g of dichloroethane and 25-35 g of polyphosphoric acid into a 500-1000 ml three-necked bottle, carrying out reflux reaction for 8-10 hours, cooling, and adding into 300-500 g of ice water.
Preferably, in the S2, 25.8g of the intermediate a, 300g of dichloroethane and 30g of polyphosphoric acid are taken and put into a 500ml three-necked flask, and reacted under reflux for 8 hours, cooled and added into 300g of ice water.
Further, in the S3, adding 20-30 g of the intermediate b, 80-100 g of DMF and 10-20 g of a catalyst into a hydrogenation kettle, and carrying out hydrogenation reaction at a hydrogen pressure of 0.1MPa and a temperature of 20-30 ℃ for 5-10 hours; after the reaction is finished, filtering out the catalyst, adding the filtrate into 500-1000 g of ice water, and stirring to separate out a gray solid.
Preferably, in the S3, taking the intermediate b24g, DMF100g and 10g of catalyst, adding the mixture into a hydrogenation kettle, and carrying out hydrogenation reaction for 8 hours at the hydrogen pressure of 0.1Mpa and the temperature of 25 ℃; after the reaction, the catalyst was filtered off, and the filtrate was added to 500g of ice water and stirred to precipitate a gray solid.
Compared with the prior art, the invention has the beneficial effects that:
the invention takes daidzein as a raw material, and directly synthesizes equol through three steps of reactions of hydrogenation, dehydration and hydrogenation, the total yield is 50 percent, the production period and the raw material cost are reduced, and the invention is beneficial to the popularization and the application of the equol. Daidzein is adopted, and the hydrogenation reaction is directly carried out without protecting hydroxyl, so that two steps of reaction are saved, the operation steps are simplified, and the efficiency is improved; in the dehydration reaction, polyphosphoric acid is adopted to replace common phosphoric acid or sulfuric acid, so that side reactions can be reduced, the yield can be improved, and the method is environment-friendly and simple to operate.
Drawings
In order to more clearly illustrate the technical solution of the embodiment of the present invention, the drawings needed to be used in the description of the embodiment will be briefly introduced below, and it is obvious that the drawings in the following description are only for more clearly illustrating the embodiment of the present invention or the technical solution in the prior art, and for those skilled in the art, other drawings can be obtained according to the drawings without any creative effort.
FIG. 1 is a diagram showing the reaction process of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood and implemented by those skilled in the art, the present invention is further described with reference to the following specific examples, which are provided for illustration only and are not intended to limit the present invention.
The preparation method of equol shown in figure 1 is implemented according to the following steps:
s1: synthesis of the Benzochroman:
weighing 20-30 g of daidzein raw material, dissolving in 80-100 g of DMF, adding 5% palladium carbon 5-15 g into a dry and clean hydrogenation kettle, and reacting at constant temperature and constant pressure at a rotating speed of 500-800 rpm for 3-5 hours; filtering the catalyst, adding the filtrate into ice water, stirring to separate out a white solid, filtering, washing with water, and drying to obtain an intermediate a;
s2: and (3) synthesis of a condensation compound:
adding 20-30 g of the intermediate a, 300-500 g of dichloroethane and 25-35 g of polyphosphoric acid into a 500-1000 ml three-necked bottle, carrying out reflux reaction for 8-10 hours, cooling and cooling; adding the mixture into 300-500 g of ice water; taking an organic phase by layers, drying the organic phase by sodium sulfate, concentrating dichloroethane to obtain a yellow oily substance, and recrystallizing the yellow oily substance by using 90% ethanol water to obtain a white-like solid which is an intermediate b;
s3: and (3) synthesizing equol:
adding 20-30 g of the intermediate b, 80-100 g of DMF and 10-20 g of catalyst into a hydrogenation kettle, and carrying out hydrogenation reaction for 5-10 hours at the hydrogen pressure of 0.1Mpa and the temperature of 20-30 ℃; and after the reaction is finished, filtering out the catalyst, adding the filtrate into 500-1000 g of ice water, stirring to separate out a gray solid, filtering, and recrystallizing a filter cake by using 70% methanol water to obtain the product equol.
Further, the palladium carbon is 5% palladium carbon, and the daidzein raw material, the intermediate a and the intermediate b weighed in the steps S1, S2 and S3 are all 0.1 mol.
The first embodiment is as follows:
s1: synthesis of the Benzochroman:
weighing 20g of daidzein raw material, dissolving in 80g of DMF, adding 5g of 5% palladium carbon into a dry and clean hydrogenation kettle, and reacting at 25 ℃ and 0.08MPa of hydrogen pressure for 4 hours at the rotating speed of 800 revolutions; filtering the catalyst, adding the filtrate into ice water, stirring to separate out a white solid, filtering, washing with water, and drying to obtain an intermediate a with a yield of 92%;
s2: and (3) synthesis of a condensation compound:
adding the intermediate a20g, dichloroethane 400g and polyphosphoric acid 25g into a 800ml three-necked bottle, carrying out reflux reaction for 10 hours, cooling and cooling; adding into 500g of ice water; taking an organic phase by layers, drying the organic phase by sodium sulfate, concentrating dichloroethane to obtain a yellow oily substance, and recrystallizing the yellow oily substance by using 90% ethanol water to obtain a white-like solid which is an intermediate b with the yield of 73%;
s3: and (3) synthesizing equol:
adding the intermediate b20g, DMF80g and 20g of catalyst into a hydrogenation kettle, and carrying out hydrogenation reaction for 5 hours at the hydrogen pressure of 0.1Mpa and the temperature of 20 ℃; after the reaction is finished, filtering out the catalyst, adding the filtrate into 1000g of ice water, stirring to separate out a gray solid, filtering, and recrystallizing the filter cake by using 70% methanol water to obtain the product equol.
Example two:
s1: synthesis of the Benzochroman:
weighing 25.4g (0.1mol) of daidzein, dissolving the daidzein in 100g of DMF, putting 10g of 5% palladium carbon into a dry and clean hydrogenation kettle, reacting for 3 hours at the temperature of 25 ℃ and the hydrogen pressure of 0.08Mpa under the condition of 500 revolutions, completely reacting by using a point plate, filtering a catalyst, adding filtrate into ice water, stirring to separate out a white solid, filtering, washing with water, and drying to obtain a intermediate a 24g, wherein the yield is 93%;
s2: and (3) synthesis of a condensation compound:
adding 25.8g (0.1mol) of intermediate a, 300g of dichloroethane and 30g of polyphosphoric acid into a 500ml three-necked bottle, carrying out reflux reaction for 8 hours, cooling, adding the cooled product into 300g of ice water, layering to obtain an organic phase, drying the organic phase with sodium sulfate, concentrating the dichloroethane to obtain a yellow oily substance, and recrystallizing with 90% ethanol water to obtain 18g of a white-like solid, namely the yield of the intermediate b is 75%;
s3: and (3) synthesizing equol:
and (3) taking the intermediate b24g (0.1mol), DMF100g and 10g of catalyst, adding into a hydrogenation kettle, carrying out hydrogenation reaction for 8 hours at the hydrogen pressure of 0.1Mpa and the temperature of 25 ℃, filtering out the catalyst after the reaction is finished, adding the filtrate into 500g of ice water, stirring to separate out a gray solid, filtering, and recrystallizing the filter cake with 70% methanol water to obtain the product equol.
Example three:
s1: synthesis of the Benzochroman:
weighing 30g of daidzein raw material, dissolving in 90g of DMF, adding 15g of 5% palladium carbon into a dry and clean hydrogenation kettle, and reacting at 25 ℃ and 0.08MPa of hydrogen pressure for 5 hours at the rotation speed of 650 revolutions; filtering the catalyst, adding the filtrate into ice water, stirring to separate out a white solid, filtering, washing with water, and drying to obtain an intermediate a with the yield of 90%;
s2: and (3) synthesis of a condensation compound:
adding 30g g of intermediate a, 500g of dichloroethane and 35g of polyphosphoric acid into a 1000ml three-necked bottle, carrying out reflux reaction for 9 hours, cooling and cooling; adding into 400g of ice water; taking an organic phase by layers, drying the organic phase by sodium sulfate, concentrating dichloroethane to obtain a yellow oily substance, and recrystallizing the yellow oily substance by using 90% ethanol water to obtain a white-like solid which is an intermediate b with the yield of 72%;
s3: and (3) synthesizing equol:
adding the intermediate b30g, DMF90g and 15g of catalyst into a hydrogenation kettle, and carrying out hydrogenation reaction for 10 hours at the hydrogen pressure of 0.1MPa, the hydrogen pressure of 0.1MPa and the temperature of 30 ℃; after the reaction is finished, filtering out the catalyst, adding the filtrate into 800g of ice water, stirring to separate out a gray solid, filtering, and recrystallizing the filter cake by using 70% methanol water to obtain the product equol.
The invention takes daidzein as a raw material, and directly synthesizes equol through three steps of reactions of hydrogenation, dehydration and hydrogenation, the total yield is 50 percent, the production period and the raw material cost are reduced, and the invention is beneficial to the popularization and the application of the equol.
Key points and protection points of the invention:
daidzein is adopted, and the hydrogenation reaction is directly carried out without protecting hydroxyl, so that two steps of reaction are saved, the operation steps are simplified, and the efficiency is improved; in the dehydration reaction, polyphosphoric acid is adopted to replace common phosphoric acid or sulfuric acid, so that side reactions can be reduced, the yield can be improved, and the method is environment-friendly and simple to operate.
The details of the present invention not described in detail are prior art.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of equol is characterized by comprising the following steps:
s1: synthesis of the Benzochroman:
weighing a plurality of daidzein raw materials, dissolving the daidzein raw materials in DMF (dimethyl formamide), adding palladium carbon into a dry and clean hydrogenation kettle, and reacting for a plurality of hours at constant temperature and constant pressure according to the same rotating speed; filtering the catalyst, adding the filtrate into ice water, stirring to separate out a white solid, filtering, washing with water, and drying to obtain an intermediate a;
s2: and (3) synthesis of a condensation compound:
adding a plurality of intermediates a, dichloroethane and polyphosphoric acid into a three-necked bottle, performing reflux reaction, cooling and cooling; adding into ice water; taking an organic phase by layers, drying the organic phase by sodium sulfate, concentrating dichloroethane to obtain a yellow oily substance, and recrystallizing the yellow oily substance by using 90% ethanol water to obtain a white-like solid which is an intermediate b;
s3: and (3) synthesizing equol:
adding the intermediate b, DMF and a catalyst into a hydrogenation kettle, and reacting for several hours at constant temperature and constant pressure at the same rotating speed; after the reaction is finished, filtering out the catalyst, adding the filtrate into ice water, stirring to separate out a gray solid, filtering, and recrystallizing the filter cake by using 70% methanol water to obtain the product equol.
2. The method of claim 1, wherein the palladium on carbon is 5% palladium on carbon, and the daidzein starting material, intermediate a, and intermediate b weighed in steps S1, S2, and S3 are all 0.1 mol.
3. The method according to claim 1, wherein the intermediate a obtained in S1 is 24g, and the yield is 93%.
4. The method according to claim 1, wherein the intermediate b obtained in S2 is 18g, and the yield is 75%.
5. The method of claim 1, wherein in S1, 20-30 g of daidzein, 80-100 g of DMF, and 5-15 g of Pd on C are weighed; the temperature is 20-30 ℃, the hydrogen pressure is 0.08Mpa, the rotating speed is 500-800 r, and the reaction time is 3-5 hours.
6. The method of claim 1, wherein in S1, daidzein is weighed as raw material 25.4g, DMF is weighed as 100g, Pd on C is weighed as 10 g; the temperature is 25 ℃, the hydrogen pressure is 0.08Mpa, the rotating speed is 500 r, and the reaction time is 3 hours.
7. The method for preparing equol according to claim 1, wherein in S2, 20-30 g of the intermediate a, 300-500 g of dichloroethane and 25-35 g of polyphosphoric acid are taken, added into a 500-1000 ml three-necked bottle, refluxed for 8-10 hours, cooled, and added into 300-500 g of ice water.
8. The method according to claim 1, wherein in S2, intermediate a25.8g, dichloroethane 300g, and polyphosphoric acid 30g are taken and put into a 500ml three-necked flask, and subjected to reflux reaction for 8 hours, cooled, and added to 300g of ice water.
9. The method for preparing equol according to claim 1, wherein in S3, 20-30 g of the intermediate b, 80-100 g of DMF, and 10-20 g of the catalyst are added into a hydrogenation kettle, and the hydrogenation reaction is carried out under the hydrogen pressure of 0.1MPa and at the temperature of 20-30 ℃ for 5-10 hours; after the reaction is finished, filtering out the catalyst, adding the filtrate into 500-1000 g of ice water, and stirring to separate out a gray solid.
10. The method for preparing equol according to claim 1, wherein in S3, intermediate b24g, DMF100g, and catalyst 10g are added into a hydrogenation kettle, and hydrogenation is carried out under hydrogen pressure of 0.1MPa and at 25 ℃ for 8 hours; after the reaction, the catalyst was filtered off, and the filtrate was added to 500g of ice water and stirred to precipitate a gray solid.
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| WO2005103025A1 (en) * | 2004-04-21 | 2005-11-03 | Novogen Research Pty Ltd | Isoflavene synthetic method and catalyst |
| CN101006999A (en) * | 1996-08-30 | 2007-08-01 | 诺沃根研究有限公司 | Therapeutic methods and compositions involving isoflavones |
| WO2010018199A1 (en) * | 2008-08-14 | 2010-02-18 | System Biologie Ag | Synthesis of equol |
| TW201041862A (en) * | 2009-05-20 | 2010-12-01 | Univ Kaohsiung Medical | Processes for preparing isoflavonoids using 7-benzyloxy-3-(4-methoxyphenyl)-2H-1-benzopyran as starting material |
| CN102633763A (en) * | 2012-04-11 | 2012-08-15 | 黑龙江大学 | Preparation method of (S)-equol |
| JP2015044770A (en) * | 2013-08-28 | 2015-03-12 | 国立大学法人北海道大学 | Production method of optically active 3-substituted chroman-4-ol compound |
| CN105777693A (en) * | 2014-12-22 | 2016-07-20 | 王靖林 | Synthetic method for equol |
-
2019
- 2019-09-16 CN CN201910868788.0A patent/CN110590727A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101006999A (en) * | 1996-08-30 | 2007-08-01 | 诺沃根研究有限公司 | Therapeutic methods and compositions involving isoflavones |
| WO2005103025A1 (en) * | 2004-04-21 | 2005-11-03 | Novogen Research Pty Ltd | Isoflavene synthetic method and catalyst |
| WO2010018199A1 (en) * | 2008-08-14 | 2010-02-18 | System Biologie Ag | Synthesis of equol |
| TW201041862A (en) * | 2009-05-20 | 2010-12-01 | Univ Kaohsiung Medical | Processes for preparing isoflavonoids using 7-benzyloxy-3-(4-methoxyphenyl)-2H-1-benzopyran as starting material |
| CN102633763A (en) * | 2012-04-11 | 2012-08-15 | 黑龙江大学 | Preparation method of (S)-equol |
| JP2015044770A (en) * | 2013-08-28 | 2015-03-12 | 国立大学法人北海道大学 | Production method of optically active 3-substituted chroman-4-ol compound |
| CN105777693A (en) * | 2014-12-22 | 2016-07-20 | 王靖林 | Synthetic method for equol |
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Application publication date: 20191220 |