CN101220016A - Method for synthesizing 4-hydroxyl coumarin and derivant thereof - Google Patents
Method for synthesizing 4-hydroxyl coumarin and derivant thereof Download PDFInfo
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- CN101220016A CN101220016A CNA2007103080455A CN200710308045A CN101220016A CN 101220016 A CN101220016 A CN 101220016A CN A2007103080455 A CNA2007103080455 A CN A2007103080455A CN 200710308045 A CN200710308045 A CN 200710308045A CN 101220016 A CN101220016 A CN 101220016A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
A specific technique of a method for synthesizing 4-hydroxycoumarin and the derivatives thereof is as follows: taking a phenol or the derivatives thereof and an Meldrum's acid as the raw materials, using a thin layer method to monitor and then decompressing to remove an acetone after complete reaction, with no necessity of separating an intermediate product, directly carrying out intermolecular dehydration with an ito agent or a polyphosphoric and ring-closing reaction and finally adding water to precipitate a sedimentation, and filtrating and then recrystallizing to get a final product---4-hydroxycoumarin and the derivatives thereof. The proportion of the phenol, the derivatives of the phenol, the Meldrum's acid, the ito agent or the polyphosphoric is 1.0mmol:1.0mmol:1-3ml or 1 to 2g. The temperature of intermolecular ring-closing reaction when adding the ito agent is 60 DEG C to 70 DEG C; and the reaction time is 1 to 5 hours. The temperature of intermolecular ring-closure reaction when adding the polyphosphoric is 110 DEG C to 120DEG C; and the reaction time is 3 to 7 hours. The method has the advantages of easy available raw materials, mild reaction condition, simple operation condition and less pollution. Furthermore, the yield varies from medium to excellence; no catalyst is needed; and the method also assures a high yield ratio.
Description
Technical field:
The present invention relates to phenol and Michaelis acid (Meldrum ' s acid, isopropylidene malonate) is raw material, the method for synthetic 4 hydroxy coumarin of one kettle way and derivative thereof.
Technical background:
4 hydroxy coumarin and derivative thereof are that a class has some biological activity, also are simultaneously the intermediates of synthetic many medicine, agricultural chemicals, dyestuff.It can prepare anticoagulation rodenticide (as warfarin Coumatetralyl etc.), anti-mycotic agent and treatment cardiovascular disease medicine (as anti-coagulants such as Aceno-coumarol, temparin, Syncumars).The medical science report points out that 4 hydroxy coumarin also has researching value in the research of cancer therapy drug.4 hydroxy coumarin and derivative thereof also can be used to synthetic Wedelolactone compounds, and Wedelolactone is a kind of main component of herbal medicine Yerbadetajo Herb, and it has hemostasis, effect such as control haematemesis, hematuria, have blood in stool.
The method of existing synthetic 4 hydroxy coumarin:
Method 1:
Method 2:
Method 3:
Method 4:
Method 5:
Method 6:
Above-mentioned several method 1,2,3 reaction process are long, complex process, and agents useful for same is more, and reagent is expensive; Method 4 technologies are simple, and raw material is also more cheap, but this synthetic route temperature of reaction height uses a large amount of sodium Metal 99.5s in the scale operation, industrial hazard level is increased greatly, and yield is lower; Method 5 need be used ZnCl
2, POCl
3As acylting agent, condensing agent requires anhydrous, and the reaction conditions strictness has a large amount of hydrogenchloride to get rid of in the reaction, the post-reaction treatment difficulty, and yield is lower; Used o-hydroxyacetophenone costs an arm and a leg in the method 6.
Summary of the invention:
The object of the invention is to provide the method for a kind of synthetic 4 hydroxy coumarin and derivative thereof.This method reaction conditions gentleness is carried out under normal pressure, and operational condition is simple, and raw material is easy to get, and pollutes and lacks, and productive rate is therefrom waited until good, does not need catalyzer.
For achieving the above object, first kind of technical scheme that the present invention adopts is as follows: with phenol or derivatives thereof and Michaelis acid is raw material, and through the thin-layer method monitoring, after reacting completely, acetone is removed in decompression; Intermediate product need not separate, directly and her rattan reagent (Eaton ' s Reagent) carry out intramolecular dehydration, ring-closure reaction adds elutriation at last and goes out precipitation, filtration, recrystallization obtains final product, i.e. 4 hydroxy coumarin and derivative thereof, reaction formula is as follows:
Wherein:
Substituent R can be one or more electron-donating groups or electron-withdrawing group, and phenol derivmives blend biology, Michaelis acid and her rattan ratio of reagents are 1.0mmol: 1.0mmol: 1-3mL; The ring-opening reaction temperature of Michaelis acid is 80-100 ℃, and the reaction times is 0.5-3 hour; Adding her the intramolecular ring-closing reaction temperature of rattan reagent generation is 60-70 ℃, and the reaction times is 1-5 hour.
The above-mentioned synthetic 4 hydroxy coumarin and the method for derivative thereof, described substituent R electron-donating group can be alkyl, alkoxyl group can also be phenyl ring; Electron-withdrawing group can be bromine, or the substituting group of iodine.
The above-mentioned synthetic 4 hydroxy coumarin and the method for derivative thereof, described reactant phenol derivatives can be thiophenol or toluene-.
The above-mentioned synthetic 4 hydroxy coumarin and the method for derivative thereof, the recyclable utilization of intermediary by product acetone further realizes cleaner production.
For achieving the above object, second kind of technical scheme that the present invention adopts is as follows: with phenol or derivatives thereof and Michaelis acid is raw material, and through the thin-layer method monitoring, after reacting completely, acetone is removed in decompression; Intermediate product need not separate, directly and polyphosphoric acid carry out intramolecular dehydration, ring-closure reaction adds elutriation at last and goes out precipitation, filtration, recrystallization obtains final product, i.e. 4 hydroxy coumarin and derivative thereof, reaction formula is as follows:
Wherein:
Substituent R can be one or more electron-donating groups or electron-withdrawing group, and phenol or derivatives thereof, Michaelis acid and polyphosphoric acid ratio are 1.0mmol: 1.0mmol: 1-2g; The ring-opening reaction temperature of Michaelis acid is 90-100 ℃, and the reaction times is 3-9 hour; The intramolecular ring-closing reaction that the adding polyphosphoric acid takes place is temperature required to be 110-120 ℃, and the reaction times is 3-7 hour.
The above-mentioned synthetic 4 hydroxy coumarin and the method for derivative thereof, described substituent R electron-donating group can be alkyl, alkoxyl group can also be phenyl ring; Electron-withdrawing group can be bromine, or the substituting group of iodine.
The above-mentioned synthetic 4 hydroxy coumarin and the method for derivative thereof, described phenol derivatives are ortho-methyl phenol or p methoxy phenol or bromophenol or thiophenol.
The method of described synthetic 4 hydroxy coumarin and derivative thereof, the recyclable utilization of intermediary by product acetone further realizes cleaner production.
Advantage of the present invention:
1. the present invention is a synthesis under normal pressure, and temperature requirement is not high, and facility investment is few, and is easy to operate and safe.
2. cost of the present invention is low, and raw material is simple, is easy to get, and the biological and directly Hybrid Heating reaction of Michaelis acid of phenol derivmives blend need not add catalyzer.
3, refer to that phenol derivmives blend biology and Michaelis acid-respons gained intermediate product productive rate are higher, need not separate, can carry out next step reaction.
4, the present invention is synthetic for one kettle way, and technical process is simple, and yield is higher.
5. good economy performance of the present invention can be synthesized multiple 4 hydroxy coumarin and derivative thereof, comprises 4-hydroxyl thiocoumarin.
6. reaction process difficulty of the present invention is low, easy and simple to handle, and product separates easily, just can separate by simply being separated; And product only needs recrystallization can obtain pure product.
7. the present invention is environmentally friendly.The reaction corrosion is little, and the three wastes are handled burden and obviously reduced, and have reached the requirement of cleaner production, help large-scale commercial production.
8. the unique by product acetone that produces among the present invention can also be recycled as a kind of organic solvent, and is good in economic efficiency.
Embodiment:
Below by embodiment, the present invention is described in detail in detail, yet the invention is not restricted to following embodiment.
Embodiment 1:
With phenol or derivatives thereof and Michaelis acid (Meldrum ' s acid) is raw material, and through thin-layer method (TLC) monitoring, after reacting completely, intermediary by product acetone is removed in decompression, and the recyclable utilization of acetone further realizes cleaner production; Intermediate product need not separate, directly and her rattan reagent (Eaton ' s Reagent) carry out intramolecular dehydration, ring-closure reaction adds elutriation at last and goes out precipitation, filtration, recrystallization obtains final product, i.e. 4 hydroxy coumarin and derivative thereof, reaction formula is as follows:
Wherein:
Substituent R can be one or more electron-donating groups or electron-withdrawing group, and described substituent R electron-donating group can be alkoxyl groups such as alkyl such as methyl, ethyl, the tertiary butyl, methoxyl group, oxyethyl group, can also be phenyl ring; Electron-withdrawing group can be bromine, or the substituting group of iodine.
Phenol derivmives blend biology, Michaelis acid and her rattan ratio of reagents are 1.0mmol: 1.0mmol: 3mL; The ring-opening reaction temperature of Michaelis acid is 100 ℃, and the reaction times is 3 hours; Adding her the intramolecular ring-closing reaction temperature of rattan reagent generation is 60-70 ℃, and the reaction times is 1-5 hour.But described reactant phenol derivatives can be the thiophenol toluene-.
Embodiment 2
Add phenol (1.0mmol) in the 10mL round-bottomed flask, Michaelis acid (1.0mmol) mixes, and heated and stirred is 3 hours under 100 ℃ of conditions, is cooled to room temperature.Vacuum filtration is removed residual acetone; And acetone recycled.Add her rattan reagent of 3mL, heated and stirred is 5 hours under 70 ℃ of conditions, be cooled to room temperature, add 20mL water while stirring, be cooled to room temperature again, filter thick product, get 4 hydroxy coumarin with 3-5mL ethanol and 1-3mL water recrystallization, yellow solid, productive rate 60.5%, fusing point: 213.0-214.3 ℃.
Embodiment 3
Add p-tert-butylphenol (1.0mmol) in the 10mL round-bottomed flask, Michaelis acid (1.0mmol) mixes, and heated and stirred is 3 hours under 100 ℃ of conditions, is cooled to room temperature.Vacuum filtration is removed residual acetone; And acetone recycled.Add her rattan reagent of 3mL, heated and stirred is 1 hour under 70 ℃ of conditions, be cooled to room temperature, add 20mL water while stirring, be cooled to room temperature again, filter thick product, get 4-hydroxyl-6-tertiary butyl basic note legumin with 3-5mL ethanol and 1-3mL water recrystallization, yellow powder, productive rate 82.6%, fusing point: 216.0-218.2 ℃.
Embodiment 4
In the 10mL round-bottomed flask, add 2,4-DI-tert-butylphenol compounds (1.0mmol), Michaelis acid (1.0mmol) mixes, and heated and stirred is 3 hours under 100 ℃ of conditions, is cooled to room temperature.Vacuum filtration is removed residual acetone; And acetone recycled.Add her rattan reagent of 3mL, heated and stirred is 2 hours under 60 ℃ of conditions, be cooled to room temperature, add 20mL water while stirring, be cooled to room temperature again, filter thick product, get 4-hydroxyl-6 with 3-5mL ethanol and 1-3mL water recrystallization, 8-di-t-butyl tonka bean camphor, yellow solid, productive rate 78.2%, fusing point: 262.2-263.5 ℃.
Embodiment 5
Add naphthyl alcohol (1.0mmol) in the 10mL round-bottomed flask, Michaelis acid (1.0mmol) mixes, and heated and stirred is 2 hours under 90 ℃ of conditions, is cooled to room temperature.Vacuum filtration is removed residual acetone; And acetone recycled.Add her rattan reagent of 3mL, heated and stirred is 1 hour under 70 ℃ of conditions, is cooled to room temperature, add 20ml water while stirring, filter thick product, get 4-hydroxyl-benzo [h] tonka bean camphor with 3-5mL ethanol and 1-3mL water recrystallization, yellow solid, productive rate 81.2%, fusing point: 278.8-280.0 ℃.
Embodiment 6
Add p bromophenol (1.0mmol) in the 10mL round-bottomed flask, Michaelis acid (1.0mmol) mixes, and heated and stirred is 3 hours under 100 ℃ of conditions, is cooled to room temperature.Vacuum filtration is removed residual acetone; And acetone recycled.Add her rattan reagent of 3mL, heated and stirred is 5 hours under 70 ℃ of conditions, is cooled to room temperature, add 20ml water while stirring, filter thick product, get 6-bromo-4 hydroxy coumarin with 3-5mL ethanol and 1-3mL water recrystallization, yellow solid, productive rate 56.3%, fusing point: 276.2-278.3 ℃.
Embodiment 7
Add thiophenol or toluene-(1.0mmol) in the 10mL round-bottomed flask, Michaelis acid (1.0mmol) mixes, and heated and stirred is 1 hour under 90 ℃ of conditions, is cooled to room temperature.Vacuum filtration is removed acetone; And acetone recycled.Add her rattan reagent of 3mL, heated and stirred is 3 hours under 70 ℃ of conditions, be cooled to room temperature, add 20mL water while stirring, be cooled to room temperature again, filter thick product, get 4-hydroxyl thiocoumarin with 3-5mL ethanol and 1-3mL water recrystallization, white crystal, productive rate: 47.6%, fusing point: 212.2-213.5 ℃.
Embodiment 8
With phenol or derivatives thereof and Michaelis acid is raw material, and through the thin layer chromatography scanning monitoring, after reacting completely, intermediary by product acetone is removed in decompression; The recyclable utilization of acetone further realizes cleaner production; Intermediate product need not separate, directly and 84% polyphosphoric acid (PPA) carry out intramolecular dehydration, closed loop obtains final product, i.e. 4 hydroxy coumarin and derivative thereof, reaction formula is as follows:
Wherein:
Substituent R can be one or more electron-donating groups or electron-withdrawing group, and described substituent R electron-donating group can be alkyl such as methyl, ethyl, the tertiary butyl, and alkoxyl groups such as methoxyl group, oxyethyl group can also be phenyl ring; Electron-withdrawing group can be bromine, or the substituting group of iodine.Phenol or derivatives thereof, Michaelis acid and 84% polyphosphoric acid (PPA) ratio are 1.0mmol: 1.0mmol: 1-2g; The ring-opening reaction temperature of Michaelis acid is 90-100 ℃, and the reaction times is 3-9 hour; Add that intramolecular ring-closing reaction that 84% polyphosphoric acid (PPA) takes place is temperature required to be 110-120 ℃, the reaction times is 3-7 hour.
Embodiment 9
Add phenol (1.0mmol) in the 10mL round-bottomed flask, Michaelis acid (1.0mmol) mixes, and heated and stirred is 3 hours under 100 ℃ of conditions, is cooled to room temperature.Vacuum filtration is removed residual acetone; And acetone recycled.Add 2g PPA, heated and stirred is 9 hours under 110 ℃ of conditions, is cooled to room temperature, add 20-25mL water while stirring, be cooled to room temperature again, filter thick product, get 4 hydroxy coumarin with 3-5mL acetate and 1-3mL water recrystallization, yellow solid, productive rate 54.9%.
Embodiment 10
Add ortho-methyl phenol (1.0mmol) in the 10mL round-bottomed flask, Michaelis acid (1.0mmol) mixes, and heated and stirred is 3 hours under 100 ℃ of conditions, is cooled to room temperature.Vacuum filtration is removed residual acetone, and acetone is recycled.Add 2g 84% polyphosphoric acid (PPA), heated and stirred is 7 hours under 110 ℃ of conditions, be cooled to room temperature, add 3mL1mol/L HCl, transfer PH to 3-5 with 2mol/L NaOH while stirring, be cooled to room temperature again, filter thick product, get 4-hydroxyl-8-methylcoumarin, yellow powder with 3-5mL acetate and 1-3mL water recrystallization, productive rate 69.3%, fusing point: 231.1-233.4 ℃.
Embodiment 11
Add p methoxy phenol (1.0mmol) in the 10mL round-bottomed flask, Michaelis acid (1.0mmol) mixes, and heated and stirred is 3 hours under 100 ℃ of conditions, is cooled to room temperature.Vacuum filtration is removed residual acetone, and acetone is recycled.Add 2g 84% polyphosphoric acid (PPA), heated and stirred is 7 hours under 110 ℃ of conditions, be cooled to room temperature, add 15-25mL water, be cooled to room temperature again, filter thick product, get 4-hydroxyl-6-methoxy coumarin with 3-5mL acetate and 1-3mL water recrystallization, yellow powder, productive rate 72.6%, fusing point: 254.4-254.7 ℃.
Embodiment 12
Add p bromophenol (1.0mmol) in the 10mL round-bottomed flask, Michaelis acid (1.0mmol) mixes, and heated and stirred is 3 hours under 100 ℃ of conditions, is cooled to room temperature.Vacuum filtration is removed residual acetone, and acetone is recycled.Add 2g 84% polyphosphoric acid (PPA), heated and stirred is 7 hours under 110 ℃ of conditions, is cooled to room temperature, adds 3mL1mol/L HCl, transfer PH to 3-5 with 2mol/L NaOH while stirring, be cooled to room temperature again, filter thick product, be cooled to room temperature again, filter thick product, get 6-bromo-4 hydroxy coumarin, yellow powder, productive rate 54.3% with 3-5mL acetate and 1-3mL water recrystallization.
Embodiment 13
Add thiophenol (1.0mmol) in the 10mL round-bottomed flask, Michaelis acid (1.0mmol) mixes, and heated and stirred is 1 hour under 90 ℃ of conditions, is cooled to room temperature.Vacuum filtration is removed acetone; And acetone recycled.Add 2g PPA, heated and stirred is 8 hours under 110 ℃ of conditions, is cooled to room temperature, add 20-25mL water while stirring, be cooled to room temperature again, filter thick product, get 4-hydroxyl thiocoumarin, white crystal, productive rate: 56.4% with 3-5mL ethanol and 1-3mL water recrystallization.
Claims (8)
1. the method for synthetic 4 hydroxy coumarin and derivative thereof is characterized in that:
With phenol or derivatives thereof and Michaelis acid is raw material, and through the thin-layer method monitoring, after reacting completely, acetone is removed in decompression; Intermediate product need not separate, directly and her rattan reagent carry out intramolecular dehydration, ring-closure reaction adds elutriation at last and goes out precipitation, filtration, recrystallization obtains final product, i.e. 4 hydroxy coumarin and derivative thereof, reaction formula is as follows:
Wherein:
Substituent R can be one or more electron-donating groups or electron-withdrawing group, and phenol derivmives blend biology, Michaelis acid and her rattan ratio of reagents are 1.0mmol: 1.0mmol: 1-3mL; The ring-opening reaction temperature of Michaelis acid is 80-100 ℃, and the reaction times is 0.5-3 hour; Adding her the intramolecular ring-closing reaction temperature of rattan reagent generation is 60-70 ℃, and the reaction times is 1-5 hour.
2. the method for synthetic 4 hydroxy coumarin according to claim 1 and derivative thereof is characterized in that: described substituent R electron-donating group can be alkyl, and alkoxyl group can also be phenyl ring; Electron-withdrawing group can be bromine, or the substituting group of iodine.
3. the method for synthetic 4 hydroxy coumarin according to claim 1 and derivative thereof is characterized in that: described reactant phenol derivatives can be thiophenol or toluene-.
4. the method for synthetic 4 hydroxy coumarin according to claim 1 and derivative thereof is characterized in that: the recyclable utilization of intermediary by product acetone.
5. the method for synthetic 4 hydroxy coumarin and derivative thereof is characterized in that:
With phenol or derivatives thereof and Michaelis acid is raw material, and through the thin-layer method monitoring, after reacting completely, acetone is removed in decompression; Intermediate product need not separate, directly and polyphosphoric acid carry out intramolecular dehydration, ring-closure reaction adds elutriation at last and goes out precipitation, filtration, recrystallization obtains final product, i.e. 4 hydroxy coumarin and derivative thereof, reaction formula is as follows:
Wherein:
Substituent R can be one or more electron-donating groups or electron-withdrawing group, and phenol or derivatives thereof, Michaelis acid and polyphosphoric acid ratio are 1.0mmol: 1.0mmol: 1-2g; The ring-opening reaction temperature of Michaelis acid is 90-100 ℃, and the reaction times is 3-9 hour; The intramolecular ring-closing reaction that the adding polyphosphoric acid takes place is temperature required to be 110-120 ℃, and the reaction times is 3-7 hour.
6. the method for synthetic 4 hydroxy coumarin according to claim 5 and derivative thereof is characterized in that: described substituent R electron-donating group can be alkyl, and alkoxyl group can also be phenyl ring; Electron-withdrawing group can be bromine, or the substituting group of iodine.
7. the method for synthetic 4 hydroxy coumarin according to claim 5 and derivative thereof is characterized in that: described phenol derivatives is ortho-methyl phenol or p methoxy phenol or bromophenol or thiophenol.
8. the method for synthetic 4 hydroxy coumarin according to claim 5 and derivative thereof is characterized in that: the recyclable utilization of intermediary by product acetone.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965150A (en) * | 2014-05-28 | 2014-08-06 | 广州康臣药物研究有限公司 | Scopoletin derivative as well as preparation method and application thereof |
| CN111234130A (en) * | 2020-03-25 | 2020-06-05 | 陕西科技大学 | Michelic acid modified polycarboxylic acid high-efficiency water reducing agent and preparation method thereof |
| CN111234131A (en) * | 2020-03-25 | 2020-06-05 | 陕西科技大学 | Gluconolactone-based polycarboxylic acid water reducing agent and preparation method thereof |
| CN115160280A (en) * | 2022-06-07 | 2022-10-11 | 贵州农业职业学院 | Method for synthesizing flavanone compound |
-
2007
- 2007-12-31 CN CNA2007103080455A patent/CN101220016A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965150A (en) * | 2014-05-28 | 2014-08-06 | 广州康臣药物研究有限公司 | Scopoletin derivative as well as preparation method and application thereof |
| CN103965150B (en) * | 2014-05-28 | 2016-06-15 | 广州康臣药物研究有限公司 | Scopoletin derivant and its preparation method and application |
| CN111234130A (en) * | 2020-03-25 | 2020-06-05 | 陕西科技大学 | Michelic acid modified polycarboxylic acid high-efficiency water reducing agent and preparation method thereof |
| CN111234131A (en) * | 2020-03-25 | 2020-06-05 | 陕西科技大学 | Gluconolactone-based polycarboxylic acid water reducing agent and preparation method thereof |
| CN111234131B (en) * | 2020-03-25 | 2023-08-08 | 山东易和建材科技有限公司 | Glucolactone-based polycarboxylate water reducer and preparation method thereof |
| CN111234130B (en) * | 2020-03-25 | 2023-08-29 | 安新县金运化工原料有限公司 | Mi's acid modified polycarboxylic acid high-efficiency water reducer and preparation method thereof |
| CN115160280A (en) * | 2022-06-07 | 2022-10-11 | 贵州农业职业学院 | Method for synthesizing flavanone compound |
| CN115160280B (en) * | 2022-06-07 | 2023-08-04 | 贵州农业职业学院 | Synthesis method of flavonoid compound |
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Open date: 20080716 |