CN102701933A - Method for synthesizing curcumin through catalysis of alumina supported potassium fluoride solid base - Google Patents
Method for synthesizing curcumin through catalysis of alumina supported potassium fluoride solid base Download PDFInfo
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- CN102701933A CN102701933A CN201210171457XA CN201210171457A CN102701933A CN 102701933 A CN102701933 A CN 102701933A CN 201210171457X A CN201210171457X A CN 201210171457XA CN 201210171457 A CN201210171457 A CN 201210171457A CN 102701933 A CN102701933 A CN 102701933A
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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
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides a green synthetic method of curcumin, which comprises the steps as follows: alumina supported potassium fluoride solid base is taken as a catalyst, and boric anhydride is used for protecting active methylene groups of diacetone; diacetone and 4-hydroxyl-3-methoxy-benzaldehyde are dissolved in a polar aprotic solvent, and condensation reaction is performed; a hydrophobic organic solvent is added, the catalyst is filtered out and recovered for reutilization; dilute hydrochloric acid is added for hydrolysis; liquid separation and washing are carried out; the solvent is removed through rotary evaporation; and recrystallization and drying are carried out so as to obtain curcumin. The green synthetic method has the advantages as follows: the operation of the synthetic method is simple, the reaction yield coefficient is high, the product purity is high, and zero environmental contamination can be achieved; the catalyst is convenient to prepare, is economical to buy, achieves good stability, and can be reused through simple treatment or no treatment; the catalyst and products are easy to be separated, and the reaction condition is mild; and the green synthetic method is a green aseptic synthetic route, and achieves a favorable industrialized prospect.
Description
Technical field
The present invention relates to a kind of compound method of curcumine, especially a kind of is the green method of catalyst methyl ethyl diketone and the synthetic curcumine of 4-hydroxy 3-methoxybenzene formaldehyde with the alumina load Potassium monofluoride.
Background technology
Curcumine is a kind of natural pigment that from ancient plant medicinal material turmeric, extracts, and the content in turmeric is about 3%～6%.Curcumine is used to food dye and traditional Chinese medicine always, because of it has anti-inflammatory, anti-oxidant, antibiotic, antitumor, reducing blood-fat, prevents aging and many effects such as promote longevity, becomes the research focus of natural drug industry in recent years.Curcumine is as a kind of comparatively ideal yellow natural pigment, nontoxic, strong coloring force, good dispersivity, fast light heat-resisting.Curcumine also has important application aspect functional cosmetics.For example Shiaeibo company has found out facially because of the mechanism of wrinkle appears in ultraviolet ray, and is that staple is succeeded in developing the medicament " root tuber of aromatic turmeric is smart " that suppresses to form wrinkle with the curcumine.
At present, the synthetic route of curcumine nearly all obtains through methyl ethyl diketone and 4-hydroxy 3-methoxybenzene formaldehyde condensation, and wherein boron trioxide is the active methylene radical that is used for protecting methyl ethyl diketone.Its reaction equation is following:
According to patent CN 101454267A; Curcumine is through obtain as follows: adopting senior property, aprotic solvent, is catalyzer with aliphatics or aromatic aliphatic amine, uses azeotrope to remove the water that dereaction produces; Make Vanillin and methyl ethyl diketone carry out condensation, carry out aftertreatment subsequently.The curcumine productive rate that this method obtains is better, and the catalyzer relative low price of reaction use.But this catalyst separating difficulty can not be recycled, and causes the wasting of resources, and the mankind are had certain injury, has increased the weight of the pollution of environment.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, the environment-friendly preparation method thereof of curcumine under the effect of a kind of alumina load Potassium monofluoride catalyzed by solid base is provided.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is:
1. a certain amount of boron trioxide is dissolved in solvent orange 2 A, adds the methyl ethyl diketone reaction, with tributyl borate as dewatering agent.Boron trioxide with respect to 0.5～1 mole of % of methyl ethyl diketone is used, and the reaction times is 10-40min, and temperature of reaction is 45-75 ℃, and solvent orange 2 A is non-proton type polar solvent, includes but not limited to DMF, DMAC, HMP etc.
2. add 4-hydroxy 3-methoxybenzene formaldehyde and alumina load Potassium monofluoride solid base catalyst, continue reaction.After reaction finishes, add solvent B, heat filtering is recycled alumina load Potassium monofluoride solid base catalyst.The mol ratio of 4-hydroxy 3-methoxybenzene formaldehyde and methyl ethyl diketone is 1.8～1: 1～4, and the reaction times is 0.5～10h, and temperature of reaction is 70～130 ℃.Solvent B is a hydrophobic organic solvent, includes but not limited to ETHYLE ACETATE, hexanaphthene, 1,2-ethylene dichloride etc.The catalyzer that uses is an alumina load Potassium monofluoride solid base catalyst; This catalyst levels is 0.5～15wt.% of raw material 4-hydroxy 3-methoxybenzene formaldehyde quality; The massfraction of load KF is for to be 5～40wt.% of catalyzer total amount, and calcining temperature is 120～550 ℃ in the catalyst preparation process.Catalyzer after reaction is accomplished can directly use or use methanol wash after filtering, the dry repeated use.
3. in mixture, add excessive 0.4mol/L dilute hydrochloric acid solution and accomplish reaction.Reaction times is 0.5～2h, and temperature of reaction is 40～65 ℃.Standing demix, water layer merges organic layer with solvent B extraction, and water is washed till neutrality, and rotary evaporation removes and desolvates, and recrystallization obtains orange-yellow crystal, drying.
Compared with prior art, positively effect of the present invention is: this compound method method is simple to operate, and reaction yield is high; Good product purity, environmentally safe, Preparation of Catalyst convenience, purchase economy, good stability; Through simple process or do not handle reusablely, catalyzer is easy to separate with product, and product postprocessing is simple; Be a green clean synthetic route, have environment-friendly function.Therefore, the prepared solid alkali of alumina load Potassium monofluoride is expected to become the environment-friendly catalyst of new generation of the synthetic curcumine of catalysis.
Embodiment
Through embodiment the present invention is elaborated below, but should not be regarded as limitation of the present invention.
Embodiment 1: in having the 100ml there-necked flask of whisking appliance, TM, reflux condensing tube, drying tube, add boron trioxide 5mmol, DMF 1ml after the dissolving, adds in the 5mmol methyl ethyl diketone.Be warming up to 65 ℃, add tributyl borate 10mmol, stir 10min.Add 4-hydroxy 3-methoxybenzene formaldehyde 9mmol subsequently, stirring and dissolving is warming up to 95 ℃, reaction 6h.Add 20ml ETHYLE ACETATE, after temperature is reduced to 50 ℃, add 20ml0.4mol/L dilute hydrochloric acid solution reaction 1h.Standing demix, water layer merge organic layer with ethyl acetate extraction three times, and water is washed till neutrality, and rotary evaporation removes and desolvates, and recrystallization obtains orange-yellow crystal, drying.Productive rate is 31.9%.
Embodiment 2: in having the 100ml there-necked flask of whisking appliance, TM, reflux condensing tube, drying tube, add boron trioxide 5mmol, DMF 1ml after the dissolving, adds in the 5mmol methyl ethyl diketone.Be warming up to 65 ℃, add tributyl borate 10mmol, stir 10min.Add 4-hydroxy 3-methoxybenzene formaldehyde 9mmol subsequently, stirring and dissolving.Add the 15wt.%KF/Al after 450 ℃ of calcinings
2O
30.1g, be heated to 90 ℃, reaction 4h.Add 20ml ETHYLE ACETATE, filtered while hot is with the catalyst recovery utilization.Reaction solution adds the 20ml0.4mol/L dilute hydrochloric acid solution, 50 ℃ of reaction 1h.Standing demix, water layer merge organic layer with ethyl acetate extraction three times, and water is washed till neutrality, and rotary evaporation removes and desolvates, and recrystallization obtains orange-yellow crystal, drying.Productive rate is 62%.
Embodiment 3: in having the 100ml there-necked flask of whisking appliance, TM, reflux condensing tube, drying tube, add boron trioxide 5mmol, DMF 1ml after the dissolving, adds in the 5mmol methyl ethyl diketone.Be warming up to 65 ℃, add tributyl borate 10mmol, stir 10min.Add 4-hydroxy 3-methoxybenzene formaldehyde 9mmol subsequently, stirring and dissolving.Add the 37wt.%KF/Al after 450 ℃ of calcinings
2O
30.1g, be heated to 90 ℃, reaction 4h.Add 20ml ETHYLE ACETATE, filtered while hot is with the catalyst recovery utilization.Reaction solution adds the 20ml0.4mol/L dilute hydrochloric acid solution, 50 ℃ of reaction 1h.Standing demix, water layer merge organic layer with ethyl acetate extraction three times, and water is washed till neutrality, and rotary evaporation removes and desolvates, and recrystallization obtains orange-yellow crystal, drying.Productive rate is 45%.
Embodiment 4: in having the 100ml there-necked flask of whisking appliance, TM, reflux condensing tube, drying tube, add boron trioxide 5mmol, DMF 1ml after the dissolving, adds in the 5mmol methyl ethyl diketone.Be warming up to 65 ℃, add tributyl borate 10mmol, stir 10min.Add 4-hydroxy 3-methoxybenzene formaldehyde 9mmol subsequently, stirring and dissolving.Add the 15wt.%KF/Al after 450 ℃ of calcinings
2O
30.3g, be heated to 90 ℃, reaction 4h.Add 20ml ETHYLE ACETATE, filtered while hot is with the catalyst recovery utilization.Reaction solution adds the 20ml0.4mol/L dilute hydrochloric acid solution, 50 ℃ of reaction 1h.Standing demix, water layer merge organic layer with ethyl acetate extraction three times, and water is washed till neutrality, and rotary evaporation removes and desolvates, and recrystallization obtains orange-yellow crystal, drying.Productive rate is 57%.
Embodiment 5: in having the 100ml there-necked flask of whisking appliance, TM, reflux condensing tube, drying tube, add boron trioxide 5mmol, DMF 1ml after the dissolving, adds in the 5mmol methyl ethyl diketone.Be warming up to 65 ℃, add tributyl borate 10mmol, stir 10min.Add 4-hydroxy 3-methoxybenzene formaldehyde 9mmol subsequently, stirring and dissolving.Add 10%KF/Al after 250 ℃ of calcinings
2O
30.3g, be heated to 90 ℃, reaction 4h.Add 20ml ETHYLE ACETATE, filtered while hot is with the catalyst recovery utilization.Reaction solution adds the 20ml0.4mol/L dilute hydrochloric acid solution, 50 ℃ of reaction 1h.Standing demix, water layer merge organic layer with ethyl acetate extraction three times, and water is washed till neutrality, and rotary evaporation removes and desolvates, and recrystallization obtains orange-yellow crystal, drying.Productive rate is 63.2%.
The above only is a preferred implementation of the present invention, should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the present invention's design.Can also make some improvement and retouching, these improvement and retouching also should be regarded as in protection scope of the present invention.
Claims (2)
1. method that adopts the synthetic curcumine of alumina load Potassium monofluoride catalyzed by solid base; It is characterized in that: one, boron trioxide is dissolved in non-proton type polar solvent; This non-proton type polar solvent includes but not limited to DMF, DMAC, HMP; Add methyl ethyl diketone reaction then, with tributyl borate as dewatering agent; Two, add 4-hydroxy 3-methoxybenzene formaldehyde and alumina load Potassium monofluoride solid base catalyst, continue reaction.After reaction finishes, add hydrophobic organic solvent, this hydrophobic organic solvent includes but not limited to ETHYLE ACETATE, hexanaphthene, 1, the 2-ethylene dichloride, and heat filtering is recycled alumina load Potassium monofluoride solid base catalyst then; Three, in filtrating, add excessive 0.4mol/L dilute hydrochloric acid solution and accomplish reaction.Standing demix, water layer merges organic layer with hydrophobic organic solvent extraction three times, and water is washed till neutrality, and rotary evaporation removes and desolvates, and recrystallization obtains orange-yellow crystal, drying.
2. a kind of method that adopts the synthetic curcumine of alumina load Potassium monofluoride catalyzed by solid base according to claim 1; The catalyzer that it is characterized in that the use of second step is an alumina load Potassium monofluoride solid base catalyst; This catalyst levels is 0.5～15wt.% of raw material 4-hydroxy 3-methoxybenzene formaldehyde quality; The massfraction of charge capacity KF is 5～40wt.% of catalyzer total amount; Calcining temperature in the catalyst preparation process is 120～550 ℃, and the catalyzer after reaction is accomplished can directly use or use methanol wash after filtering, and dry back is reused.
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| CN201210171457XA CN102701933A (en) | 2012-05-30 | 2012-05-30 | Method for synthesizing curcumin through catalysis of alumina supported potassium fluoride solid base |
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| CN201210171457XA CN102701933A (en) | 2012-05-30 | 2012-05-30 | Method for synthesizing curcumin through catalysis of alumina supported potassium fluoride solid base |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107616925A (en) * | 2017-10-11 | 2018-01-23 | 郭迎庆 | A kind of preparation method of washable hair dye |
| CN114717610A (en) * | 2022-05-16 | 2022-07-08 | 中国铝业股份有限公司 | Method for reducing potassium content in aluminum electrolysis fluorine-carrying aluminum oxide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5144089A (en) * | 1991-10-21 | 1992-09-01 | Uop | 2-ethyl-2-hexenal by aldol condensation of butyraldehyde in a continuous process |
| CN1206396A (en) * | 1995-11-03 | 1999-01-27 | 基因复制公司 | Process for synthesis of curcumin-related compounds |
| CN101289378A (en) * | 2007-04-18 | 2008-10-22 | 中国科学院大连化学物理研究所 | Process for synthesizing chalcone and derivates thereof by using ion liquid |
| CN101454267A (en) * | 2006-03-29 | 2009-06-10 | 帝斯曼知识产权资产管理有限公司 | Curcumin synthesis |
-
2012
- 2012-05-30 CN CN201210171457XA patent/CN102701933A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5144089A (en) * | 1991-10-21 | 1992-09-01 | Uop | 2-ethyl-2-hexenal by aldol condensation of butyraldehyde in a continuous process |
| CN1206396A (en) * | 1995-11-03 | 1999-01-27 | 基因复制公司 | Process for synthesis of curcumin-related compounds |
| CN101454267A (en) * | 2006-03-29 | 2009-06-10 | 帝斯曼知识产权资产管理有限公司 | Curcumin synthesis |
| CN101289378A (en) * | 2007-04-18 | 2008-10-22 | 中国科学院大连化学物理研究所 | Process for synthesizing chalcone and derivates thereof by using ion liquid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107616925A (en) * | 2017-10-11 | 2018-01-23 | 郭迎庆 | A kind of preparation method of washable hair dye |
| CN114717610A (en) * | 2022-05-16 | 2022-07-08 | 中国铝业股份有限公司 | Method for reducing potassium content in aluminum electrolysis fluorine-carrying aluminum oxide |
| CN114717610B (en) * | 2022-05-16 | 2023-08-08 | 中国铝业股份有限公司 | Method for reducing potassium content in aluminum electrolysis fluorine-carrying aluminum oxide |
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Application publication date: 20121003 |