CN106748705B - Method for artificially synthesizing curcumin and derivatives thereof - Google Patents
Method for artificially synthesizing curcumin and derivatives thereof Download PDFInfo
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Abstract
The invention discloses a method for artificially synthesizing curcumin and derivatives thereof. The method takes calcium acetylacetonate as an acetylacetone source, and obtains an intermediate (I) curcumin calcium salt through claisen-Schmitt ester condensation reaction with a corresponding benzaldehyde derivative and dehydration under the catalysis of a dehydrating agent tri-n-butyl borate; and hydrolyzing the intermediate (I) by a one-pot method to obtain a crude product, and purifying the crude product to obtain a final product curcumin and derivatives thereof. Compared with the acetylacetone boric acid complex method, the method uses the calcium acetylacetonate to enable the acetylacetone group active site to be more accurate and activated in the reaction process, thereby reducing the generation of by-products and improving the yield of the curcumin and derivatives thereof.
Description
Technical Field
The invention relates to the technical field of medicines, in particular to a method for artificially synthesizing curcumin and derivatives thereof.
Background
Curcumin is the main component of turmeric, and turmeric is the rhizome of a plant in the family of zingiberaceae, belongs to a blood-activating medicine in traditional Chinese medicines, is originally recorded in Xin Xiu Ben Cao, has the effects of activating qi stagnation, dispelling wind and activating blood to stop pain, and is commonly used for treatment such as cholagogue, anti-inflammation, antibiosis and the like. Curcumin is also the main yellow pigment in curry and mustard, belongs to a natural phenolic antioxidant, is a common seasoning and an edible pigment, and has numerous physiological and pharmacological activities: anticancer, antioxidant, antiinflammatory, antirheumatic, antihypertensive, anticholesterol, anticoagulant, analgesic, etc. Curcumin has wide pharmacological action and has the main characteristics of anticancer, antioxidation and anti-inflammatory. U.S. VITY journal of vitamin report: the main pharmacological actions of curcumin include antioxidation, anti-inflammation, anticoagulation, lipid-lowering, anti-atherosclerosis, anti-aging, free radical elimination, tumor growth inhibition and the like. "
The method mainly comprises the steps of reacting an acetylacetone boric acid complex with vanillin or benzaldehyde derivatives to obtain curcumin or derivatives thereof, wherein the reaction degree is incomplete, the central control judgment condition is harsh, the separation of products, reactants and solvents is difficult, the post-treatment steps of the products are complicated, the three wastes are more, and the method does not meet the trend of green chemistry and the requirements of modern chemical industry. The use of boron element is avoided, so that the generation of three wastes can be greatly reduced, the pollution to the environment is reduced, the separation is easy, the process is relatively simple, the reaction cost can be reduced, and the yield of the target product is high. Therefore, the synthesis of curcumin and derivatives thereof by using calcium acetylacetonate as a raw material meets the requirements of green economy and green chemistry.
At present, the supply source of the acetylacetone group is mainly boron complex of acetylacetone when the curcumin and the derivatives thereof are synthesized, and the yield of the curcumin and the derivatives thereof can reach 60 percent when the acetylacetone source participates in reaction. However, the method for synthesizing curcumin and derivatives thereof has unstable active site selectivity of intermediates; the reaction process is limited by various factors such as temperature, water content, reaction time and the like; the post-treatment process is not easy to realize continuous production and has low production efficiency and the like. Therefore, the method is difficult to industrially produce and always stays in the laboratory research stage of the ten-gram-level synthesis.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for artificially synthesizing curcumin and derivatives thereof. According to the method, calcium acetylacetonate is selected as an acetylacetone supply source, wherein the content of acetylacetone is 80%, and the method has high reaction activity and selectivity. The conversion rate of the acetylacetone source is high, the selectivity of the curcumin and the derivatives thereof is high, namely, the method for synthesizing the curcumin and the derivatives thereof by using calcium acetylacetonate as a raw material is economical and efficient, and further the problem of industrial production of the synthesized curcumin and the derivatives thereof is solved, namely, the method comprises the following steps of adding acetylacetone salt: calcium acetylacetonate enables the acetylacetone group to react with vanillin or benzaldehyde derivatives with high selectivity and stability to generate curcumin or derivatives thereof. The method has simple post-treatment method and less three wastes.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
calcium acetylacetonate is used as an acetylacetone source, and the intermediate (I) curcumin (derivative) calcium salt is obtained after the claisen-Schmitt ester condensation reaction with a corresponding benzaldehyde derivative and dehydration under the catalysis of a dehydrating agent tri-n-butyl borate; and hydrolyzing the intermediate (I) by a one-pot method to obtain a crude product, and purifying the crude product to obtain a final product curcumin (derivative).
The specific reaction equation of the invention is as follows:
the specific method of the invention comprises the following steps:
(1) adding calcium acetylacetonate and vanillin (benzaldehyde derivatives) in a reactor according to a molar ratio of 1: 4-10, and adding a certain mass of dimethylformamide (serving as a solvent, and taking 100 times of the amount of the calcium acetylacetonate as the best amount);
(2) heating n-butylamine (as a catalyst, the amount of 1 time of the calcium acetylacetonate is optimal) and tributylborate (as a water removal agent, the amount of 9.6 times of the calcium acetylacetonate is optimal) to 40-65 ℃, and then dropwise adding the mixture into the reactor; and (3) reacting in a reactor at the temperature of 50-90 ℃ and the stirring speed of 20r/min in a dry environment. The reaction temperature is preferably 60-90 ℃.
(3) And (3) pressing the reaction liquid obtained after the reaction in the step (2) into a hydrolysis kettle, adding water with the molar weight being 3.75-7.5 times that of the dimethylformamide in the step (1), adjusting the pH to 1-5 with hydrochloric acid, hydrolyzing at normal temperature, and centrifuging to separate curcumin or derivatives thereof.
(4) And (4) drying the curcumin or the derivative thereof separated in the step (3), and packaging the product.
The mother liquor after the reaction in the step (3) mainly comprises dimethylformamide, water, calcium chloride and a small amount of vanillin (benzaldehyde derivative). The mother liquor can be recycled.
The drying environment in the step (2) is preferably a water content of 1000ppm or less.
And (3) performing centrifugal separation in the step (3), wherein a teflon-lined turbo centrifuge is used as the centrifuge. The invention relates to a method for synthesizing curcumin and derivatives thereof by taking calcium acetylacetonate as a raw material, which comprises the step of reacting calcium acetylacetonate and vanillin (benzaldehyde derivatives) in a reactor.
The invention has the beneficial effects that:
1. the liquid phase result shows that when the existing preparation method is used for preparing curcumin and derivatives thereof, the α -site substitution product of the acetylacetone is about 15 percent, but the method of the invention reduces the product to less than 1 percent, macroscopically embodied in the yield of the curcumin and the derivatives thereof, the existing preparation method has the yield of the curcumin of about 60 percent, and the preparation method of the invention has the yield of 80-90 percent, therefore, the method of the invention reduces the waste of raw materials and the generation of byproducts;
2. the calcium acetylacetonate used in the invention is used as the intermediate of curcumin or derivatives thereof generated by the acetylacetone source, and the hydrolysis condition is milder. In the existing curcumin preparation method, hydrolysis needs to be carried out at about 80 ℃; the hydrolysis method can be completely hydrolyzed only at normal temperature, insoluble substances contained in the product are almost zero, and the obtained product is purer;
3. compared with the prior art, the method has the advantages of simple process, mild conditions, green chemical concept conformity, suitability for industrial production and the like.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1
Firstly, drying calcium acetylacetonate at the temperature of 60 ℃ in vacuum; measuring the water content by a Fischer reagent method, and obtaining the acetylacetone-calcium acetylacetonate as the supply source after the water content is qualified.
49.1Kg of calcium acetylacetonate, 125Kg of vanillin, 1500Kg of dimethylformamide and 460Kg of tri-n-butyl borate are placed in a reactor, heated to 55 ℃ and stirred for dissolution. Heating 15Kg of n-butylamine to 40 ℃ by a heater, dropwise adding into a reactor within 30 minutes, and reacting at the reaction temperature of 60 ℃, the stirring speed of 20r/min and normal pressure. Pressing the reacted reaction liquid into a hydrolysis kettle, adding 1500Kg of water, adjusting the pH to 5, stirring at normal temperature for hydrolysis for 12h, discharging and centrifuging; centrifuging to obtain crude curcumin product, and drying to obtain refined curcumin product 136.7Kg, with yield of 90% and purity of 99%. Packaging the final product; the mother liquor is recycled and reused.
During the reaction, the reaction solution in the reactor was analyzed, and the analysis results are shown in Table 1.
Example 2
Firstly, drying calcium acetylacetonate at the temperature of 60 ℃ in vacuum; measuring the water content by a Fischer reagent method, and obtaining the acetylacetone-calcium acetylacetonate as the supply source after the water content is qualified.
49.1Kg of calcium acetylacetonate, 166Kg of isovanillin, 1500Kg of dimethylformamide and 460Kg of tri-n-butyl borate are placed in a reactor, heated to 88 ℃ and stirred for dissolution. Heating 15Kg of n-butylamine to 40 ℃ by a heater, dropwise adding into a reactor within 30 minutes, and reacting at the reaction temperature of 60 ℃, the stirring speed of 20r/min and normal pressure. Pressing the reacted reaction solution into a hydrolysis kettle, adding 3000Kg of water, adjusting the pH to 5, stirring at normal temperature for hydrolysis for 12h, discharging and centrifuging; centrifuging to obtain crude product of isovanillin-curcumin, drying to obtain refined product of isovanillin-curcumin 135.1Kg with yield of 89% and purity of 98.5%, and packaging the product; the mother liquor is recycled and reused.
During the reaction, the reaction solution in the reactor was analyzed, and the analysis results are shown in Table 1.
Example 3
Firstly, drying calcium acetylacetonate at the temperature of 60 ℃ in vacuum; measuring the water content by a Fischer reagent method, and obtaining the acetylacetone-calcium acetylacetonate as the supply source after the water content is qualified.
49.1Kg of calcium acetylacetonate, 168Kg of p-hydroxybenzaldehyde, 1500Kg of dimethylformamide and 460Kg of tri-n-butyl borate are placed in a reactor, heated to 68 ℃ and stirred for dissolution. Heating 15Kg of n-butylamine to 40 ℃ by a heater, dropwise adding into a reactor within 30 minutes, and reacting at the reaction temperature of 60 ℃, the stirring speed of 20r/min and normal pressure. Pressing the reacted reaction liquid into a hydrolysis kettle, adding 3500Kg of water, adjusting the pH to 5, stirring at normal temperature for hydrolysis for 12h, discharging and centrifuging; centrifuging to obtain a crude bisdemethoxycurcumin product, drying to obtain refined bisdemethoxycurcumin product 114.4Kg, with yield of 90% and purity of 98.9%, and packaging the product; the mother liquor is recycled and reused.
During the reaction, the reaction solution in the reactor was analyzed, and the analysis results are shown in Table 1.
Example 4
Firstly, drying calcium acetylacetonate at the temperature of 60 ℃ in vacuum; measuring the water content by a Fischer reagent method, and obtaining the acetylacetone-calcium acetylacetonate as the supply source after the water content is qualified.
49.1Kg of calcium acetylacetonate, 280Kg of p-methoxybenzaldehyde, 1500Kg of dimethylformamide and 460Kg of tri-n-butyl borate are placed in a reactor, heated to 70 ℃ and stirred for dissolution. Heating 15Kg of n-butylamine to 40 ℃ by a heater, dropwise adding into a reactor within 30 minutes, and reacting at the reaction temperature of 65 ℃, the stirring speed of 20r/min and normal pressure. Pressing the reacted reaction solution into a hydrolysis kettle, adding 2000Kg of water, adjusting the pH to 3, stirring at normal temperature for hydrolysis for 12h, discharging and centrifuging; centrifuging to obtain a crude product of bisdemethoxycurcumin dimethyl ether, drying to obtain a refined product of bisdemethoxycurcumin dimethyl ether of 110.9Kg, with yield of 80% and purity of 99%, and packaging the product; the mother liquor is recycled and reused.
During the reaction, the reaction solution in the reactor was analyzed, and the analysis results are shown in Table 1.
Example 5
Firstly, drying calcium acetylacetonate at the temperature of 60 ℃ in vacuum; measuring the water content by a Fischer reagent method, and obtaining the acetylacetone-calcium acetylacetonate as the supply source after the water content is qualified.
49.1Kg of calcium acetylacetonate, 200Kg of p-benzyloxybenzaldehyde, 1500Kg of dimethylformamide and 460Kg of tri-n-butyl borate were charged into a reactor, and the mixture was heated to 75 ℃ and dissolved by stirring. Heating 15Kg of n-butylamine to 40 ℃ by a heater, dropwise adding into a reactor within 30 minutes, and reacting at the reaction temperature of 70 ℃, the stirring speed of 20r/min and normal pressure. Pressing the reacted reaction solution into a hydrolysis kettle, adding 5000Kg of water, adjusting the pH to 1, stirring at normal temperature for hydrolysis for 12h, discharging and centrifuging; centrifuging to obtain a crude bisdemethoxycurcumin dibenzyl ether product, drying to obtain 147.8Kg of a refined bisdemethoxycurcumin dibenzyl ether product, wherein the yield is 90 percent, the purity is 99 percent, and finally packaging the product; the mother liquor is recycled and reused.
During the reaction, the reaction solution in the reactor was analyzed, and the analysis results are shown in Table 1.
Example 6
Firstly, drying calcium acetylacetonate at the temperature of 60 ℃ in vacuum; measuring the water content by a Fischer reagent method, and obtaining the acetylacetone-calcium acetylacetonate as the supply source after the water content is qualified.
49.1Kg of calcium acetylacetonate, 190Kg of 3, 5-dihydroxybenzaldehyde, 1500Kg of dimethylformamide and 460Kg of tri-n-butyl borate are placed in a reactor, heated to 85 ℃ and stirred for dissolution. Heating 15Kg of n-butylamine to 40 ℃ by a heater, dropwise adding into a reactor within 30 minutes, and reacting at the reaction temperature of 66 ℃, the stirring speed of 20r/min and normal pressure. Pressing the reacted reaction liquid into a hydrolysis kettle, adding 3500Kg of water, adjusting the pH to 2, stirring at normal temperature for hydrolysis for 12h, discharging and centrifuging; centrifuging to obtain crude product of 3, 5-dihydroxybenzaldehyde-curcumin, drying to obtain refined product of 3, 5-dihydroxybenzaldehyde-curcumin 120.6Kg, with yield 86% and purity 95%, and packaging the final product; the mother liquor is recycled and reused.
During the reaction, the reaction solution in the reactor was analyzed, and the analysis results are shown in Table 1.
Example 7
Firstly, drying calcium acetylacetonate at the temperature of 60 ℃ in vacuum; measuring the water content by a Fischer reagent method, and obtaining the acetylacetone-calcium acetylacetonate as the supply source after the water content is qualified.
49.1Kg of calcium acetylacetonate, 170Kg of salicylaldehyde, 1500Kg of dimethylformamide and 460Kg of tri-n-butyl borate are placed in a reactor, heated to 80 ℃ and stirred to dissolve. Heating 15Kg of n-butylamine to 40 ℃ by a heater, dropwise adding into a reactor within 30 minutes, and reacting at the reaction temperature of 69 ℃, at the stirring speed of 20r/min and under normal pressure. Pressing the reacted reaction liquid into a hydrolysis kettle, adding 2500Kg of water, adjusting the pH to 3, stirring at normal temperature for hydrolysis for 12h, discharging and centrifuging; centrifuging to obtain crude salicylaldehyde-curcumin product, drying to obtain refined salicylaldehyde-curcumin product 104.2Kg, with yield of 82% and purity of 96%, and packaging the product; the mother liquor is recycled and reused.
During the reaction, the reaction solution in the reactor was analyzed, and the analysis results are shown in Table 1.
Example 8
Firstly, drying calcium acetylacetonate at the temperature of 60 ℃ in vacuum; measuring the water content by a Fischer reagent method, and obtaining the acetylacetone-calcium acetylacetonate as the supply source after the water content is qualified.
49.1Kg of calcium acetylacetonate, 160Kg of benzaldehyde, 1500Kg of dimethylformamide and 460Kg of tri-n-butyl borate are placed in a reactor, heated to 90 ℃ and stirred for dissolution. Heating 15Kg of n-butylamine to 40 ℃ by a heater, dropwise adding into a reactor within 30 minutes, and reacting at the reaction temperature of 61 ℃, the stirring speed of 20r/min and normal pressure. Pressing the reacted reaction solution into a hydrolysis kettle, adding 2000Kg of water, adjusting the pH to 5, stirring at normal temperature for hydrolysis for 12h, discharging and centrifuging; centrifuging to obtain a crude product of the dehydroxydemethoxycurcumin, drying to obtain 102.5Kg of refined dehydroxycurcumin product with the yield of 90 percent and the purity of 99 percent, and finally packaging the product; the mother liquor is recycled and reused.
During the reaction, the reaction solution in the reactor was analyzed, and the analysis results are shown in Table 1.
Example 9
Firstly, drying calcium acetylacetonate at the temperature of 60 ℃ in vacuum; measuring the water content by a Fischer reagent method, and obtaining the acetylacetone-calcium acetylacetonate as the supply source after the water content is qualified.
49.1Kg of calcium acetylacetonate, 170Kg of m-hydroxybenzaldehyde, 1500Kg of dimethylformamide and 460Kg of tri-n-butyl borate are placed in a reactor, heated to 66 ℃ and stirred for dissolution. Heating 15Kg of n-butylamine to 40 ℃ by a heater, dropwise adding into a reactor within 30 minutes, and reacting at the reaction temperature of 69 ℃, at the stirring speed of 20r/min and under normal pressure. Pressing the reacted reaction solution into a hydrolysis kettle, adding 3000Kg of water, adjusting the pH value to 1, stirring at normal temperature for hydrolysis for 12h, discharging and centrifuging; centrifuging to obtain a crude bisdemethoxy-iso-curcumin product, drying to obtain 109.3Kg of refined bisdemethoxy-iso-curcumin product with yield of 86% and purity of 98%, and finally packaging the product; the mother liquor is recycled and reused.
During the reaction, the reaction solution in the reactor was analyzed, and the analysis results are shown in Table 1.
Example 10
Firstly, drying calcium acetylacetonate at the temperature of 60 ℃ in vacuum; measuring the water content by a Fischer reagent method, and obtaining the acetylacetone-calcium acetylacetonate as the supply source after the water content is qualified.
49.1Kg of calcium acetylacetonate, 190Kg of 2, 4-dihydroxybenzaldehyde, 1500Kg of dimethylformamide and 460Kg of tri-n-butyl borate are placed in a reactor, heated to 60 ℃ and stirred for dissolution. Heating 15Kg of n-butylamine to 40 ℃ by a heater, dropwise adding into a reactor within 30 minutes, and reacting at the reaction temperature of 60 ℃, the stirring speed of 20r/min and normal pressure. Pressing the reacted reaction liquid into a hydrolysis kettle, adding 2500Kg of water, adjusting the pH to 3, stirring at normal temperature for hydrolysis for 12h, discharging and centrifuging; centrifuging to obtain crude 2, 4-dihydroxybenzaldehyde-curcumin, drying to obtain refined 2, 4-dihydroxybenzaldehyde-curcumin of 124.9Kg, with yield of 89% and purity of 98%, and packaging the final product; the mother liquor is recycled and reused.
During the reaction, the reaction solution in the reactor was analyzed, and the analysis results are shown in Table 1.
Example 11
Firstly, drying calcium acetylacetonate at the temperature of 60 ℃ in vacuum; measuring the water content by a Fischer reagent method, and obtaining the acetylacetone-calcium acetylacetonate as the supply source after the water content is qualified.
49.1Kg of calcium acetylacetonate, 160Kg of 3,4, 5-trihydroxybenzaldehyde, 1500Kg of dimethylformamide and 460Kg of tri-n-butyl borate are placed in a reactor, heated to 50 ℃ and stirred for dissolution. Heating 15Kg of n-butylamine to 40 ℃ by a heater, dropwise adding into a reactor within 30 minutes, and reacting at the reaction temperature of 50 ℃, the stirring speed of 20r/min and normal pressure. Pressing the reacted reaction liquid into a hydrolysis kettle, adding 2700Kg of water, adjusting the pH to be 4, stirring at normal temperature for hydrolysis for 12h, discharging and centrifuging; centrifuging to obtain crude product of 3,4, 5-trihydroxybenzaldehyde-curcumin, drying to obtain refined product of 3,4, 5-trihydroxybenzaldehyde-curcumin 138.1Kg, with yield of 90% and purity of 98%, and packaging the final product; the mother liquor is recycled and reused.
During the reaction, the reaction solution in the reactor was analyzed, and the analysis results are shown in Table 1.
TABLE 1 analysis of reactor off-gas*
*Data were collected at 16h after the reaction.
The data in the table show that when the method for synthesizing the curcumin and the derivatives thereof by using the calcium acetylacetonate as the raw material is used, the conversion rate of the calcium acetylacetonate and the selectivity of the curcumin or the derivatives thereof are still higher when the calcium acetylacetonate reacts with the corresponding benzaldehyde derivatives for 16 hours, the method also reduces three wastes in post-treatment, and has higher raw material utilization rate and atom economy.
If the reaction temperature is lower than 60 ℃, the conversion rate of the calcium acetylacetonate is very low; above 90 ℃, the activity of the reactants and the selectivity of curcumin are very low.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and all embodiments are within the scope of the present invention as long as the requirements of the present invention are met.
Claims (5)
1. A method for artificially synthesizing curcumin and derivatives thereof comprises the steps of taking calcium acetylacetonate as an acetylacetone source, carrying out claisen-Schmitt ester condensation reaction with corresponding benzaldehyde derivatives, and dehydrating under the catalysis of a dehydrating agent tri-n-butyl borate to obtain a product intermediate (I) curcumin calcium salt; then hydrolyzing the intermediate (I) by a one-pot method to obtain a crude product, and purifying the crude product to obtain a final product curcumin or curcumin derivative;
the reaction equation is as follows:
the method specifically comprises the following steps:
adding calcium acetylacetonate and benzaldehyde derivatives into a reactor, and then adding a solvent dimethylformamide for mixing;
heating catalyst n-butylamine and water removing agent tri-n-butyl borate to 40-65 ℃, then dropwise adding the catalyst n-butylamine and the water removing agent tri-n-butyl borate into the reactor in the step (1), and reacting at the temperature of 60-90 ℃ and the stirring speed of 20r/min in a dry environment to obtain a reaction solution;
pressing the reaction liquid obtained after the reaction in the step (2) into a hydrolysis kettle, adding a certain amount of water, adjusting the pH value to 1-5, hydrolyzing at normal temperature, and centrifugally separating curcumin or curcumin derivatives;
step (4), drying the curcumin or curcumin derivative separated in the step (3), and packaging the product;
the preparation method is characterized in that the molar ratio of calcium acetylacetonate to benzaldehyde derivative is 1: 4-10; the mol ratio of the calcium acetylacetonate, the n-butylamine and the tri-n-butyl borate is 1: 1: 9.6; the molar ratio of the calcium acetylacetonate to the dimethylformamide is 1: 100.
2. The method for artificially synthesizing curcumin and its derivatives as claimed in claim 1, wherein the benzaldehyde derivative is vanillin.
3. The method for artificially synthesizing curcumin and its derivatives as claimed in claim 1, wherein the water content in the dry environment in step (2) is less than or equal to 1000 ppm.
4. The method for artificially synthesizing curcumin and its derivatives as claimed in claim 1, wherein the mother liquor separated in step (3) can be recycled.
5. The process for artificially synthesizing curcumin and its derivatives as claimed in claim 1, wherein the centrifuge used in the step (3) is a turbo centrifuge lined with polytetrafluoroethylene.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103910615A (en) * | 2014-04-09 | 2014-07-09 | 西安雅森生物技术有限公司 | Method for synthesizing curcumin |
| EP2857379A1 (en) * | 2012-05-08 | 2015-04-08 | Asac Compañía De Biotecnología E Investigación SA | Method for the synthesis of curcumin |
| CN105152892A (en) * | 2015-09-30 | 2015-12-16 | 聊城大学 | 3, 3'-hydroxy curcumin analogue and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2857379A1 (en) * | 2012-05-08 | 2015-04-08 | Asac Compañía De Biotecnología E Investigación SA | Method for the synthesis of curcumin |
| CN103910615A (en) * | 2014-04-09 | 2014-07-09 | 西安雅森生物技术有限公司 | Method for synthesizing curcumin |
| CN105152892A (en) * | 2015-09-30 | 2015-12-16 | 聊城大学 | 3, 3'-hydroxy curcumin analogue and preparation method and application thereof |
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| Calcium hydroxide: An efficient and mild base for one-pot synthesis of curcumin and it’s analogues;Pramod S. Kulkarni etal;《Acta Chimica Slovaca》;20131231;第6卷(第1期);151 * |
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