Method for extracting coumarin from lavender
By preparing polyacrylamide molecules rich in high affinity for coumarin, using intermolecular action forces, the problems of low extraction efficiency and poor selectivity of coumarin in traditional extraction methods are solved, and efficient and low-cost coumarin extraction is achieved, with an extraction purity of more than 99.9%.
Patent Information
- Application Number
- CN202411923366.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-25
- Publication Date
- 2025-03-28
AI Technical Summary
The traditional method of extracting coumarin from lavender has the problem of low extraction efficiency and poor selectivity, which leads to high cost and low extraction efficiency.
By preparing polyacrylamide host molecules rich in holes with extremely high affinity with coumarin, coumarin in lavender is efficiently adsorbed and extracted coumarin from lavender using intermolecular forces such as hydrogen bonding and π-π stacking.
The efficient and selective extraction of coumarin is achieved, and the extraction purity can reach more than 99.9%, which reduces the use of organic solvents, improves the extraction efficiency and reduces the cost.
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of natural compound extraction, in particular to a method for extracting coumarin from lavender. Technical Background
[0002] As an important natural organic compound, coumarin is widely used in medicine, spices, cosmetics and other fields. Traditional methods of extracting coumarin from lavender, such as solvent extraction, often have problems such as low extraction efficiency and poor selectivity for coumarin. With the continuous development of modern molecular technology, it provides a new opportunity for more efficient and accurate separation and extraction of coumarin from lavender.
[0003] There are differences in the forces between molecules of different substances. For example, hydrogen bonds, van der Waals forces, π-π interactions, etc., behave differently between different molecules. Based on these differences, targeted extraction methods can be designed. For coumarin, its molecular structure is different from other components in lavender, resulting in different intermolecular forces between it and specific adsorbents or separation media. By utilizing the specificity of this intermolecular force, efficient and selective extraction of coumarin can be achieved. This extraction technology based on different intermolecular forces can overcome the drawbacks of traditional extraction methods, reduce the use of organic solvents, improve the extraction purity and extraction efficiency of coumarin, open up new and more advantageous ways for the extraction of coumarin in lavender, promote the further development of coumarin-related industries in the direction of green and high efficiency, and meet the growing market demand for high-quality coumarin. Summary of the invention
[0004] The present invention discloses a set of technical methods for extracting coumarin from lavender by utilizing the difference in the forces between different molecules, which solves the problem of low efficiency and high cost caused by low selectivity in the traditional method of extracting coumarin from lavender.
[0005] The technical solution of the present invention is: a method for extracting coumarin from lavender is:
[0006] (1) Preparation of functional template: Add acrylamide monomer aqueous solution and coumarin to the reaction flask, introduce nitrogen to evacuate the air, heat in a water bath, add ammonium sulfate aqueous solution under stirring to initiate the reaction, and then add tetramethylethylenediamine aqueous solution to accelerate the reaction. After a period of time, the reaction stops, and the functional template of the uneluted template molecule is deposited at the bottom of the reaction flask. The functional template of the uneluted template molecule is filtered out from the solution, washed with deionized water, filtered, and then placed in an acidified ethanol solution for ultrasonic desorption and filtered. The filter cake is washed with ethanol several times and filtered, and the product is dried to obtain the functional template.
[0007] (2) Extracting coumarin from lavender: Add 1 / 10 of the weight of dry lavender to ethanol, heat in a water bath, condense and reflux, and concentrate the obtained solution using a rotary evaporator to obtain a concentrated extract. The concentrated extract is mixed with the functional template in (1), heated, stirred and refluxed to obtain a functional template that adsorbs coumarin. The functional template that adsorbs coumarin is washed with ethanol, and coumarin is extracted with a Soxhlet extractor using acidified ethanol as a solvent. The obtained solution is neutralized with a 1% sodium hydroxide aqueous solution, and slowly added to petroleum ether under stirring. The precipitated solid is coumarin.
[0008] Wherein, the concentration of the aqueous solution of acrylamide monomer described in (1) is 20%; the purity of coumarin is greater than 99.99%; the concentration of the aqueous solution of ammonium sulfate is 0.03%; and the concentration of the aqueous solution of tetramethylethylenediamine is 0.03%.
[0009] Among them, the ratio of acrylamide monomer, coumarin, ammonium sulfate aqueous solution and tetramethylethylenediamine aqueous solution in (1) is 1g: (0.01-0.05)g: (0.1-0.3)g: (0.1-0.3)g.
[0010] In (1), the water bath heating temperature is 50-60° C., the stirring speed is 25-30 RPM, and the reaction time is 60-90 minutes.
[0011] Wherein, the acidified ethanol in (1) is a 1% sulfuric acid ethanol solution; the number of times of washing the product with deionized water, acidified ethanol, and ethanol is 3 times or more.
[0012] Wherein, the power of ultrasonic desorption in (1) is 20-40w, and the ultrasonic time is 0.5-1 hour.
[0013] The water bath heating temperature in (2) is 65-75° C., and the concentration multiple is 2-4 times.
[0014] The ratio of the concentrated extract in (2) to the functional template in (1) is 1 g:10 g (concentrated solution: functional template), the heating reflux temperature is 65-75° C., and the reflux time is 2-4 hours.
[0015] The acidified ethanol in (2) is a 1% sulfuric acid ethanol solution, and the extraction conditions using a Soxhlet extractor are as follows: the ratio of the functional template for adsorbing coumarin to the acidified ethanol is 1 g:10 g, and the extraction is refluxed at 75° C. for 60 minutes; the pH after neutralization with a 1% sodium hydroxide aqueous solution is between 7 and 8.
[0016] The technical effect of the present invention is that a polyacrylamide main molecule rich in holes with extremely high affinity for coumarin is prepared by utilizing the difference in the forces between different molecules. The main molecule can efficiently adsorb coumarin monomers in lavender extract by virtue of the holes with extremely high affinity for coumarin, and the main molecule can be reused after being activated, thereby realizing efficient, rapid and low-cost extraction of coumarin.
[0017] The present invention utilizes the hydrogen bonding force and π-π stacking between the amide group in acrylamide and the carbonyl group and carbon-carbon double bond in coumarin to prepare a high-molecular-weight mixed organic matter of polyacrylamide that uniformly integrates coumarin, and after protonating the coumarin therein to weaken the affinity between polyacrylamide and coumarin, a polyacrylamide polymer rich in holes with high affinity for coumarin is formed after solvent elution. The functional group structure of the treated polyacrylamide polymer does not change, but the three-dimensional structure of the space leaves specific holes. The polyacrylamide with specific holes can be re-adsorbed and combined when it contacts coumarin again, and after acidification and elution again, the extraction of coumarin and the reuse of the main molecule are realized. The purity of coumarin extracted from the main molecule prepared by this technology can reach more than 99.9%, showing extremely high extraction accuracy and efficiency. DETAILED DESCRIPTION
[0018] To better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments. It should be understood by those skilled in the art that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.
[0019] Example 1
[0020] 20g of 20% aqueous solution of acrylamide monomer and 0.01g of coumarin with a purity of more than 99.99% were added to the reaction flask, and after nitrogen was introduced to evacuate the air, 0.1g of 0.03% aqueous solution of ammonium sulfate was added at a water bath heating of 50°C and a stirring speed of 25RPM to initiate the reaction, and then 0.1g of 0.03% aqueous solution of tetramethylethylenediamine was added to accelerate the reaction. After 60 minutes of reaction, the functional template of the uneluted template molecule deposited at the bottom of the reaction flask was obtained. The functional template of the uneluted template molecule was filtered out from the solution, washed with deionized water, filtered 3 times, and then placed in a 1% ethanol solution of sulfuric acid, ultrasonically desorbed at a power of 20w for 30 minutes, and the product was filtered, and the filter cake was washed with ethanol and filtered 3 times, and the product was dried to obtain 3.276g of the functional template.
[0021] Example 2
[0022] 20g of 20% aqueous solution of acrylamide monomer and 0.01g of coumarin with a purity of more than 99.99% were added to the reaction flask, and after nitrogen was introduced to evacuate the air, 0.3g of 0.03% aqueous solution of ammonium sulfate was added at a stirring speed of 30RPM at 50°C to initiate the reaction, and then 0.3g of 0.03% aqueous solution of tetramethylethylenediamine was added to accelerate the reaction. After 90 minutes of reaction, the functional template of the uneluted template molecule deposited at the bottom of the reaction flask was obtained. The functional template of the uneluted template molecule was filtered out from the solution, washed with deionized water, filtered 3 times, and then placed in a 1% ethanol solution of sulfuric acid, ultrasonically desorbed at a power of 20w for 60 minutes, and the product was filtered, and the filter cake was washed with ethanol and filtered 3 times, and the product was dried to obtain 3.372g of the functional template.
[0023] Example 3
[0024] 20g of 20% aqueous solution of acrylamide monomer and 0.01g of coumarin with a purity of more than 99.99% were added to the reaction flask, and after nitrogen was introduced to evacuate the air, 0.1g of 0.03% aqueous solution of ammonium sulfate was added at a water bath heating of 60°C and a stirring speed of 25RPM to initiate the reaction, and then 0.1g of 0.03% aqueous solution of tetramethylethylenediamine was added to accelerate the reaction. After 60 minutes of reaction, the functional template of the uneluted template molecule deposited at the bottom of the reaction flask was obtained. The functional template of the uneluted template molecule was filtered out from the solution, washed with deionized water, filtered 3 times, and then placed in a 1% ethanol solution of sulfuric acid, ultrasonically desorbed at a power of 40w for 30 minutes, and the product was filtered, and the filter cake was washed with ethanol and filtered 3 times, and the product was dried to obtain 3.402g of the functional template.
[0025] Example 4
[0026] 20g of 20% acrylamide monomer aqueous solution and 0.05g coumarin with a purity of more than 99.99% were added to the reaction bottle, and after nitrogen was passed to evacuate the air, 0.1g of 0.03% ammonium sulfate aqueous solution was added at a 60°C water bath and a stirring speed of 30RPM to initiate the reaction, and then 0.1g of 0.03% tetramethylethylenediamine aqueous solution was added to accelerate the reaction. After 60 minutes of reaction, the functional template of the uneluted template molecule deposited at the bottom of the reaction bottle was obtained. The functional template of the uneluted template molecule was filtered out from the solution, washed with deionized water, filtered 3 times, and then placed in a 1% sulfuric acid ethanol solution, ultrasonically desorbed at a power of 40w for 60 minutes, and the product was filtered, and the filter cake was washed with ethanol and filtered 3 times, and the product was dried to obtain 3.318g of the functional template.
[0027] Example 5
[0028] Add 1 / 10 of the weight of ethanol dried lavender to ethanol, heat in a water bath at 65°C, condense and reflux for 3 hours, and concentrate the obtained solution by 2 times using a rotary evaporator to obtain a concentrated extract. Mix the above concentrated extract with 1g:10g (concentrated solution: functional template) of Example 3, heat at 65°C, stir and reflux for 2 hours to obtain a functional template that adsorbs coumarin. Use ethanol to wash the above functional template that adsorbs coumarin, use acidified ethanol as a solvent, use a Soxhlet extractor at 75°C to extract coumarin for 60 minutes, and neutralize the obtained solution with 1% sodium hydroxide aqueous solution to a pH of 7.5, slowly add petroleum ether under stirring, and the precipitated solid is coumarin. The mass of coumarin obtained after drying is 0.084g.
[0029] Example 6
[0030] Add 1 / 10 of the weight of ethanol dried lavender to ethanol, heat in a water bath at 65°C, condense and reflux for 3 hours, and concentrate the obtained solution 4 times using a rotary evaporator to obtain a concentrated extract. Mix the above concentrated extract with 1g:10g (concentrated solution: functional template) of Example 3, heat at 75°C, stir and reflux for 2 hours to obtain a functional template that adsorbs coumarin. Use ethanol to wash the above functional template that adsorbs coumarin, use acidified ethanol as a solvent, use a Soxhlet extractor at 75°C to extract coumarin for 60 minutes, and neutralize the obtained solution with 1% sodium hydroxide aqueous solution to a pH of 7.5, slowly add petroleum ether under stirring, and the precipitated solid is coumarin. The mass of coumarin obtained after drying is 0.102g.
[0031] Example 7
[0032] Add 1 / 10 of the weight of ethanol dried lavender to ethanol, heat in a water bath at 65°C, condense and reflux for 3 hours, and concentrate the obtained solution by 2 times using a rotary evaporator to obtain a concentrated extract. Mix the above concentrated extract with 1g:10g (concentrated solution: functional template) of Example 3, heat at 65°C, stir and reflux for 4 hours to obtain a functional template that adsorbs coumarin. Use ethanol to wash the above functional template that adsorbs coumarin, use acidified ethanol as a solvent, use a Soxhlet extractor at 75°C to extract coumarin for 60 minutes, and neutralize the obtained solution with 1% sodium hydroxide aqueous solution to a pH of 7.5, slowly add petroleum ether under stirring, and the precipitated solid is coumarin. The mass of coumarin obtained after drying is 0.091g.
[0033] Example 8
[0034] Add 1 / 10 of the weight of ethanol dried lavender to ethanol, heat in a water bath at 65°C, condense and reflux for 3 hours, and concentrate the obtained solution by 2 times using a rotary evaporator to obtain a concentrated extract. Mix the above concentrated extract with 1g:10g (concentrated solution: functional template) of Example 3, heat at 75°C, stir and reflux for 2 hours to obtain a functional template that adsorbs coumarin. Use ethanol to wash the above functional template that adsorbs coumarin, use acidified ethanol as a solvent, use a Soxhlet extractor at 75°C to extract coumarin for 60 minutes, and neutralize the obtained solution with 1% sodium hydroxide aqueous solution to a pH of 7.5, slowly add petroleum ether under stirring, and the precipitated solid is coumarin. The mass of coumarin obtained after drying is 0.099g.
[0035] Comparative Example 1
[0036] The preparation of the functional template was carried out completely according to the method of Example 3, except that the template molecule, coumarin, was replaced by its derivative coumarin-6-carboxaldehyde, and the extraction of coumarin from lavender was carried out completely according to the method of Example 6. The mass of the coumarin obtained after drying was 0.011 g.
[0037] Comparative Example 2
[0038] The preparation of the functional template was carried out completely according to the method of Example 3, except that the functional monomer, acrylamide, was replaced by 1-chloroacrylamide, and the mass of the obtained functional template was 1.033 g. When extracting coumarin from lavender, the method of Example 6 was carried out completely. The mass of the coumarin obtained after drying was 0.028 g.
[0039] Comparative Example 3
[0040] The preparation of the functional template was carried out completely according to the method of Example 3, except that the functional monomer, acrylamide, was replaced by 1-chloroacrylamide, and the template molecule, coumarin, was replaced by its derivative, coumarin-6-carboxaldehyde. When extracting coumarin from lavender, it was carried out completely according to the method of Example 6. The mass of the coumarin obtained after drying was 0.000 g.
[0041] In comparative example 1, the template molecule, coumarin, was replaced by its derivative, coumarin-6-carboxaldehyde. Although coumarin-6-carboxaldehyde is a derivative of coumarin and has a similar structure, the final yield of coumarin extracted is very low. This is because although coumarin-6-carboxaldehyde has only one more aldehyde group than coumarin, its steric hindrance and electron cloud distribution have changed, and the selectivity of the holes created using coumarin-6-carboxaldehyde as a template for coumarin is not high.
[0042] In comparative example 2, the functional monomer, acrylamide, is replaced by 1-chloroacrylamide. The chlorine atom is an electron-withdrawing group. The addition of chlorine greatly reduces the electron cloud density on the double bond in the molecule and increases the spatial position, which is not conducive to the collision between molecules, so the final polymerization yield is greatly reduced. The formed poly 1-chloroacrylamide disperses the electron density on the nitrogen atom due to the migration of the electron cloud to the chlorine atom, weakens the strength of the hydrogen bond, and thus weakens the binding strength between coumarin and the functional template, and finally the efficiency of extracting coumarin is greatly reduced.
[0043] In Control Example 3, both the functional monomer and the template molecule were changed, resulting in significant changes in the shape, size, and position of the functional group of the cavity, and ultimately a loss of selectivity for coumarin.
[0044] The coumarin extracted in the above Examples 5-8 and Control Examples 1-2 was tested for purity using a high performance liquid chromatograph (HPLC) and a nuclear magnetic resonance spectrometer (NMR) (the extracted products in Control Examples 1-2 are not necessarily coumarin, and the type and position of the functional groups need to be measured to determine the structure). The final results are shown in Table 1.
[0045] Table 1 Purity of coumarin extracted from Examples 5-8 and Comparative Examples 1-2
[0046] Case Coumarin purity Example 5 99.98％ Example 6 99.99％ Example 7 99.99％ Example 8 99.99％ Comparative Example 1 1.13％ Comparative Example 2 0.92％
[0047] It can be seen from Table 1 that the coumarin extracted in Examples 5-8 is all above 99.9%, which reflects the high selectivity of the method of the present invention for extracting coumarin. Slightly adjusting the functional monomer or template molecule will eventually cause a change in the selectivity of the functional template, which reflects the high selectivity of the method of the present invention for coumarin.
[0048] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.
Claims
1. A method for extracting coumarin from lavender, characterized in that: The preparation method of the functional template is: (1-1) Add acrylamide monomer aqueous solution and coumarin to a reaction flask, purge the air with nitrogen, heat in a water bath, add ammonium sulfate aqueous solution under stirring to initiate the reaction, and then add tetramethylethylenediamine aqueous solution to accelerate the reaction. After a period of time, the reaction stops, and a functional template of uneluted template molecules is obtained at the bottom of the reaction flask. (1-2) The functional template of the uneluted template molecule described in (1-1) is filtered out from the solution, washed with deionized water, filtered, and then placed in an acidified ethanol solution for ultrasonic desorption and filtered. The filter cake obtained is washed and filtered with ethanol multiple times, and the obtained product is dried to obtain the functional template.
2. The method for preparing the functional template according to claim 1 is characterized in that: The concentration of the acrylamide monomer aqueous solution is 20%; the purity of coumarin is greater than 99.99%; the concentration of the ammonium sulfate aqueous solution is 0.03%; and the concentration of the tetramethylethylenediamine aqueous solution is 0.03%.
3. The method for preparing the functional template according to claim 1 is characterized in that: The ratio of the acrylamide monomer, coumarin, ammonium sulfate aqueous solution and tetramethylethylenediamine aqueous solution is 1g: (0.01-0.05)g: (0.1-0.3)g: (0.1-0.3)g.
4. The method for preparing the functional template according to claim 1 is characterized in that: The water bath heating temperature is 50-60° C., the stirring speed is 25-30 RPM, and the reaction time is 60-90 minutes.
5. The method for preparing the functional template according to claim 1 is characterized in that: The acidified ethanol is a 1% sulfuric acid ethanol solution; the times of washing the product with deionized water, acidified ethanol and ethanol are all 3 times or more.
6. The method for preparing the functional template according to claim 1 is characterized in that: The power of ultrasonic desorption is 20-40w, and the ultrasonic time is 0.5-1 hour.
7. A method for extracting coumarin from lavender, characterized in that: The method for extracting coumarin from lavender: (2-1) Add 1 / 10 the weight of dry lavender to ethanol, heat in a water bath, condense and reflux for 3 hours, and concentrate the obtained solution using a rotary evaporator to obtain a concentrated extract. (2-2) The concentrated extract obtained in (2-1) is mixed with the functional template in (1-2), and the mixture is heated, stirred and refluxed to obtain a functional template that adsorbs coumarin. (2-3) Use ethanol to clean the functional template adsorbing coumarin in (2-2), use acidified ethanol as a solvent, and extract coumarin with a Soxhlet extractor. After the obtained solution is neutralized with a 1% sodium hydroxide aqueous solution, it is slowly added into petroleum ether under stirring, and the precipitated solid is coumarin.
8. The method for extracting coumarin from lavender according to claim 7, characterized in that: (2-1) The water bath heating temperature is 65-75°C and the concentration multiple is 2-4 times.
9. The method for extracting coumarin from lavender according to claim 7, characterized in that: The concentrated extract in (2-2) and the functional template in (1-2) are mixed in a ratio of 1 g:10 g (concentrated solution: functional template), and the heating reflux temperature is 65-75° C. and the reflux time is 2-4 hours.
10. The method for extracting coumarin from lavender according to claim 7, characterized in that: (2-3) The acidified ethanol is a 1% sulfuric acid ethanol solution, and the extraction conditions using a Soxhlet extractor are as follows: the ratio of the coumarin adsorbed functional template to the acidified ethanol is 1 g:10 g, and the extraction is refluxed at 75°C for 60 minutes; The pH after neutralization with 1% sodium hydroxide aqueous solution is between 7 and 8.