CN111170834A - Preparation method of isoeugenol - Google Patents
Preparation method of isoeugenol Download PDFInfo
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- CN111170834A CN111170834A CN202010115356.5A CN202010115356A CN111170834A CN 111170834 A CN111170834 A CN 111170834A CN 202010115356 A CN202010115356 A CN 202010115356A CN 111170834 A CN111170834 A CN 111170834A
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- C07C41/01—Preparation of ethers
- C07C41/32—Preparation of ethers by isomerisation
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Abstract
The invention discloses a preparation method of isoeugenol, which takes eugenol as a raw material and VK-TA18S and sodium sulfite as catalysts to react under the conditions of heating and illumination to obtain the isoeugenol. The method has the characteristics of easy separation of the catalyst from reactants, repeated use, no corrosion to a reactor, reduction of catalytic public hazard, good selectivity and the like. The method realizes a synthesis process route with good selectivity, high conversion rate, low cost and environmental protection.
Description
Technical Field
The invention belongs to the technical field of essences and spices, and relates to a preparation method of isoeugenol.
Background
Isoeugenol, chemical name: 4-propenyl-2-methoxyphenol, molecular formula C10H12O 2; light yellow slightly thick liquid, which is insoluble in water and glycerol, and is soluble in organic solvents such as ethanol; has soft, sweet and clear spicy fragrance and fragrance like the pink and the clove; the preparation method is mainly used for preparing spice and vanillin, and can be used for preparing essential oil such as cananga odorata and nutmeg; can also be used for preparing edible essence with raspberry, peach, spicy flavor and clove flavor; also is a raw material of semi-synthetic vanillin.
Because the structure of the isoeugenol has cis-form and trans-form, the synthesized isoeugenol is mostly a mixture of cis-form and trans-form isomers. However, cis-isoeugenol is generally required to have a cis-proportion of not more than 10% in a cis-trans mixture when used as a commercial product because of its toxicity.
The existing methods for synthesizing isoeugenol mainly fall into three categories.
One is heating eugenol with water as solvent in the presence of potassium hydroxide, isomerizing eugenol to obtain isoeugenol, wherein the reaction temperature is 160-200 ℃ usually, and the reaction time is 4-15 h. The biggest defect of the method is that the obtained isoeugenol has higher cis-structure proportion, generally about 30 percent, and the product meeting the requirements can be obtained only by separating and purifying by other methods and reducing the cis-structure. Therefore, the whole production process is complex and the production cost is high.
And secondly, the isoeugenol is obtained by isomerizing the isoeugenol under the action of catalysts such as ruthenium, palladium and the like, and the method is mild relative to reaction conditions. Although the proportion of cis-structure can be reduced to a certain extent by this method, the requirements of the product are still not met, and further processing is required. And because of using expensive ruthenium, palladium and other heavy metal catalyst, difficult to recycle, not only increase the production cost, but also can cause environmental pollution after discharging.
And thirdly, heating eugenol by taking a glycol solvent as a reaction solvent in the presence of potassium hydroxide, and isomerizing the eugenol to obtain the isoeugenol, wherein the reaction temperature is usually 160-170 ℃, and the reaction time is 6-8 hours. After the reaction was completed, extraction was performed with toluene. Although the proportion of cis-structure can be reduced to a large extent in this way, there are also certain limitations. For example, (1) the reaction conditions are relatively severe; (2) a large amount of solvent is used in the reaction process, so that the environment is easily polluted (3), and the production process is relatively complicated. In addition, with the increasing awareness of environmental protection, green chemistry has become a requirement and a direction for future chemical development. Therefore, it is important to find a synthetic process route with good selectivity, high conversion rate, low cost and environmental friendliness to meet the current market demand.
Disclosure of Invention
The invention aims to provide a method for preparing isoeugenol and provide the isoeugenol prepared by the method. The method takes eugenol as a raw material, VK-TA18S and sodium sulfite as catalysts, and the isoeugenol is obtained by reaction under the conditions of heating and illumination.
The technical scheme is as follows:
a preparation method of isoeugenol comprises the following steps:
(1) preparation of reaction solution
Mixing eugenol, a catalyst and sodium sulfite to obtain a mixture, introducing nitrogen into the mixture reaction system, introducing the nitrogen for 30-60min, starting a heating lamp, controlling the temperature in the reaction, reacting for a certain time under the illumination condition, and keeping the nitrogen introduction into the system uninterruptedly in the reaction process. Then, the reaction solution was cooled to room temperature to obtain a reaction solution containing isoeugenol.
(2) Catalyst recovery
Filtering the reaction liquid containing the isoeugenol obtained in the step (1), recovering the catalyst, washing the obtained filter cake with water according to the volume ratio of the filter cake to distilled water of 1: 1-1: 2, and drying the washed filter cake for later use;
(3) preparation of the final product
And (3) distilling the filtrate obtained in the step (2) to obtain the final product isoeugenol.
Further, in step (1), the catalyst used is a photo-oxidation catalyst of VK-TA18S type.
According to a preferred embodiment of the invention, in the step (1), the eugenol, the catalyst and the sodium sulfite are uniformly mixed according to the weight ratio of 1 (0-1) to (1-5).
Further, in the step (1), nitrogen is introduced into the system for the purpose of removing oxygen from the system.
Preferably, in the step (1), the obtained mixture is heated and reacted at the temperature of 50-60 ℃.
Further, in the step (1), the lamp used is an LED lamp.
Preferably, in step (1), the resulting mixture is reacted under light conditions for 5 to 20 hours.
Further, in the step (2), the obtained filter cake is washed for 2-3 times according to the same washing mode.
Preferably, in the step (3), the distillation is conducted under reduced pressure at a pressure of 0.1 to 0.3MPa and a temperature of 20 to 140 ℃.
The invention also relates to the final product of the isoeugenol prepared by the preparation method, wherein the content of the isoeugenol is 99.9 percent by weight, and the yield is more than 95 percent.
The invention has the beneficial effects that:
the method has the characteristics of easy separation of the catalyst from reactants, repeated use, no corrosion to a reactor, reduction of catalytic public hazard, good selectivity and the like. The method realizes a synthesis process route with good selectivity, high conversion rate, low cost and environmental protection.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to specific examples.
The invention relates to a preparation method of isoeugenol, which comprises the following steps:
(1) preparation of reaction solution
The eugenol, the VK-TA18S and the sodium sulfite are uniformly mixed according to the weight ratio of 1 (0-1) to (1-5) to obtain a mixture, nitrogen is introduced into a mixture reaction system, oxygen in the system is removed, after 30-60min of nitrogen introduction, a heating LED lamp is started, the reaction temperature is controlled to be 50-60 ℃, the reaction is carried out for 5-20h under the illumination condition, and the nitrogen introduction into the system is kept uninterrupted in the reaction process. Then, the reaction solution was cooled to room temperature to obtain a reaction solution containing isoeugenol.
VK-TA18S used in the present invention is a photo-oxidation catalyst. Photocatalytic oxidation is an advanced oxidation technology which develops rapidly in nearly 20 years, has the characteristics of mild reaction conditions, strong oxidation capacity, wide application range and the like, and has become a research hotspot at home and abroad.
The nitrogen is introduced in the invention to eliminate the oxygen in the reaction system, and the oxygen mainly has two hazards in the reaction system (1) to increase side reactions; (2) the activity of the catalyst is reduced, resulting in a slow progress of the reaction. Therefore, oxygen in the system must be excluded before the reaction, and nitrogen is continuously supplied to the system during the reaction.
The nitrogen is introduced for 30-60min reasonably, preferably 30-50 min, and more preferably 35-45 min.
In the present invention, the reaction internal temperature is set to 50 to 60 ℃ which is the optimum temperature for the reaction. If the heating reflux temperature is lower than 50-60 ℃, the reaction is relatively slow, and the progress of the reaction is influenced; if the heating reflux temperature is higher than 50-60 ℃, side reactions are increased, and excessive energy is consumed, so that the production cost is increased.
The lamp used in the invention is an LED energy-saving lamp. The commonly used incandescent lamp consumes 95% of the electric energy to heat, and only 5% of the electric energy is actually converted into the light energy needed by us. Meanwhile, the method has the advantages of quick thermal evaporation and short service life: (1000 hours), high infrared ray content, easy vibration, low color temperature, etc. The LED energy-saving lamp basically converts all electric energy into light energy required by people. Meanwhile, the color developing agent has the advantages of energy conservation, long service life (more than 50000 hours), no infrared radiation, impact resistance, small influence of vibration, good color developing performance and the like. The LED energy-saving lamp is a novel energy source and environment-friendly green light source product, and is a modern development trend.
The reaction is reasonable for 5 to 20 hours under the illumination condition in the invention, preferably 10 to 20 hours, and more preferably 15 to 18 hours.
(2) Catalyst recovery
Filtering the reaction liquid containing the isoeugenol obtained in the step (1), recovering the catalyst, washing the obtained filter cake with water according to the volume ratio of the filter cake to distilled water of 1: 1-2, washing for 1-5 times according to the same washing mode, and drying the washed filter cake for later use;
wherein the volume ratio of the filter cake to the water is reasonable from 1:1 to 1:2, preferably from 1:1 to 1:1.8, and more preferably from 1:1 to 1: 1.5.
The number of washing times is preferably 1 to 5, more preferably 2 to 4, and most preferably 2 to 3.
(3) Preparation of the final product
And (3) distilling the filtrate obtained in the step (2) to obtain the final product isoeugenol.
In the invention, the distillation is carried out under the conditions of pressure of 0.1-0.3 MPa and temperature of 20-140 ℃. Vacuum distillation is currently the most used, simplest, fastest purification method and is well known to those skilled in the art.
The invention also provides the final product of the isoeugenol prepared by the preparation method, wherein the content of the isoeugenol is 99.9 percent by weight, the content of the trans-isoeugenol is more than 90 percent by weight, and the yield is more than 95 percent.
The resulting isoeugenol product was analyzed by conventional HPLC under the following conditions:
using an instrument: hippocastane high performance liquid chromatograph Essentia LC-15C;
the determination method comprises the following steps: an area external standard method;
the measurement conditions were as follows: nucleosi17-C18 (phi 4.6X 250mm, 10 μm) was used as analytical column, and the mobile phase was methanol-water (5: 95); column temperature: 25 ℃; detection wavelength: 203 nm; flow rate: 1.0 ml/min.
The determination result shows that the content of the product isoeugenol prepared by the method is 99.9 percent.
The yield was calculated from the mass of eugenol and the mass of the product according to the following equation:
the yield is (A x D)/(C x B) 100%
A: quality of the product
B: molecular weight of the product
C: quality of eugenol
D: molecular weight of eugenol
The yield of the isoeugenol synthesized by the method is more than 95 percent.
Example 1: preparation of isoeugenol according to the invention
(1) Preparation of reaction solution
Eugenol, VK-TA18S and sodium sulfite are evenly mixed according to the weight ratio of 1:0.1:1.5 to obtain a mixture, nitrogen is introduced into a mixture reaction system, oxygen in the system is removed, after 30min of nitrogen introduction, heating and an LED lamp are started, the reaction internal temperature is controlled at 50 ℃, the reaction is carried out for 5h under the illumination condition, and the nitrogen is continuously introduced into the system in the reaction process. Then, the reaction solution was cooled to room temperature to obtain a reaction solution containing isoeugenol.
(2) Catalyst recovery
Filtering the reaction liquid containing the isoeugenol obtained in the step (1), recovering the catalyst, washing the obtained filter cake with water according to the volume ratio of the filter cake to the distilled water of 1:1, washing for 1 time according to the same washing mode, and drying the washed filter cake for later use;
(3) preparation of the final product
And (3) distilling the filtrate obtained in the step (2) under the pressure of 0.1MPa and at the temperature of 20-130 ℃ under reduced pressure to obtain a final product of isoeugenol, wherein the content of isoeugenol is 95% by weight, the content of trans-isoeugenol is 50% by weight, and the yield is 60%.
Example 2: preparation of isoeugenol according to the invention
(1) Preparation of reaction solution
The eugenol, the VK-TA18S and the sodium sulfite are uniformly mixed according to the weight ratio of 1:0.3:2 to obtain a mixture, nitrogen is introduced into a mixture reaction system, oxygen in the system is removed, after the nitrogen is introduced for 35min, a heating lamp and an LED lamp are started, the reaction internal temperature is controlled to be 52 ℃, the reaction is carried out for 10h under the illumination condition, and the nitrogen is continuously introduced into the system in the reaction process. Then, the reaction solution was cooled to room temperature to obtain a reaction solution containing isoeugenol.
(2) Catalyst recovery
Filtering the reaction liquid containing the isoeugenol obtained in the step (1), recovering the catalyst, washing the obtained filter cake with water according to the volume ratio of the filter cake to the distilled water of 1:1.1, washing for 2 times according to the same washing mode, and drying the washed filter cake for later use;
(3) preparation of the final product
And (3) distilling the filtrate obtained in the step (2) under the pressure of 0.2MPa and the temperature of 23-130 ℃ under reduced pressure to obtain a final product of isoeugenol, wherein the content of the isoeugenol is 90% by weight, the content of the trans-isoeugenol is 70% by weight, and the yield is 80%.
Example 3: preparation of isoeugenol according to the invention
(1) Preparation of reaction solution
The eugenol, the VK-TA18S and the sodium sulfite are uniformly mixed according to the weight ratio of 1:0.3:3 to obtain a mixture, nitrogen is introduced into a mixture reaction system, oxygen in the system is removed, after the nitrogen is introduced for 45min, a heating lamp and an LED lamp are started, the reaction internal temperature is controlled to be 55 ℃, the reaction is carried out for 16h under the illumination condition, and the nitrogen is continuously introduced into the system in the reaction process. Then, the reaction solution was cooled to room temperature to obtain a reaction solution containing isoeugenol.
(2) Catalyst recovery
Filtering the reaction liquid containing the isoeugenol obtained in the step (1), recovering the catalyst, washing the obtained filter cake with water according to the volume ratio of the filter cake to the distilled water of 1:1.5, washing for 3 times according to the same washing mode, and drying the washed filter cake for later use;
(3) preparation of the final product
And (3) distilling the filtrate obtained in the step (2) under the pressure of 0.2MPa and at the temperature of 25-135 ℃ under reduced pressure to obtain a final product of isoeugenol, wherein the content of isoeugenol is 99.9 percent by weight, the content of trans-isoeugenol is 93 percent by weight, and the yield is 97 percent.
Example 4: preparation of isoeugenol according to the invention
(1) Preparation of reaction solution
Eugenol, VK-TA18S and sodium sulfite are evenly mixed according to the weight ratio of 1:0.6:4 to obtain a mixture, nitrogen is introduced into a mixture reaction system, oxygen in the system is removed, after 50min of nitrogen introduction, heating and an LED lamp are started, the reaction internal temperature is controlled at 56 ℃, the reaction is carried out for 18h under the illumination condition, and the nitrogen is continuously introduced into the system in the reaction process. Then, the reaction solution was cooled to room temperature to obtain a reaction solution containing isoeugenol.
(2) Catalyst recovery
Filtering the reaction liquid containing the isoeugenol obtained in the step (1), recovering the catalyst, washing the obtained filter cake with water according to the volume ratio of the filter cake to distilled water of 1:1.6, washing for 3 times according to the same washing mode, and drying the washed filter cake for later use;
(3) preparation of the final product
And (3) distilling the filtrate obtained in the step (2) under the pressure of 0.3MPa and at the temperature of 20-140 ℃ under reduced pressure to obtain a final product of isoeugenol, wherein the content of isoeugenol is 99.9 percent by weight, the content of trans-isoeugenol is 92 percent by weight, and the yield is 95 percent.
Example 5: preparation of isoeugenol according to the invention
(1) Preparation of reaction solution
Eugenol, VK-TA18S and sodium sulfite are evenly mixed according to the weight ratio of 1:0.8:4.5 to obtain a mixture, nitrogen is introduced into a mixture reaction system, oxygen in the system is removed, after the nitrogen is introduced for 55min, a heating lamp and an LED lamp are started, the reaction internal temperature is controlled at 58 ℃, the reaction is carried out for 19h under the illumination condition, and the nitrogen is continuously introduced into the system in the reaction process. Then, the reaction solution was cooled to room temperature to obtain a reaction solution containing isoeugenol.
(2) Catalyst recovery
Filtering the reaction liquid containing the isoeugenol obtained in the step (1), recovering the catalyst, washing the obtained filter cake with water according to the volume ratio of the filter cake to distilled water of 1:1.8, washing for 4 times according to the same washing mode, and drying the washed filter cake for later use;
(3) preparation of the final product
And (3) distilling the filtrate obtained in the step (2) under the pressure of 0.2MPa and the temperature of 40-138 ℃ under reduced pressure to obtain a final product of isoeugenol, wherein the content of isoeugenol is 99.5 percent by weight, the content of trans-isoeugenol is 92 percent by weight, and the yield is 93 percent.
Example 6: preparation of isoeugenol according to the invention
(1) Preparation of reaction solution
The eugenol, the VK-TA18S and the sodium sulfite are uniformly mixed according to the weight ratio of 1:1:5 to obtain a mixture, nitrogen is introduced into a mixture reaction system, oxygen in the system is removed, after the nitrogen is introduced for 60min, a heating and LED lamp is started, the reaction temperature is controlled at 60 ℃ in the reaction system, the reaction is carried out for 20h under the illumination condition, and the nitrogen is continuously introduced into the system in the reaction process. Then, the reaction solution was cooled to room temperature to obtain a reaction solution containing isoeugenol.
(2) Catalyst recovery
Filtering the reaction liquid containing the isoeugenol obtained in the step (1), recovering the catalyst, washing the obtained filter cake with water according to the volume ratio of the filter cake to distilled water of 1:2, washing for 5 times according to the same washing mode, and drying the washed filter cake for later use;
(3) preparation of the final product
And (3) distilling the filtrate obtained in the step (2) under the pressure of 0.1MPa and the temperature of 30-128 ℃ under reduced pressure to obtain a final product of isoeugenol, wherein the content of isoeugenol is 99.0 percent by weight, the content of trans-isoeugenol is 90 percent by weight, and the yield is 90 percent.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.
Claims (10)
1. The preparation method of isoeugenol is characterized by comprising the following steps:
(1) preparation of reaction solution
Mixing eugenol, a catalyst and sodium sulfite to obtain a mixture, introducing nitrogen into a mixture reaction system, after introducing the nitrogen for 30-60min, starting a heating lamp, controlling the temperature in the reaction, reacting for a certain time under the illumination condition, keeping the system to be continuously introduced with the nitrogen in the reaction process, and then cooling to room temperature to obtain a reaction liquid containing isoeugenol;
(2) catalyst recovery
Filtering the reaction liquid containing the isoeugenol obtained in the step (1), recovering the catalyst, washing the obtained filter cake with water according to the volume ratio of the filter cake to distilled water of 1: 1-1: 2, and drying the washed filter cake for later use;
(3) preparation of the final product
And (3) distilling the filtrate obtained in the step (2) to obtain the final product isoeugenol.
2. The process for the preparation of isoeugenol as claimed in claim 1, wherein in step (1) the catalyst used is a photooxidation catalyst of type VK-TA 18S.
3. The method for preparing isoeugenol as claimed in claim 1, wherein in the step (1), eugenol, the catalyst and sodium sulfite are uniformly mixed in a weight ratio of 1 (0-1) to (1-5).
4. The method for producing isoeugenol as claimed in claim 1, wherein in the step (1), nitrogen gas is introduced into the system for the purpose of removing oxygen from the system.
5. The method for producing isoeugenol according to claim 1, wherein in the step (1), the obtained mixture is heated and reacted at a temperature of 50 to 60 ℃.
6. The method for producing isoeugenol as claimed in claim 1, wherein in step (1), the lamp used is an LED lamp.
7. The method for producing isoeugenol according to claim 1, wherein in step (1), the obtained mixture is reacted under light for 5 to 20 hours.
8. The method for producing isoeugenol according to claim 1, wherein in the step (2), the obtained filter cake is washed 2 to 3 times in the same washing manner.
9. The method for producing isoeugenol according to claim 1, wherein in the step (3), the distillation is conducted under reduced pressure at a pressure of 0.1 to 0.3MPa and a temperature of 20 to 140 ℃.
10. The final product isoeugenol obtained by the method according to any one of claims 1 to 9, wherein the isoeugenol is 99.9% by weight and the yield is more than 95%.
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|---|---|---|---|---|
| CN103012080A (en) * | 2011-09-28 | 2013-04-03 | 章婉盈 | Process for synthesizing semi-synthetic spice |
| CN103626643A (en) * | 2013-12-03 | 2014-03-12 | 南昌航空大学 | Preparation method for synthesizing vanillin by using natural eugenol as raw material |
| CN103848728A (en) * | 2014-03-19 | 2014-06-11 | 淄博职业学院 | Synthesis method of isoeugenol |
| CN109232200A (en) * | 2018-09-13 | 2019-01-18 | 重庆欣欣向荣精细化工有限公司 | A kind of preparation method of isoeugenol |
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- 2020-02-25 CN CN202010115356.5A patent/CN111170834B/en active Active
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| CN103012080A (en) * | 2011-09-28 | 2013-04-03 | 章婉盈 | Process for synthesizing semi-synthetic spice |
| CN103626643A (en) * | 2013-12-03 | 2014-03-12 | 南昌航空大学 | Preparation method for synthesizing vanillin by using natural eugenol as raw material |
| CN103848728A (en) * | 2014-03-19 | 2014-06-11 | 淄博职业学院 | Synthesis method of isoeugenol |
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