Green synthesis method of borneol
By using the method of synthetic camphor, organic solvent and dual metal doped carbon/carbon carbon catalysts, the problem of long response time in the existing borneol preparation method, catalyst preparation, and low income are achieved. Green and energy -saving preparation, product revenue is as high as 98%.
Patent Information
- Application Number
- CN202411413901.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-11
- Publication Date
- 2025-01-24
AI Technical Summary
The existing methods of ice ice preparation have problems such as long reaction time, complicated catalyst preparation and low yield, and lack of green, energy-saving and efficient preparation methods.
Synthetic camphor is used as raw material, organic solvent and bimetal-doped palladium carbon/ruthenium carbon catalyst are added, the reaction conditions are adjusted to carry out the reaction, and finally the catalyst is removed and concentrated to obtain the product.
The efficient preparation of borneol is achieved, and the product yield reaches 98%. The process is simple, green and efficient, and reduces production costs and waste generation.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of chemical synthesis, and in particular to a green synthesis method of borneol. Background Art
[0002] Synthetic borneol, also known as synthetic borneol, is a white flaky crystalline substance with a cool and fragrant smell. It has antibacterial, anti-inflammatory, analgesic, and antipyretic effects, and is widely used in the fields of medicine, food, cosmetics, etc.
[0003] In the pharmaceutical field, synthetic borneol has a wide range of uses. First, it can be used as an antibacterial agent with a strong antibacterial effect. It has a strong inhibitory effect on common pathogens such as Staphylococcus aureus, Escherichia coli, Shigella dysenteriae, and can be used to treat various infectious diseases. Secondly, synthetic borneol also has an anti-inflammatory effect and can be used to treat various inflammatory diseases, such as otitis media, rhinitis, pneumonia, etc. In addition, synthetic borneol can also be used as an analgesic and antipyretic, and has a significant alleviating effect on various pain and fever symptoms. In the food field, synthetic borneol also has a wide range of applications. Due to its cool taste and fragrance, synthetic borneol can be added as a food additive to various foods, such as chewing gum, candy, beverages, etc. It can improve the taste and fragrance of food, and can also inhibit the growth of bacteria and maintain the hygiene and safety of food. In the cosmetics field, synthetic borneol also has a wide range of uses. Due to its antibacterial and anti-inflammatory effects, synthetic borneol can be used to make various antibacterial and anti-inflammatory cosmetics, such as creams, lotions, facial masks, etc. At the same time, due to its fragrant taste and cool feeling, synthetic borneol can also be added to cosmetics as a fragrance and cooling agent, bringing a comfortable use experience to users.
[0004] With the continuous progress of science and technology and the continuous expansion of application fields, the use of synthetic borneol will become more and more extensive. However, the current borneol is generally prepared by esterification of a-pinene and oxalic acid in the presence of a catalyst, and then washed, distilled light oil, saponified distilled brain, coarse crystallization, refined crystallization and drying. The current catalyst is boric acid, metatitanic acid, titanium dioxide, aluminum sulfate and zirconium sulfate, which often require programmed temperature rise. The borneol preparation method generally has the problems of long reaction time, cumbersome catalyst preparation and low yield. How to find a green, energy-saving, simple process and high-yield borneol preparation method has always been a hot topic studied by industry insiders. The inventor has proposed a green, energy-saving and efficient preparation method. Summary of the invention
[0005] In view of the shortcomings of the prior art, the object of the present invention is to provide a green synthesis method of borneol.
[0006] The above-mentioned object of the present invention is achieved through the following technical solutions: A green synthesis method of borneol comprises the following steps: S1, using synthetic camphor as raw material; S2, adding organic solvent and catalyst; S3, after adjusting the reaction conditions, carry out the reaction; S4, after removing the catalyst, concentrate to obtain the product.
[0007] The applicant pioneered the use of synthetic camphor as a raw material to prepare borneol, then added an organic solvent and a catalyst, adjusted the reaction conditions, and then reacted. After removing the catalyst, the product was concentrated. This reaction is green and energy-saving, has a simple process and a high yield. The reaction is as follows: .
[0008] The organic solvent includes ethyl acetate and / or petroleum ether, the mass ratio of ethyl acetate to synthetic camphor is (5-8):1, the mass ratio of petroleum ether to synthetic camphor is (5-7):3, and the organic solvent also includes toluene, tertiary methyl ether, and n-heptane.
[0009] The catalyst is a bimetallic doped palladium carbon catalyst or a bimetallic doped ruthenium carbon catalyst, and the mass ratio of the catalyst to synthetic camphor is (0.03-0.07):1.
[0010] It is important to point out that the selection of the mass ratio between ethyl acetate, bimetallic doped palladium carbon / ruthenium carbon catalyst and synthetic camphor achieved unexpected results, with the product yield reaching 98%. This process has effectively improved the product yield and is simple in process.
[0011] The preparation method of the bimetallic doped palladium carbon / ruthenium carbon catalyst comprises the following steps: Step 1, preparing a palladium carbon / ruthenium carbon carrier: weighing activated carbon and adding it into deionized water, slowly dropping the prepared palladium chloride / ruthenium chloride precursor salt solution into the activated carbon carrier, and using sodium carbonate solution to maintain the pH value of the mixture at 9.3-9.7, filtering and washing after standing to obtain a palladium carbon carrier; Step 2, prepare catalyst AL-Zn-Pd / C or Cu-Zn-Ru / C: weigh aluminum triacetylacetonate / copper glycinate and zinc glucose, add them into deionized water to prepare a solution doped with metallic aluminum and zinc, add it dropwise to the above-mentioned carrier palladium carbon / ruthenium carbon, adjust the pH value to 9.3-9.7 with sodium carbonate solution, stir, let stand, filter, wash to obtain a solid sample, dry and grind into powder, reduce in hydrogen for 3 hours to obtain catalyst Al-Zn-Pd / C or Al-Zn-Ru / C, and then use it for hydrogenation.
[0012] The concentration of the palladium chloride / ruthenium chloride precursor salt solution in step 1 is 0.2-0.3 mol / L.
[0013] The mass ratio of aluminum to zinc in the doped metal aluminum and zinc solution in the catalyst AL-Zn-Pd / C prepared in step 2 is (1.5-2.5):1; the mass ratio of copper to zinc in the doped metal copper and zinc solution in the catalyst Cu-Zn-Ru / C prepared in step 2 is (1.5-2.5):3.
[0014] In the step 2, after the solid sample is ground into powder, it is reduced in hydrogen at a temperature of 400-600° C. for 3 hours.
[0015] The specific preparation method of the catalyst is disclosed above. The catalyst is specially designed by the applicant for synthesizing borneol. When used in synthesizing borneol, it plays a good catalytic role and accelerates the rate of the specific chemical reaction of converting camphor into borneol and isoborneol. The use of the catalyst can also reduce the amount of required reactants, save energy and raw materials, and thus reduce production costs; the catalyst can be recovered and reused after the reaction is completed, which helps to reduce costs and waste.
[0016] In the step S3, when adjusting the reaction conditions, the nitrogen gas was replaced 3 times and the hydrogen gas was replaced 3 times.
[0017] In step S3, during the reaction, the temperature is 95-105° C., the hydrogen pressure is 2.5-3.5 MPa, and the reaction takes 9-11 hours.
[0018] In step S4, before removing the catalyst, sampling is performed for central control, and after the sampling is qualified, the catalyst is removed.
[0019] The reaction conditions and steps are disclosed above. The reaction conditions are also specially designed for this process. Combined with the raw materials and proportions, catalysts and reaction adjustments of this process, the entire scheme can not only achieve a yield of 98%, but also has a simple process, green and efficient.
[0020] In summary, the present invention includes at least one of the following beneficial technical effects: 1. The applicant pioneered the use of synthetic camphor as a raw material to prepare borneol, then added an organic solvent and a catalyst, adjusted the reaction conditions, and then reacted. After removing the catalyst, the product was concentrated. This reaction is green and energy-saving, has a simple process and a high yield; 2. The specific preparation method of the catalyst is disclosed. The catalyst is specially designed by the applicant for the synthesis of borneol. When used in the synthesis of borneol, it plays a good catalytic role and accelerates the rate of the specific chemical reaction of converting camphor into borneol and isoborneol. The use of the catalyst can also reduce the amount of required reactants, save energy and raw materials, and thus reduce production costs; the catalyst can be recovered and reused after the reaction is completed, which helps to reduce costs and waste; 3. The reaction conditions and steps are disclosed. The reaction conditions are also specially designed for this process. Combined with the raw materials and proportions, catalysts and reaction adjustments of this process, the entire scheme can not only achieve a yield of 98%, but also the process is simple, green and efficient. DETAILED DESCRIPTION
[0021] The present invention is described in further detail below. Preparation Example 1 of Bimetallic Palladium Carbon Catalyst
[0022] Step 1, prepare carrier palladium carbon: first weigh 10 grams of pretreated activated carbon, add 150 grams of deionized water and stir to disperse evenly, according to the required metal loading, slowly add 100 ml of the prepared 0.25 mol / L palladium chloride precursor salt solution to the pretreated activated carbon carrier under magnetic stirring, while adding sodium carbonate solution to ensure that the pH of the mixture is stable at 9.5, let stand at 40°C for 8 hours, then filter, and wash thoroughly with deionized water to obtain the carrier palladium carbon.
[0023] Step 2, prepare the catalyst AL-Zn-Pd / C: weigh 2.5 grams of aluminum triacetylacetonate and 3 grams of zinc glucose in a beaker, add 300 grams of deionized water, stir with ionization to fully disperse and mix, and prepare a solution with a mass ratio of 2:1 doped with metal aluminum and zinc. Add it dropwise to the above palladium carbon, and then adjust the pH value to 9.5 with 0.1 mol / L sodium carbonate aqueous solution, measure it in real time with a pH meter, stir at 1000 rpm for 3 hours after the dripping, then let it stand for 5 hours, filter, and wash it with deionized water to obtain a solid sample, which is placed at 90°C for 5 hours in vacuum drying and ground into powder. Take the above sample and place it in a U-shaped reactor, reduce it in hydrogen at 500°C for 3 hours to obtain the catalyst Al-Zn-Pd / C, and take it out for hydrogenation. Preparation Example 2-3
[0024] The difference between Preparation Example 2-3 and Preparation Example 1 is that the concentration of the palladium chloride precursor salt solution in step 1 is different, the concentration of Preparation Example 2 is 0.2 mol / L, and the concentration of Preparation Example 3 is 0.3 mol / L. Preparation Example 4-5
[0025] The difference between Preparation Example 4-5 and Preparation Example 1 is that the mass ratio of aluminum to zinc in the prepared metal aluminum and zinc doped solution in step 2 is different, that is, 1.5:1 in Preparation Example 4 and 2.5:1 in Preparation Example 5. Preparation Example 6-7
[0026] The difference between Preparation Example 6-7 and Preparation Example 1 is that the temperature conditions after the solid sample is ground into powder in step 2 are different. Preparation Example 6 is at a temperature of 400°C, and Preparation Example 7 is at a temperature of 600°C. Preparation Example 8 of Bimetallic Ruthenium-Carbon Catalyst
[0027] Step 1, prepare carrier ruthenium carbon: first weigh 10 grams of pretreated activated carbon, add 250 grams of deionized water and stir to disperse evenly, slowly add 100 ml of the prepared 0.2 mol / L ruthenium trichloride precursor salt solution to the pretreated activated carbon carrier under magnetic stirring, and add sodium carbonate solution to ensure that the pH of the mixture is stable at 9.5, let it stand at 40°C for 8 hours, then filter and wash thoroughly with deionized water to obtain the carrier ruthenium carbon.
[0028] Step 2, prepare the catalyst Cu-Zn-Ru / C: weigh 2 grams of copper glycinate and 3 grams of zinc glucose in a beaker, add 300 grams of deionized water, stir and disperse thoroughly with ionization, and prepare a solution with a mass ratio of 1:1 doped with metallic copper and zinc. Add it dropwise to the above ruthenium carbon, and then adjust the pH value to 9.5 with 0.1 mol / L sodium carbonate aqueous solution, measure it in real time with a pH meter, stir at 800 rpm for 3 hours after the dripping, then let it stand for 5 hours, filter, and wash it with deionized water to obtain a solid sample, which is placed at 90°C for 5 hours in vacuum drying and ground into powder. Take the above sample and place it in a U-shaped reactor, reduce it in hydrogen at 500°C for 3 hours to obtain the catalyst Cu-Zn-Ru / C, and take it out for hydrogenation.
[0029] Catalyst testing: The prepared catalysts were characterized and analyzed by X-ray diffraction (XDR), scanning electron microscopy (SEM) and inductively coupled plasma spectroscopy (ICP-AES). Preparation Examples 9-10
[0030] The difference between Preparation Examples 9-10 and Preparation Example 1 is that the concentrations of the ruthenium trichloride precursor salt solution in step 1 are different, the concentration in Preparation Example 2 is 0.2 mol / L, and the concentration in Preparation Example 3 is 0.3 mol / L. Preparation Example 11-12
[0031] The difference between Preparation Examples 11-12 and Preparation Example 1 is that the mass ratio of aluminum to zinc in the prepared doped metal aluminum and zinc solution in step 2 is different, that is, 1.5:1 in Preparation Example 4 and 2.5:1 in Preparation Example 5. Preparation Examples 13-14
[0032] The difference between Preparation Examples 13-14 and Preparation Example 1 is that the temperature conditions after the solid sample is ground into powder in step 2 are different, Preparation Example 6 is at a temperature of 400°C, and Preparation Example 7 is at a temperature of 600°C. Example 1 of preparing borneol
[0033] In an autoclave, 100 g of synthetic camphor, 700 g of ethyl acetate, and other organic solvents: toluene, tertiary methyl ether, petroleum ether, and n-heptane were added. The weight ratio of each of the added weight of toluene, tertiary methyl ether, petroleum ether, and n-heptane to the synthetic camphor was 5:1. 5 g of the catalyst obtained in Preparation Example 1 was replaced with nitrogen 3 times and hydrogen 3 times. The reaction was carried out at a temperature of 100°C and a hydrogen pressure of 3 MPa for 10 hours. After the sampling control was qualified, the catalyst was filtered out and concentrated to obtain the product with a borneol content of 62%, an isoborneol content of 35%, and a yield of 98%. Example 2-3
[0034] The difference between Example 2-3 and Example 1 is that the mass ratio of ethyl acetate to synthetic camphor is different. The mass of ethyl acetate added in Example 2 is 500 g, and the mass added in Example 3 is 700 g. Embodiment 4-5
[0035] The difference between Example 4-5 and Example 1 is that the mass ratio of the catalyst to the synthetic camphor is different. The mass of the catalyst added in Example 4 is 3 g, and the mass added in Example 5 is 7 g. Embodiment 6-7
[0036] The difference between Example 6-7 and Example 1 is that the reaction conditions are different. The reaction conditions in Example 6 are: temperature 95°C, hydrogen pressure 2.5Mpa, and reaction time 9h; the reaction conditions in Example 7 are: temperature 105°C, hydrogen pressure 3.5Mpa, and reaction time 11h. Embodiment 8-20
[0037] The difference between Examples 8-20 and Example 1 is that different catalysts are used, as shown in the following table.
[0038]
[0039] The yields obtained in Examples 2-20 were all greater than 94%, but the yield of Example 1 exceeded expectations by reaching 98%, and the product obtained in Example 1 had a borneol content of 62% and an isoborneol content of 35%. Embodiment 21
[0040] Example 21: In an autoclave, 150 g of synthetic camphor, 300 g of petroleum ether, and other organic solvents: toluene, tert-methyl ether, and n-heptane were added. The weight ratio of each of the added weight of toluene, tert-methyl ether, and n-heptane to the synthetic camphor was 5:1. 5 g of the catalyst obtained in Preparation Example 2 was added, and the mixture was replaced with nitrogen 3 times and hydrogen 3 times. The mixture was reacted at a temperature of 180°C and a hydrogen pressure of 2 MPa for 10 hours. After the sampling was qualified, the catalyst was filtered out and concentrated to obtain the product with a borneol content of 66.1%, an isoborneol content of 30.3%, and a yield of 98%. Example 22-
[0041] Example 22-The difference from Example 21 is that a different catalyst is used, see the table below.
[0042] Examples 35-36
[0043] The difference between Examples 35-36 and Example 1 is that the mass ratio of petroleum ether to synthetic camphor is different. The mass of petroleum ether added in Example 35 is 250 g, and the mass added in Example 36 is 350 g. Examples 37-38
[0044] The difference between Examples 37-38 and Example 1 is that the mass ratio of the catalyst to the synthetic camphor is different. The mass of the catalyst added in Example 37 is 3 g, and the mass added in Example 38 is 7 g. Examples 39-40
[0045] The difference between Examples 39-40 and Example 1 is that the reaction conditions are different. The reaction conditions in Example 39 are: temperature 95°C, hydrogen pressure 2.5Mpa, and reaction time 9h; the reaction conditions in Example 40 are: temperature 105°C, hydrogen pressure 3.5Mpa, and reaction time 11h.
[0046] The yields obtained in Examples 41-42 are all good, especially in Example 21, the borneol content is 66.1%, the isoborneol content is 30.3%, and the yield reaches 98%. The applicant will continue to make innovative breakthroughs in the field of chemical synthesis, and hopes to develop other greener and more efficient methods in the future to make more contributions to society.
[0047] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, a person skilled in the art may make non-creative modifications to the present embodiment as needed, but such modifications are protected by the Patent Law as long as they are within the scope of the present application.
Claims
1. A green synthesis method of borneol, characterized in that: The following steps are involved: S1, using synthetic camphor as raw material; S2, adding organic solvent and catalyst; S3, after adjusting the reaction conditions, carry out the reaction; S4, after removing the catalyst, concentrate to obtain the product.
2. The green synthesis method of borneol according to claim 1, characterized in that: The organic solvent includes ethyl acetate and / or petroleum ether, the mass ratio of ethyl acetate to synthetic camphor is (5-8):1, the mass ratio of petroleum ether to synthetic camphor is (5-7):3, and the organic solvent also includes toluene, tertiary methyl ether, and n-heptane.
3. The green synthesis method of borneol according to claim 1, characterized in that: The catalyst is a bimetallic doped palladium carbon catalyst or a bimetallic doped ruthenium carbon catalyst, and the mass ratio of the catalyst to synthetic camphor is (0.03-0.07):
1.
4. The green synthesis method of borneol according to claim 3, characterized in that: The preparation method of the bimetallic doped palladium carbon / ruthenium carbon catalyst comprises the following steps: Step 1, preparing a palladium carbon / ruthenium carbon carrier: weighing activated carbon and adding it into deionized water, slowly dropping the prepared palladium chloride / ruthenium chloride precursor salt solution into the activated carbon carrier, and using sodium carbonate solution to maintain the pH value of the mixture at 9.3-9.7, filtering and washing after standing to obtain a palladium carbon carrier; Step 2, prepare catalyst AL-Zn-Pd / C or Cu-Zn-Ru / C: weigh aluminum triacetylacetonate / copper glycinate and zinc glucose, add them into deionized water to prepare a solution doped with metallic aluminum and zinc, add it dropwise to the above-mentioned carrier palladium carbon / carrier ruthenium carbon, adjust the pH value to 9.3-9.7 with sodium carbonate solution, stir, let stand, filter, wash to obtain a solid sample, dry and grind into powder, reduce in hydrogen for 3 hours to obtain catalyst Al-Zn-Pd / C or Cu-Zn-Ru / C, and then use it for hydrogenation.
5. The green synthesis method of borneol according to claim 4, characterized in that: The concentration of the palladium chloride or ruthenium chloride precursor salt solution in step 1 is 0.2-0.3 mol / L.
6. The green synthesis method of borneol according to claim 4, characterized in that: The mass ratio of aluminum to zinc in the doped metal aluminum and zinc solution in the catalyst AL-Zn-Pd / C prepared in step 2 is (1.5-2.5):1; the mass ratio of copper to zinc in the doped metal copper and zinc solution in the catalyst Cu-Zn-Ru / C prepared in step 2 is (1.5-2.5):
3.
7. The green synthesis method of borneol according to claim 4, characterized in that: In the step 2, after the solid sample is ground into powder, it is reduced in hydrogen at a temperature of 400-600° C. for 3 hours.
8. The green synthesis method of borneol according to claim 1, characterized in that: In the step S3, when adjusting the reaction conditions, the nitrogen gas was replaced 3 times and the hydrogen gas was replaced 3 times.
9. The green synthesis method of borneol according to claim 1, characterized in that: In step S3, during the reaction, the temperature is 95-105° C., the hydrogen pressure is 2.5-3.5 MPa, and the reaction takes 9-11 hours.
10. The green synthesis method of borneol according to claim 1, characterized in that: In step S4, before removing the catalyst, sampling is performed for central control, and after the sampling is qualified, the catalyst is removed.