CN111302911A - Preparation method of m-hydroxybenzaldehyde - Google Patents
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Abstract
The invention relates to a preparation method of m-hydroxybenzaldehyde, which comprises the following steps: (1) adding m-cresol and acetic anhydride into a stainless steel reaction kettle, and reacting to obtain m-acetoxytoluene; (2) adding an organic solvent, a free radical initiator and a brominating agent into a product obtained by the reaction in the step (1) for reaction, and obtaining m-acetoxyl dibromotoluene through reduction, washing and desolventizing after the reaction; (3) and (3) adding water and carbonate into the product obtained by the reaction in the step (2), and hydrolyzing, filtering, decoloring, recrystallizing and drying to obtain the m-hydroxybenzaldehyde. The invention solves the technical problems of more impurities, complicated steps, low yield, complex product post-treatment method, serious pollution and the like in the synthesis of m-hydroxybenzaldehyde in the prior art, and can be widely applied to the technical field of organic synthesis.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of m-hydroxybenzaldehyde.
Background
The m-hydroxy benzaldehyde is an important fine chemical raw material and is mainly used in the fields of medicine synthesis, spice production and electroplating industry. At present, two methods of nitration reaction, reduction reaction, diazotization hydrolysis, acetylation reaction of m-cresol, chlorination reaction and hydrolysis reaction of benzaldehyde are mostly adopted in the industrial production of m-hydroxybenzaldehyde. Because the two methods have more reaction steps and more associated byproducts, especially m-cresol acetylation and chlorination processes, polychlorinated products are generated due to stronger chlorine activity, so that m-hydroxybenzaldehyde has small yield, low purity and high cost, the market demand can not be met far away, and the chlorine belongs to high-volatility and high-toxicity gas and is extremely harmful to the bodies of workers once leaked; and the discharge amount of three wastes in the synthesis method is quite serious, and the environment is seriously polluted.
Disclosure of Invention
The invention aims to solve the defects of the technology and provide a method for preparing m-hydroxybenzaldehyde, which has the advantages of simple reaction path, higher yield, less impurity content and simple and easy product post-treatment method.
Therefore, the invention provides a preparation method of m-hydroxybenzaldehyde, which is characterized by comprising the following steps:
(1) preparation of m-acetoxytoluene: adding a certain amount of m-cresol into a stainless steel reaction kettle, adding a certain amount of acetic anhydride, heating to 130-135 ℃, carrying out heat preservation reaction for 5 hours, then carrying out reduced pressure distillation to 120 ℃ to recover a byproduct acetic acid, and obtaining an intermediate product, namely m-acetoxytoluene;
(2) preparation of m-acetoxydibromotoluene: sequentially adding a certain amount of organic solvent, a free radical initiator and a brominating agent into a product obtained by the reaction in the step (1), heating to 65-90 ℃, and carrying out heat preservation reaction for 10-15 hours; after the reaction is finished, adding water for washing, simultaneously adding a reducing agent to remove residual brominating agent, recovering a water layer after the washing is finished, and decompressing and recovering an organic solvent from an organic layer after the washing is finished to obtain an orange-colored sticky substance, namely m-acetoxyl dibromotoluene;
(3) preparation of m-hydroxybenzaldehyde: adding a certain amount of water and carbonate into the product obtained by the reaction in the step (2), heating to reflux, carrying out heat preservation reaction for 10-15 hours, filtering out solid residues while the solution is hot, cooling to below 10 ℃ to precipitate a solid, and then filtering; and putting the solid obtained by filtering into a decoloring kettle, adding water and activated carbon, heating, refluxing and decoloring for 1 hour, keeping the refluxing and decoloring temperature at 70-80 ℃, filtering to remove the activated carbon while the solid is hot after decoloring is finished, cooling to 10 ℃, performing suction filtration, recycling the water layer, and drying the obtained solid at 75 ℃ to obtain the final product, namely the m-hydroxybenzaldehyde.
Preferably, in the step (1), the molar ratio of the m-cresol to the acetic anhydride is 1: 1-1.3.
Preferably, in the step (2), the mass ratio of the organic solvent, the free radical initiator and the m-acetoxy toluene is 1-4:0.03-0.1: 1; the molar ratio of bromine atoms in the brominating agent to m-acetoxy toluene is 2-3: 1.
Preferably, the brominating agent in the step (2) is one or more of NBS and dibromohydantoin.
Preferably, in the step (2), the organic solvent is halogenated alkane or halogenated aromatic hydrocarbon, specifically one or more of dichloroethane, carbon tetrachloride, tetrachloroethane, and chlorobenzene.
Preferably, in the step (2), the radical initiator is a mixture of an organic peroxide and an azo initiator, and the mass ratio of the organic peroxide to the azo initiator is 1: 1-3.
Preferably, the organic peroxide is one or more of cyclohexanone peroxide, dibenzoyl peroxide and tert-butyl hydroperoxide, and the azo initiator is one or more of azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the reducing agent in the step (2) is one or more of sodium sulfite, sodium bisulfite and sodium thiosulfate, and the added reducing agent is an aqueous solution, wherein the mass percentage concentration of the aqueous solution of the reducing agent is 20%.
Preferably, in the step (3), the molar ratio of the carbonate to the m-acetoxydibromotoluene is 1-1.1: 1.
Preferably, in the step (3), the carbonate is one or more of sodium carbonate, potassium carbonate, calcium carbonate and barium carbonate.
Preferably, in the step (3), the adding amount of the activated carbon is 1-5% of the total mass of the decoloring system.
The invention provides a preparation method of m-hydroxybenzaldehyde, which has the following beneficial effects:
the preparation method of m-hydroxybenzaldehyde provided by the invention comprises the steps of firstly adding m-cresol and acetic anhydride into a stainless steel reaction kettle, and reacting to obtain m-acetoxy toluene; adding an organic solvent, a free radical initiator and a brominating agent into the product obtained by the reaction in the step (1) for reaction, and reducing, washing and desolventizing the product after the reaction to obtain m-acetoxyl dibromotoluene; and (3) finally, adding water and carbonate into the product obtained by the reaction in the step (2), and hydrolyzing, filtering, decoloring, recrystallizing and drying to obtain the m-hydroxybenzaldehyde.
In the step (2), a bromination process is used for replacing a chlorination process, and a brominating agent reacts with m-acetoxy toluene to obtain m-acetoxy dibromotoluene. The reaction is carried out in an organic solvent, the organic solvent dissolves and disperses a brominating agent, and hydrogen atoms on methyl groups in m-acetoxy toluene are replaced by bromine atoms on the brominating agent under the catalysis of a free radical initiator to obtain the m-acetoxy dibromotoluene. The free radical initiator used in the reaction is a mixture of organic peroxide and azo initiator, the brominating agent belongs to weak halogenating reagent, only a single free radical initiator is used, other polyhalogenation reaction is easy to occur, generated monobromide is more, reaction by-products are more, the yield of acetoxy dibromotoluene is low, the synergistic effect of the diradical initiator can promote the generation of dibromide, generated impurities are few, the yield of acetoxy dibromotoluene is high, and the yield of m-hydroxybenzaldehyde obtained by subsequent hydrolysis is high.
Reducing the remaining brominating agent in the step (2) into a water phase by using a reducing agent, carrying out bromination reaction together with the byproduct obtained in the step (2) to obtain the brominating agent again, and recycling the brominating agent; the organic solvent can be recycled by simple distillation. In addition, in the whole reaction process, little wastewater is discharged in the three steps, energy conservation and emission reduction are realized, the environment is protected, the final product yield can reach more than 87%, and the product purity can reach more than 99%.
Detailed Description
The present invention will be further described with reference to specific examples to assist understanding of the invention. The method used in the invention is a conventional method if no special provisions are made; the raw materials and the apparatus used are, unless otherwise specified, conventional commercially available products.
Example 1
A preparation method of m-hydroxybenzaldehyde comprises the following steps:
preparation of m-acetoxytoluene: 216kg of m-cresol is taken and added into a stainless steel reaction kettle, 220kg of acetic anhydride is added, the liquid is colorless and transparent, the temperature is raised to 130-135 ℃, after 5 hours of heat preservation reaction (GC controlled detection for m-cresol residue is less than 0.5 percent), the reduced pressure distillation is carried out until 120 ℃ to recover the acetic acid as a byproduct, the remainder is an intermediate product of m-acetoxy toluene, about 294kg, and the yield is 98 percent.
Preparation of m-acetoxydibromotoluene: adding 37.5kg of the intermediate product obtained in the step (1) into a stainless steel reaction kettle, adding 150kg of dichloroethane, 1kg of dibenzoyl peroxide, 3.75kg of azobisisobutyronitrile and 110kg of dibromohydantoin, heating to 65 ℃, and carrying out heat preservation reaction for 10 hours, wherein the system is changed into orange turbid shape from yellow turbid shape, then into orange semi turbid shape, then into bromine red transparent shape, and then into bromine red turbid shape. And after the reaction is completed, adding 200kg of water for washing, simultaneously adding a sodium sulfite aqueous solution to remove the residual brominating agent, recovering a water layer after the washing is completed, washing an obtained organic layer, and recovering the organic solvent under reduced pressure to obtain an orange-colored sticky substance, namely the m-acetoxyl dibromotoluene.
Preparation of m-hydroxybenzaldehyde: adding 200kg of water and 15kg of calcium carbonate into the material obtained in the step (2), heating to reflux, keeping the temperature for reaction for 12 hours, wherein the initial color of the reaction is orange turbid, the color gradually deepens along with the prolonging of the reaction time, the color finally becomes bromine red with the separation of black solid residues, filtering the solid residues while the reaction is hot, cooling to below 10 ℃, separating out a solid product, filtering to obtain a filter cake, and obtaining a filtrate in wine red. And (3) putting the filter cake into a decoloring kettle, adding 150kg of water and 2kg of activated carbon, heating, refluxing and decoloring for 1 hour, keeping the refluxing and decoloring temperature at 70-80 ℃, filtering to remove the activated carbon while the activated carbon is hot after decoloring, cooling to 10 ℃, performing suction filtration, and drying at 75 ℃ to obtain the final product, namely the m-hydroxybenzaldehyde. The yield of m-hydroxybenzaldehyde is 87%, it is gray white to reddish crystal, purity is above 99%, melting point is 100-101 deg.C.
Example 2
A preparation method of m-hydroxybenzaldehyde comprises the following steps:
preparation of m-acetoxytoluene: 108kg of m-cresol is taken and added into a stainless steel reaction kettle, 107kg of acetic anhydride is added, the liquid is colorless and transparent, the temperature is raised to 130-135 ℃, after the heat preservation reaction is carried out for 5 hours (the m-cresol residue is detected to be less than 0.5 percent by GC), the reduced pressure distillation is carried out until the temperature reaches 120 ℃, the by-product acetic acid is recovered, the residue is the intermediate product m-acetoxy toluene, about 145.5kg, and the yield is 97 percent.
Preparation of m-acetoxydibromotoluene: adding 145.5kg of the intermediate product obtained in the step (1) into a stainless steel reaction kettle, adding 300kg of carbon tetrachloride, 2.5kg of dibenzoyl peroxide, 5kg of azobisisoheptonitrile and 363kgNBS, heating to 65 ℃, and carrying out heat preservation reaction for 11 hours, wherein the system is changed into orange turbid shape from yellow turbid shape, then changed into orange semi turbid shape, then changed into bromine red transparent shape, and then changed into bromine red turbid shape. And after the reaction is completed, adding 400kg of water for washing, simultaneously adding a sodium sulfite aqueous solution to remove the residual brominating agent, recovering a water layer after the washing is completed, washing an obtained organic layer, and recovering the organic solvent under reduced pressure to obtain an orange-colored sticky substance, namely the m-acetoxyl dibromotoluene.
Preparation of m-hydroxybenzaldehyde: adding 300kg of water and 103kg of sodium carbonate into the material obtained in the step (2), heating to reflux, keeping the temperature for reaction for 10 hours, wherein the initial color of the reaction is orange turbid, the color gradually deepens along with the prolonging of the reaction time, the color finally becomes bromine red and is accompanied with the precipitation of black solid residues, filtering the solid residues while the reaction is hot, cooling to below 10 ℃, precipitating a solid product, filtering to obtain a filter cake, and obtaining a filtrate in wine red. And (3) putting the filter cake into a decoloring kettle, adding 200kg of water and 6.5kg of activated carbon, heating, refluxing and decoloring for 1 hour, keeping the refluxing and decoloring temperature at 70 ℃, filtering to remove the activated carbon while the activated carbon is hot after decoloring, cooling to 10 ℃, performing suction filtration, and drying at 75 ℃ to obtain the final product, namely the m-hydroxybenzaldehyde. The yield of m-hydroxy benzaldehyde is 91%, it is gray white to reddish crystal, the purity is above 99.1%, and the melting point is 100.1-100.5 deg.C.
Example 3
A preparation method of m-hydroxybenzaldehyde comprises the following steps:
preparation of m-acetoxytoluene: 200kg of m-cresol is added into a stainless steel reaction kettle, 221kg of acetic anhydride is added, the liquid is colorless and transparent, the temperature is raised to 130-135 ℃, after 5 hours of heat preservation reaction (the m-cresol residue is detected to be less than 0.5 percent by GC), the reduced pressure distillation is carried out to 120 ℃ to recover the acetic acid as a byproduct, the remainder is an intermediate product of m-acetoxy toluene, about 272kg, and the yield is 98 percent.
Preparation of m-acetoxydibromotoluene: and (2) adding 272kg of the intermediate product obtained in the step (1) into a stainless steel reaction kettle, adding 680kg of tetrachloroethane, 6.8kg of cyclohexanone peroxide, 20kg of azobisisobutyronitrile and 647kg of NBS, heating to 80 ℃, keeping the temperature, reacting for 15 hours, and changing the system from yellow turbid into orange turbid, then into orange semi turbid, then into bromine red transparent, then into bromine red turbid. And after the reaction is completed, adding 600kg of water for washing, simultaneously adding a sodium bisulfite aqueous solution to remove residual brominating agent, recovering a water layer after the washing is completed, washing an obtained organic layer, and recovering an organic solvent under reduced pressure to obtain an orange-colored sticky substance, namely the m-acetoxyl dibromotoluene.
Preparation of m-hydroxybenzaldehyde: adding 400kg of water and 190kg of calcium carbonate into the material obtained in the step (2), heating to reflux, keeping the temperature for reaction for 10 hours, wherein the initial color of the reaction is orange turbid, the color gradually deepens along with the prolonging of the reaction time, the color finally becomes bromine red and is accompanied with the precipitation of black solid residues, filtering the solid residues while the reaction is hot, cooling to below 10 ℃, precipitating a solid product, filtering to obtain a filter cake, and obtaining a filtrate in wine red. And (3) putting the filter cake into a decoloring kettle, adding 400kg of water and 15kg of activated carbon, heating, refluxing and decoloring for 1 hour, keeping the refluxing and decoloring temperature at 75 ℃, filtering to remove the activated carbon while the activated carbon is hot after decoloring, cooling to 10 ℃, performing suction filtration, and drying at 75 ℃ to obtain the final product, namely the m-hydroxybenzaldehyde. The yield of m-hydroxybenzaldehyde is 94%, it is gray white to reddish crystal, the purity is above 99.5%, and the melting point is 100.5-101 deg.C.
Example 4
A preparation method of m-hydroxybenzaldehyde comprises the following steps:
preparation of m-acetoxytoluene: 220kg of m-cresol is added into a stainless steel reaction kettle, 253.5kg of acetic anhydride is added, the liquid is colorless and transparent, the temperature is raised to 130-135 ℃, the temperature is kept for 5 hours (the m-cresol residue is detected to be less than 0.5 percent by GC) and the reduced pressure distillation is carried out to 120 ℃ to recover the acetic acid as a byproduct, the remainder is an intermediate product of m-acetoxy toluene, about 302.5kg, and the yield is 99 percent.
Preparation of m-acetoxydibromotoluene: adding 302.5kg of the intermediate product obtained in the step (1) into a stainless steel reaction kettle, adding 1200kg of chlorobenzene, 4.5kg of dibenzoyl peroxide, 4.5kg of azobisisobutyronitrile and 635kg of dibromohydantoin, heating to 90 ℃, and carrying out heat preservation reaction for 13 hours, wherein the system is changed into orange turbid shape from yellow turbid shape, then changed into orange semi turbid shape, then changed into bromine red transparent shape, and then changed into bromine red turbid shape. And after the reaction is completed, adding 500kg of water for washing, simultaneously adding an ammonium thiosulfate aqueous solution to remove the residual brominating agent, recovering a water layer after the washing is completed, washing an obtained organic layer, and recovering an organic solvent under reduced pressure to obtain an orange-colored sticky substance, namely the m-acetoxyl dibromotoluene.
Preparation of m-hydroxybenzaldehyde: adding 1000kg of water and 402kg of barium carbonate into the material obtained in the step (2), heating to reflux, keeping the temperature for reaction for 15 hours, wherein the initial color of the reaction is orange turbid, the color gradually deepens along with the prolonging of the reaction time, the color finally becomes bromine red with the separation of black solid residues, filtering the solid residues while the reaction is hot, cooling to below 10 ℃, separating out a solid product, filtering to obtain a filter cake, and filtering to obtain a filtrate in wine red. And (3) putting the filter cake into a decoloring kettle, adding 450kg of water and 30kg of activated carbon, heating, refluxing and decoloring for 1 hour, keeping the refluxing and decoloring temperature at 75 ℃, filtering to remove the activated carbon while the activated carbon is hot after decoloring, cooling to 10 ℃, performing suction filtration, and drying at 75 ℃ to obtain the final product, namely the m-hydroxybenzaldehyde. The yield of the m-hydroxybenzaldehyde is 92 percent, the m-hydroxybenzaldehyde is in a crystal state from grey white to reddish, the purity is more than 99.3 percent, and the melting point is 100.3-100.7 ℃.
Example 5
A preparation method of m-hydroxybenzaldehyde comprises the following steps:
preparation of m-acetoxytoluene: 350kg of m-cresol is taken and added into a stainless steel reaction kettle, 364kg of acetic anhydride is added, the liquid is colorless and transparent, the temperature is raised to 130-135 ℃, after 5 hours of heat preservation reaction (GC controlled detection for m-cresol residue is less than 0.5 percent), the reduced pressure distillation is carried out until 120 ℃ to recover the acetic acid as a byproduct, the remainder is intermediate product m-acetoxy toluene, about 476.4kg, and the yield is 98 percent.
Preparation of m-acetoxydibromotoluene: 476.4kg of the intermediate product obtained in the step (1) is added into a stainless steel reaction kettle, 1000kg of dichloroethane, 10kg of tert-butyl hydroperoxide, 14kg of azobisisobutyronitrile and 1026kg of dibromohydantoin are added, the temperature is raised to 70 ℃, the reaction is kept for 11 hours, the system is changed into orange turbid shape from yellow turbid shape, then changed into orange semi turbid shape, then changed into bromine red transparent shape, and then changed into bromine red turbid shape. And after the reaction is completed, adding 1000kg of water for washing, simultaneously adding a sodium sulfite aqueous solution to remove the residual brominating agent, recovering a water layer after the washing is completed, washing an obtained organic layer, and recovering the organic solvent under reduced pressure to obtain an orange-colored sticky substance, namely the m-acetoxyl dibromotoluene.
Preparation of m-hydroxybenzaldehyde: adding 700kg of water and 350kg of calcium carbonate into the material obtained in the step (2), heating to reflux, keeping the temperature for reaction for 11 hours, wherein the initial color of the reaction is orange turbid, the color gradually deepens along with the prolonging of the reaction time, the color finally becomes bromine red with the separation of black solid residues, filtering the solid residues while the reaction is hot, cooling to below 10 ℃, separating out a solid product, filtering to obtain a filter cake, and obtaining a filtrate in wine red. And (3) putting the filter cake into a decoloring kettle, adding 850kg of water and 20kg of activated carbon, heating, refluxing and decoloring for 1 hour, keeping the refluxing and decoloring temperature at 80 ℃, filtering to remove the activated carbon while the activated carbon is hot after decoloring is finished, cooling to 10 ℃, performing suction filtration, and drying at 75 ℃ to obtain the final product, namely the m-hydroxybenzaldehyde. The yield of m-hydroxybenzaldehyde is 90%, it is gray white to reddish crystal, purity is above 99.6%, melting point is 100.2-100.9 deg.C.
The experimental results show that:
the m-hydroxybenzaldehyde prepared by the method has the advantages of simple reaction path, less product impurities, high yield up to more than 87%, purity up to more than 99%, and capability of meeting market requirements.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of m-hydroxybenzaldehyde is characterized by comprising the following steps:
(1) preparation of m-acetoxytoluene: adding a certain amount of m-cresol into a stainless steel reaction kettle, adding a certain amount of acetic anhydride, heating to 130-135 ℃, carrying out heat preservation reaction for 5 hours, then carrying out reduced pressure distillation to 120 ℃ to recover a byproduct acetic acid, and obtaining an intermediate product, namely m-acetoxytoluene;
(2) preparation of m-acetoxydibromotoluene: sequentially adding a certain amount of organic solvent, a free radical initiator and a brominating agent into a product obtained by the reaction in the step (1), heating to 65-90 ℃, and carrying out heat preservation reaction for 10-15 hours; after the reaction is finished, adding water for washing, simultaneously adding a reducing agent to remove residual brominating agent, recovering a water layer after the washing is finished, and decompressing and recovering an organic solvent from an organic layer after the washing is finished to obtain an orange-colored sticky substance, namely m-acetoxyl dibromotoluene;
(3) preparation of m-hydroxybenzaldehyde: adding a certain amount of water and carbonate into the product obtained by the reaction in the step (2), heating to reflux, carrying out heat preservation reaction for 10-15 hours, filtering out solid residues while the solution is hot, cooling to below 10 ℃ to precipitate a solid, and then filtering; and putting the solid obtained by filtering into a decoloring kettle, adding water and activated carbon, heating, refluxing and decoloring for 1 hour, keeping the refluxing and decoloring temperature at 70-80 ℃, filtering to remove the activated carbon while the solid is hot after decoloring is finished, cooling to 10 ℃, performing suction filtration, recycling the water layer, and drying the obtained solid at 75 ℃ to obtain the final product, namely the m-hydroxybenzaldehyde.
2. The method for preparing m-hydroxybenzaldehyde according to claim 1, characterized in that in the step (1), the molar ratio of m-cresol to acetic anhydride is 1: 1-1.3.
3. The method for preparing m-hydroxybenzaldehyde according to claim 1, characterized in that in the step (2), the mass ratio of the organic solvent, the radical initiator and the m-acetoxytoluene is 1-4:0.03-0.1: 1; the molar ratio of bromine atoms in the brominating agent to m-acetoxy toluene is 2-3: 1.
4. The method for preparing m-hydroxybenzaldehyde according to claim 1, characterized in that the brominating agent in step (2) is one or more of NBS and dibromohydantoin.
5. The method for preparing m-hydroxybenzaldehyde according to claim 1, wherein in the step (2), the organic solvent is halogenated alkane or halogenated aromatic hydrocarbon, specifically one or more of dichloroethane, carbon tetrachloride, tetrachloroethane, and chlorobenzene.
6. The method for preparing m-hydroxybenzaldehyde according to claim 1, wherein in the step (2), the radical initiator is a mixture of an organic peroxide and an azo initiator, and the mass ratio of the organic peroxide to the azo initiator is 1: 1-3.
7. The method for preparing m-hydroxybenzaldehyde according to claim 6, characterized in that the organic peroxide is one or more of cyclohexanone peroxide, dibenzoyl peroxide and tert-butyl hydroperoxide, and the azo initiator is one or more of azobisisobutyronitrile and azobisisoheptonitrile.
8. The method for preparing m-hydroxybenzaldehyde according to claim 1, characterized in that the reducing agent in step (2) is one or more of sodium sulfite, sodium bisulfite and sodium thiosulfate, and the added reducing agent is an aqueous solution, the concentration of the aqueous solution of the reducing agent is 20% by mass.
9. The method for preparing m-hydroxybenzaldehyde according to claim 1, characterized in that in the step (3), the molar ratio of the carbonate to the m-acetoxy dibromotoluene is 1-1.1: 1.
10. The method for preparing m-hydroxybenzaldehyde according to claim 1, wherein in the step (3), the carbonate is one or more of sodium carbonate, potassium carbonate, calcium carbonate and barium carbonate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112125799A (en) * | 2020-10-14 | 2020-12-25 | 重庆欣欣向荣精细化工有限公司 | Production method of vanillin isobutyrate |
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