CN113698287A - Method for preparing p-methylbenzoic acid by catalyzing carbon dioxide and methylbenzene - Google Patents
Method for preparing p-methylbenzoic acid by catalyzing carbon dioxide and methylbenzene Download PDFInfo
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Abstract
The invention relates to the technical field of preparation of p-methylbenzoic acid, and particularly relates to a method for preparing p-methylbenzoic acid by catalyzing carbon dioxide and methylbenzene. The method comprises the following steps: A. adding a catalytic material consisting of an aluminum trichloride main catalyst, a zeolite carrier and a chlorosilane cocatalyst, a toluene basic raw material and an organic solvent medium into a reactor; B. introducing carbon dioxide to perform catalytic reaction at the reaction temperature of 20-260 ℃ and the reaction pressure of normal pressure to 7.5MPa to prepare the p-toluic acid. The method takes toluene as a raw material, utilizes carbon dioxide as a carboxyl source in a resource manner, directly synthesizes p-toluic acid by a one-step method, has the highest atom utilization rate of 100 percent in the synthesis reaction, and shows the environmental economic superiority of energy conservation and emission reduction and the industrial application sustainability.
Description
Technical Field
The invention relates to the technical field of preparation of p-methylbenzoic acid, and particularly relates to a method for preparing p-methylbenzoic acid by catalyzing carbon dioxide and methylbenzene.
Background
The methyl benzoic acid is widely used as an important intermediate raw material of functional materials such as medicines, agricultural chemicals, organic high polymer materials, dyes, photosensitive materials and the like, the existence of methyl and carboxyl functional groups in an aromatic hydrocarbon molecular structure and the low toxicity characteristic expressed by group synergy enhance the applicability of the substance, and the methyl benzoic acid is further used as the intermediate raw material to carry out group conversion research to synthesize a new nontoxic green organic functional material. Recently, p-toluic acid shows advancement and multifunctionality in the research and development and application fields of medical organic functional materials and the like, for example, p-toluic acid is chloridized to form p-chloromethylbenzoic acid, and then ammoniated to form p-aminomethyl benzoic acid, so that the p-toluic acid is a hemostatic and fibrinolysis inhibitor, and is suitable for medicines for various diseases caused by overhigh activity of fibrinolytic enzyme; similarly, p-methylbenzoyl chloride and p-methylbenzamide are prepared by using p-methylbenzoic acid, and then are catalytically reduced to form p-methylbenzaldehyde, p-methylbenzonitrile and the like, so that the antihistaminic agents of acrivastine and phosphodil ([4- (2-benzothiazolyl phenylmethyl) ] diethyl phosphonate) and the like can be further synthesized, and the antihypertension and other cardiovascular diseases can be treated and health-care effects. In the application field of agricultural chemicals, p-toluic acid is used for synthesizing 2, 6-dichloro-p-toluic acid and further synthesizing the benzene bacteria amide bactericide, and the product has low toxicity. In particular, in the field of high polymer materials, p-methyl benzoic acid can be oxidized to synthesize terephthalic acid, which is used for producing ethylene terephthalate and trimethylene terephthalate and is widely used for manufacturing polyester fibers (terylene), polyester resin, plastic films, military special insulating and bulletproof materials and other polymer functional materials. Therefore, the p-toluic acid has multipurpose application characteristics in the fields of advanced fine organic functional materials, high molecular polymer organic functional materials and the like.
The prior industrial preparation method takes toluene as a basic raw material to react with C9 aromatic hydrocarbon or methanol to synthesize p-xylene, and further applies a transition metal catalyst to catalyze air or nitric acid to oxidize the p-xylene to prepare p-methylbenzoic acid.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for preparing p-toluic acid by catalyzing carbon dioxide and toluene. The method takes toluene as a raw material, utilizes carbon dioxide as a carboxyl source in a resource manner, directly synthesizes p-toluic acid through one-step reaction under the action of a catalyst, has low cost of the raw material and simple synthesis process, reduces the emission of carbon dioxide greenhouse gas, has 100 percent of highest atomic utilization rate in the synthesis reaction, and shows the environmental economic superiority of energy conservation and emission reduction and the sustainability of industrial application.
The technical scheme adopted by the invention is as follows:
a method for preparing p-toluic acid by catalyzing carbon dioxide and toluene comprises the following steps:
A. adding a catalytic material consisting of a Lewis acid main catalyst, a zeolite carrier and a chlorosilane cocatalyst, a toluene basic raw material and an organic solvent medium into a reactor;
B. introducing carbon dioxide to perform catalytic reaction at the reaction temperature of 20-260 ℃ and the reaction pressure of normal pressure to 7.5MPa to prepare the p-toluic acid.
In a preferable scheme, the chlorosilane cocatalyst is any one of phenyltrichlorosilane, phenyldimethylchlorosilane, diphenylmethylchlorosilane, triphenylchlorosilane, methyltrichlorosilane, dimethyl tert-butylchlorosilane, trimethylchlorosilane and 1H,1H,2H, 2H-perfluorooctyltrichlorosilane.
Preferably, the zeolite support is any one of ZSM, BEA and HY aluminosilicate zeolites.
In a preferable scheme, the Lewis acid main catalyst is any one of aluminum trichloride, aluminum bromide, titanium tetrachloride and stannic chloride.
Preferably, the organic solvent is any one of toluene, n-hexane, cyclohexane, dichloromethane, dichloroethane, carbon disulfide, tetrahydrofuran, dimethyl sulfoxide and methyl pyrrolidone.
In the preferable scheme, the reaction temperature is preferably 30-100 ℃, the reaction pressure is preferably 1.5-6.0 MPa, and the reaction time is 7.5-8.5 hours.
In the preferred scheme, the mass of the Lewis acid main catalyst, the zeolite carrier and the chlorosilane cocatalyst is (0.1-1): 1 (0.1-3), and the addition amount of the catalytic material is 10-200% of the mass of the substrate.
In a further scheme, the reactor is a kettle reactor or a tower reactor.
In a further scheme, the method also comprises a p-toluic acid separation process, and the p-toluic acid separation process is operated as follows: after the catalytic reaction is finished, regulating the pH value of the reaction mixture to 6-7 by using a hydrochloric acid solution, then adding dichloromethane, carrying out solid-liquid and liquid-liquid separation to obtain an organic phase, washing the organic phase to be neutral by using pure water, carrying out liquid-liquid separation, then carrying out reduced pressure evaporation and concentration on the organic phase, and finally carrying out column chromatography separation, purification and crystallization to obtain the p-toluic acid product.
In a further scheme, the adding amount of the dichloromethane is 1-10 times of the mass of the substrate.
The invention has the technical effects that:
(1) the preparation principle of the invention is as follows: preparing a solution of an aromatic toluene substrate in an organic solvent or preparing the solution of toluene as the organic solvent, controlling certain reaction temperature and pressure, and reacting with carbon dioxide under the action of a catalytic material consisting of aluminum trichloride, a zeolite carrier and chlorosilane to synthesize the p-methylbenzoic acid compound. The specific synthesis reaction equation of the invention is as follows:
the method of the invention uses aromatic toluene and carbon dioxide to prepare p-methyl benzoic acid, and has high para-selectivity. The method uses carbon dioxide as a carboxylation reagent to form carboxylic acid, replaces the traditional catalytic molecular oxygen or nitric acid method to oxidize aromatic side chain methyl to form carboxylic acid, has resource utilization characteristic in carbon dioxide reaction, is beneficial to industrial environmental economy preparation of organic carboxylic acid, improves the atom utilization rate of the reaction for preparing carboxylic acid, and has the environmental economy sustainable development characteristics of industrial application, energy conservation, emission reduction and the like.
(2) The selection of the formula of the catalytic material of the invention has the effect of improving the reaction activity of carbon dioxide and the selectivity of products on the preparation result.
(3) The preparation method of the invention has relatively mild temperature and pressure conditions and is easy for industrial application. In addition, the control values of temperature and pressure in the preparation method can effectively improve the conversion rate of reaction raw materials and the selectivity of products.
(4) The method of the invention uses ZSM, BEA and HY aluminosilicate zeolite with large specific surface area as a carrier, and the stability and activity of the catalyst can be improved by selecting the aluminosilicate zeolite as the carrier.
(5) The method can react in a solvent-free medium or an organic solvent medium, wherein the solvent-free medium is a reaction substrate toluene serving as a solvent, the organic solvent mainly comprises n-hexane, toluene, cyclohexane, dichloromethane, dichloroethane, carbon disulfide, tetrahydrofuran, dimethyl sulfoxide, methyl pyrrolidone and the like, and the toluene and the carbon disulfide have excellent medium characteristics.
(6) The preparation reaction mode of the invention can be batch reaction or continuous reaction, the reaction phase is heterogeneous reaction, the reactor can be a kettle reactor or a tower reactor, and the preparation of the compound is not influenced, namely the preparation reaction form of the invention is not limited.
Drawings
FIG. 1 shows the product p-toluic acid1H-NMR Structure analysis Spectroscopy (500MHz, CDCl)3Bruckeravance, Germany type III).
FIG. 2 shows the product of methyl benzoic acid13C-NMR Structure analysis Spectroscopy (126MHz, CDCl)3Bruckeravance, Germany type III).
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the following description is given in conjunction with the accompanying examples. It is to be understood that the following text is only intended to describe certain embodiments of the invention, and does not strictly limit the scope of the invention as specifically claimed.
Example 1
In an intelligent reactor containing 3.5g of toluene, 0.67g of 50% aluminum trichloride BEA zeolite solid carrier and 0.50g of 1H,1H,2H, 2H-perfluorooctyltrichlorosilane, carbon dioxide is introduced under magnetic stirring, and the temperature of 40 ℃ and the pressure of 3.0MPa are controlled for reaction for 8 hours. After the reaction is finished, adding dilute hydrochloric acid into the reaction mixture to adjust the pH value to 6-7, adding 10.0g of dichloromethane, separating out an organic phase through solid-liquid and liquid-liquid separation, further washing with pure water until the organic phase is neutral, finally concentrating the organic phase through liquid-liquid separation and reduced pressure evaporation, and separating and purifying the crystallized p-toluic acid through column chromatography, wherein the yield is 66.5%.
Example 2
Carbon dioxide was introduced into a reactor containing 3.5g of toluene, 0.13g of aluminum trichloride, 0.15g of BEA zeolite and 0.29g of triphenylchlorosilane under magnetic stirring, and the reaction was carried out for 8 hours at a temperature of 40 ℃ and a pressure of 3.0 MPa. After the reaction is finished, adding dilute hydrochloric acid into the reaction mixture to adjust the pH value to 6-7, adding 10.0g of dichloromethane, separating out an organic phase through solid-liquid and liquid-liquid separation, further washing with pure water until the organic phase is neutral, finally concentrating the organic phase through liquid-liquid separation and reduced pressure evaporation, and separating and purifying the crystallized p-toluic acid through column chromatography, wherein the yield is 63.5%.
Example 3
In a reactor containing 5.0mL of dichloromethane, 0.92g of toluene, 0.50g of 50% aluminum trichloride BEA zeolite solid carrier and 0.50g of triphenylchlorosilane are added into an intelligent reactor, carbon dioxide is introduced under magnetic stirring, and the temperature of 40 ℃ and the pressure of 5.0MPa are controlled for reaction for 8 hours. After the reaction is finished, adding dilute hydrochloric acid into the reaction mixture to adjust the pH value to 6-7, adding 10.0g of dichloromethane, separating out an organic phase through solid-liquid and liquid-liquid separation, further washing with pure water until the organic phase is neutral, finally concentrating the organic phase through liquid-liquid separation and reduced pressure evaporation, and separating and purifying the crystallized p-toluic acid through column chromatography, wherein the yield is 40.0%.
Example 4
In a reactor containing 5.0mL of carbon disulfide, 0.92g of toluene, 0.50g of 50% aluminum trichloride BEA zeolite solid carrier and 0.50g of trimethylchlorosilane are added into an intelligent reactor, carbon dioxide is introduced under magnetic stirring, and the temperature of 40 ℃ and the pressure of 5.0MPa are controlled for reaction for 8 hours. After the reaction is finished, adding dilute hydrochloric acid into the reaction mixture to adjust the pH value to 6-7, adding 10.0g of dichloromethane, separating out an organic phase through solid-liquid and liquid-liquid separation, further washing with pure water until the organic phase is neutral, finally concentrating the organic phase through liquid-liquid separation and reduced pressure evaporation, and separating and purifying the crystallized p-toluic acid through column chromatography, wherein the yield is 60.0%.
Example 5
In a reactor containing 5.0mL of dichloromethane, 0.92g of toluene, 0.50g of 50% aluminum trichloride BEA zeolite solid carrier and 0.50g of phenyltrichlorosilane are added, carbon dioxide is introduced under magnetic stirring, and the temperature of 80 ℃ and the pressure of 6.0MPa are controlled for reaction for 10 hours. After the reaction is finished, adding dilute hydrochloric acid into the reaction mixture to adjust the pH value to 6-7, adding 10.0g of dichloromethane, separating out an organic phase through solid-liquid and liquid-liquid separation, further washing with pure water until the organic phase is neutral, finally concentrating the organic phase through liquid-liquid separation and reduced pressure evaporation, and separating and purifying the crystallized p-toluic acid through column chromatography, wherein the yield is 46.6%.
Example 6
In a reactor containing 5.0mL of dichloromethane, 0.92g of toluene, 0.50g of 50% aluminum trichloride ZSM zeolite solid carrier and 0.50g of triphenylchlorosilane are added, carbon dioxide is introduced under magnetic stirring, and the temperature of 80 ℃ and the pressure of 6.0MPa are controlled for reaction for 10 hours. After the reaction is finished, adding dilute hydrochloric acid into the reaction mixture to adjust the pH value to 6-7, adding 10.0g of dichloromethane, separating out an organic phase through solid-liquid and liquid-liquid separation, further washing with pure water until the organic phase is neutral, finally concentrating the organic phase through liquid-liquid separation and reduced pressure evaporation, and separating and purifying the crystallized p-toluic acid through column chromatography, wherein the yield is 31.7%.
Example 7
This example is a three-group experiment, and the method is the same as example 1, except that the Lewis acid main catalyst is aluminum bromide, titanium tetrachloride and stannic chloride. The results showed yields of 61.2%, 60.6% and 62.7% for p-toluic acid, respectively.
Example 8
This example is a five-series experiment, and the method is the same as example 1, except that the chlorosilane co-catalyst is phenyl dimethylchlorosilane, diphenyl methylchlorosilane, triphenylchlorosilane, methyltrichlorosilane, dimethyl t-butylchlorosilane, respectively. The results showed yields of 60.1%, 61.3%, 60.2%, 59.7%, 58.9% for p-toluic acid, respectively.
Example 9
The present embodiment is a three-group experiment, and the method is the same as that in embodiment 1, except that the mass of the Lewis acid main catalyst, the mass of the zeolite carrier and the mass of the chlorosilane co-catalyst are sequentially selected from 0.1:1:0.1, 0.5:1:1.5 and 1:1:3, and the addition amount of the catalytic material is 10%, 100% and 200% of the mass of the substrate. The results showed yields of 58.0%, 62.3% and 61.2% for p-toluic acid, respectively.
Example 10
This example is a five-group experiment, and the difference of the method is that the reaction temperature is 20 deg.C, 30 deg.C, 50 deg.C, 100 deg.C, 260 deg.C, and the reaction pressure is atmospheric pressure, 1.5MPa, 4.0MPa, 6.0MPa, 7.5 MPa. The results showed yields of 40.1%, 59.0%, 62.3%, 61.2%, 41.6% for p-toluic acid, respectively.
The aluminum trichloride zeolite solid carrier is formed by loading anhydrous aluminum trichloride on ZSM or BEA or HY aluminosilicate zeolite. The preparation method of the aluminum trichloride zeolite solid carrier comprises the following steps: stirring and refluxing aluminum trichloride and ZSM or BEA or HY aluminosilicate zeolite in an organic solvent for 3 hours, and then performing rotary evaporation on the mixture to obtain the aluminum trichloride/zeolite solid phase liquid.
The specific process of separating the organic phase from the solid and liquid is to centrifugally separate the catalytic material and the liquid phase mixture from the reaction mixture, and then separate the aqueous phase and the organic phase from the liquid phase mixture in a separator. The organic phase comprises dichloromethane organic solvent, toluene organic raw material and organic reaction product p-toluic acid.
The specific process of liquid-liquid separation, reduced pressure evaporation and concentration of the organic phase comprises the steps of firstly distilling at normal pressure to recover a dichloromethane organic solvent, then distilling at negative pressure to recover unconverted organic raw materials such as toluene and the like, wherein the undistilled materials are organic phase concentrated solution containing organic reaction products, namely p-toluic acid.
The detection results of the p-toluic acid products of the above examples are shown in fig. 1 and fig. 2, and the results of hydrogen nuclear magnetic resonance detection analysis and carbon nuclear magnetic resonance detection analysis show that p-toluic acid is successfully and directly synthesized by one-step reaction.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention. Structures, devices, and methods of operation not specifically described or illustrated herein are generally practiced in the art without specific recitation or limitation.
Claims (10)
1. A method for preparing p-toluic acid by catalyzing carbon dioxide and toluene comprises the following steps:
A. adding a catalytic material consisting of a Lewis acid main catalyst, a zeolite carrier and a chlorosilane cocatalyst, a toluene basic raw material and an organic solvent medium into a reactor;
B. introducing carbon dioxide to perform catalytic reaction at the reaction temperature of 20-260 ℃ and the reaction pressure of normal pressure to 7.5MPa to prepare the p-toluic acid.
2. The method for preparing p-toluic acid by catalyzing carbon dioxide and toluene according to claim 1, wherein: the chlorosilane is any one of phenyl trichlorosilane, phenyl dimethylchlorosilane, diphenyl methylchlorosilane, triphenyl chlorosilane, methyl trichlorosilane, dimethyl tert-butyl chlorosilane, trimethyl chlorosilane and 1H,1H,2H, 2H-perfluorooctyl trichlorosilane.
3. The method for preparing p-toluic acid by catalyzing carbon dioxide and toluene according to claim 1, wherein: the zeolite carrier is any one of ZSM, BEA and HY aluminosilicate zeolite.
4. The method for preparing p-toluic acid by catalyzing carbon dioxide and toluene according to claim 1, wherein: the Lewis acid main catalyst is any one of aluminum trichloride, aluminum bromide, titanium tetrachloride and stannic chloride.
5. The method for preparing p-toluic acid by catalyzing carbon dioxide and toluene according to claim 1, wherein: the organic solvent is any one of toluene, n-hexane, cyclohexane, dichloromethane, dichloroethane, carbon disulfide, tetrahydrofuran, dimethyl sulfoxide and methyl pyrrolidone.
6. The method for preparing p-toluic acid by catalyzing carbon dioxide and toluene according to claim 1, wherein: the reaction temperature is preferably 30-100 ℃, the reaction pressure is preferably 1.5-6.0 MPa, and the reaction time is 7.5-8.5 hours.
7. The method for preparing p-toluic acid by catalyzing carbon dioxide and toluene according to claim 1, wherein: the mass ratio of the Lewis acid main catalyst to the zeolite carrier to the chlorosilane cocatalyst is (0.1-1) to 1 (0.1-3), and the addition amount of the catalytic material is 10-200% of the mass of the substrate.
8. The method for preparing p-toluic acid by catalyzing carbon dioxide and toluene according to claim 1, wherein: the reactor is a kettle reactor or a tower reactor.
9. The method for preparing p-toluic acid by catalyzing carbon dioxide and toluene according to claim 1, wherein: the method also comprises a p-toluic acid separation process, which is operated as follows: after the catalytic reaction is finished, regulating the pH value of the reaction mixture to 6-7 by using a hydrochloric acid solution, then adding dichloromethane, carrying out solid-liquid and liquid-liquid separation to obtain an organic phase, washing the organic phase to be neutral by using pure water, carrying out liquid-liquid separation, then carrying out reduced pressure evaporation and concentration on the organic phase, and finally carrying out column chromatography separation, purification and crystallization to obtain the p-toluic acid product.
10. The process for the catalytic production of p-toluic acid from carbon dioxide and toluene according to claim 9, wherein: the adding amount of the dichloromethane is 1-10 times of the mass of the substrate.
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