CN112374978A - Preparation method of phenylacetic acid - Google Patents
Preparation method of phenylacetic acid Download PDFInfo
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Abstract
The invention discloses a preparation method of phenylacetic acid, and relates to the technical field of organic synthesis. The preparation method of the phenylacetic acid specifically comprises the following steps: carrying out sulfoesterification reaction on alcohol, and carrying out sulfoesterification treatment on 2-butyne-1, 4-diol by using p-toluenesulfonyl chloride to obtain a product A; friedel-crafts alkylation reaction, under the catalytic action of a polymerization ionic liquid catalyst, benzene and the product A react to obtain a product B; oxidizing alkyne, taking tetrabutylammonium bromide as PCT and m-CPBA as an oxidant, and treating the product B to obtain phenylacetic acid. The preparation method of phenylacetic acid provided by the invention has the advantages of high yield of the prepared phenylacetic acid, simple operation, easy operation of reaction conditions and high safety.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of phenylacetic acid.
Background
Phenylacetic acid is an important organic chemical raw material, and the pharmaceutical industry is mainly used for producing penicillin, dibazole and other medicaments; the phenylacetic acid is chlorinated and esterified to obtain ethyl chlorophenylacetate which is used for producing broad-spectrum organophosphorus insecticide named as phenthoate and ethyl phenthoate and is also a plant growth stimulant of pesticides; phenylacetic acid has a sweet honey taste at low concentrations, and phenylacetic acid and its esters are widely used in the fragrance industry as fixative or modifier.
The production process of phenylacetic acid mainly includes benzyl cyanide acid hydrolysis, benzyl cyanide alkali hydrolysis, styrene process, benzyl chloride carbonylation synthesis, benzyl ketone process and benzyl alcohol process. The current industrialized methods mainly comprise benzyl cyanide acid hydrolysis method, benzyl cyanide alkaline hydrolysis method and benzyl chloride carbonylation synthesis method. However, in the existing synthetic method for synthesizing phenylacetic acid with industrial value, either a highly toxic raw material is selected to cause doubts about possible residues of highly toxic chemicals, or an extremely high reaction pressure condition is selected to increase the requirement on high pressure resistance of equipment and increase the unsafety factor of the production process, or the atom utilization rate in the selected synthetic method is low, so that a new green and safe synthetic method for producing phenylacetic acid is developed and is called as an important research direction of a medical intermediate and a pesticide intermediate.
Disclosure of Invention
The invention aims to provide a preparation method of phenylacetic acid, which has the advantages of excellent catalytic performance of a catalyst used in the synthesis process of an intermediate product, good thermal stability, good cycle performance and high product yield; the method can safely and effectively prepare the phenylacetic acid, and has high yield and high utilization rate of raw materials.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the structural formula of the catalyst for the phenylacetic acid preparation process is shown as a formula I:
the preparation method of the catalyst comprises the following steps:
s1: weighing monomers N-vinylimidazole and L-alpha-phosphatidylcholine-beta-arachidonoyl-gamma-stearoyl, dissolving in DMF, adding AIBN, stirring, reacting at high pressure and high temperature, vacuum drying, and grinding to obtain a product M;
s2: dissolving the product M in ethanol, adding n-bromoheptane in a dark place, stirring, centrifuging, washing and drying; then acidizing by using trifluoromethanesulfonic acid, centrifugally washing, and drying to obtain the catalyst. The polymerized ionic liquid has inherent low vapor pressure and higher thermodynamic stability of the ionic liquid, higher specific surface area and proper pore size; the acid groups contained in the L-alpha-phosphatidylcholine-beta-arachidonoyl-gamma-stearoyl are combined with acid, so that the use amount of the ionic liquid can be greatly reduced, and the utilization rate of the ionic liquid is improved; the catalyst has the composite characteristics of porous materials, polymers and ionic liquid, can be easily separated and recovered from a solvent, and has good catalytic performance; the structure combining the meso pores and the macro pores can effectively improve the mass transfer rate, thereby improving the catalytic performance of the catalyst; the catalyst prepared by the invention has good thermal stability and recycling performance.
Preferably, in step S1, the mass ratio of the monomers N-vinylimidazole to L- α -phosphatidylcholine- β -arachidonoyl- γ -stearoyl is 1: 1.8 to 2.5.
Preferably, the solid-to-liquid ratio of the product M to n-bromoheptane in step S2 is 1 g: 2-3 mL.
A method for producing phenylacetic acid, comprising:
carrying out sulfoesterification reaction on alcohol, and carrying out sulfoesterification treatment on 2-butyne-1, 4-diol by using p-toluenesulfonyl chloride to obtain a product A;
friedel-crafts alkylation reaction, under the catalytic action of the catalyst, benzene reacts with the product A to obtain a product B;
oxidizing alkyne, taking tetrabutylammonium bromide as PCT and m-CPBA as an oxidant, and treating the product B to obtain phenylacetic acid. In the preparation process of styrene, the catalyst is used in Friedel-crafts alkylation reaction process to replace AlCl3The ionic liquid is a traditional ionic liquid, is green and environment-friendly, and overcomes the defects of AlCl3The ionic liquid has high sensitivity to water, is extremely easy to hydrolyze in air, is not easy to recover after inactivation, and causes low catalytic efficiency, thereby effectively improving the yield of the product B; the utilization rate of the reaction substance is improved, and the reaction substance is easy to separate and recycle from the solvent. The whole preparation process of the phenylacetic acid has simple route operationThe reaction condition is easy to control, and the solvent can be recycled.
Preferably, the molar ratio of butyne-1, 4-diol to p-toluenesulfonyl chloride in the sulfoesterification of the alcohol is 1: 2.4 to 2.8.
Preferably, the mass ratio of the benzene, the product A and the catalyst in the Friedel-crafts alkylation reaction is 1: 3.8-3.9: 0.3 to 0.5.
Preferably, the yield of product B in the Friedel-crafts alkylation reaction is > 95%.
Preferably, the molar ratio of product B to m-CPBA in alkyne oxidation is 1: 4.5 to 5.3; the mass mol ratio of the tetrabutylammonium bromide to the product B is 1 g: 0.04 to 0.06 mol.
Preferably, the azaperone is added into the alkyne oxidation, and the adding amount is 7.34-9.36% of the mass of the tetrabutylammonium bromide. The addition of the azaperone is compounded with tetrabutylammonium bromide to promote the oxidation reaction of alkyne, improve the utilization rate of substances and further improve the yield of phenylacetic acid.
Preferably, the phenylacetic acid is produced in a yield of > 98%.
Compared with the prior art, the invention has the following beneficial effects:
the polymerization ionic liquid catalyst prepared by the invention has higher thermodynamic stability, can greatly reduce the using amount of ionic liquid and improve the catalytic activity of the ionic liquid; and has good recycling performance. The method is used for effectively improving the yield of the intermediate product in the manufacturing process of phenylacetic acid; the utilization rate of the reaction substance is improved, and the reaction substance is easy to separate and recycle from the solvent. In addition, the azaperone is added in the preparation process of the phenylacetic acid, and can be compounded with a phase transfer catalyst, so that the yield of the phenylacetic acid is effectively improved. The whole preparation process of the phenylacetic acid has the advantages of simple route operation, easily controlled reaction conditions, recoverable solvent and the like.
Therefore, the invention provides a preparation method of phenylacetic acid, and the catalyst used in the intermediate product synthesis process of the preparation method has excellent catalytic performance, good thermal stability, good cycle performance and high product yield; the method can safely and effectively prepare the phenylacetic acid, and has high yield and high utilization rate of raw materials.
Drawings
FIG. 1 is a schematic diagram showing the results of infrared absorption spectroscopy in test example 1 of the present invention;
FIG. 2 is a schematic diagram showing comparison of results of thermogravimetric analysis tests in test example 1 of the present invention;
FIG. 3 is a comparison of the results of the cycle stability test in test example 1 of the present invention;
FIG. 4 is a graph showing the comparison of the results of the test for the yield of product B in Experimental example 2 of the present invention;
FIG. 5 is a graph showing the comparison of the results of the test of the yield of phenylacetic acid in test example 2 of the present invention.
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1:
a method for preparing a catalyst for a phenylacetic acid production process, comprising:
s1: weighing monomers N-vinyl imidazole and L-alpha-phosphatidylcholine-beta-arachidonoyl-gamma-stearoyl (the mass ratio of the monomers N-vinyl imidazole to the liquid to solid is 1: 2.47), dissolving the monomers N-vinyl imidazole and L-alpha-phosphatidylcholine in DMF (the mass ratio of the monomers N-vinyl imidazole to the liquid to solid is 44.1 mL: 1g), adding AIBN (the mass ratio of the monomers N-vinyl imidazole to the monomer N-vinyl imidazole is 0.12: 1), mechanically stirring for 3h at room temperature, transferring the mixture to a 50mL high-pressure reaction kettle, and carrying out hydrothermal reaction for 24h at 100 ℃; vacuum drying at 40 deg.C until the solvent is completely evaporated, and grinding the obtained solid into powder to obtain product M;
s2: dissolving the product M in ethanol (the solid-liquid ratio is 1 g: 25mL), adding n-bromoheptane (the solid-liquid ratio of the product M to the product M is 1 g: 2.5mL) in a dark place, centrifuging and washing with a large amount of ethanol after stirring under magnetic force for 12h to remove the redundant n-bromoheptane, and drying at 60 ℃ for 12 h; then putting the mixture into anhydrous toluene solution (the volume ratio of the two is 1: 8.5) containing trifluoromethanesulfonic acid for room temperature acidification, reacting for 24h, then centrifugally washing for 3 times by using diethyl ether, and then drying for 6h at 50 ℃ to obtain the catalyst.
A method of making phenylacetic acid, comprising:
and (2) carrying out sulfoesterification reaction on alcohol, dissolving 2-butyne-1, 4-diol in a NaOH aqueous solution with the mass concentration of 27%, dropwise adding the solution into an acetonitrile solution of p-toluenesulfonyl chloride at the temperature of-1 ℃ (the molar ratio of 2-butyne-1, 4-diol to p-toluenesulfonyl chloride is 1: 2.53), continuing to react for 7 hours at the temperature after dropwise adding is completed for 1 hour, then adding a proper amount of petroleum ether and ice dilute hydrochloric acid to stop the reaction, carrying out vacuum filtration, washing a filter cake to be neutral by using ice water, and carrying out air drying to obtain a crude product, wherein the weight ratio of the crude product to the alcohol is V (ethanol): v (water) ═ 8: 2, recrystallizing to obtain a product A;
friedel-crafts alkylation reaction, placing benzene and the catalyst into a three-neck flask, and introducing N2Protecting, magnetically stirring at a constant temperature of 80 ℃ for 5min, beginning to dropwise add a benzene solution of the product A (the mass ratio of the benzene to the product A to the catalyst is 1: 3.87: 0.37), reacting for 2h, and dropwise adding dilute hydrochloric acid to terminate the reaction. Standing for 2h, performing layered filtration, washing with ice water to neutrality, adding anhydrous sodium sulfate, standing for 6h, extracting the filtrate with benzene, and performing rotary evaporation to obtain a product B;
oxidizing alkyne, taking product B, V (dichloromethane): v (glacial acetic acid) ═ 10: 1 is a solvent, tetrabutylammonium bromide (the mass molar ratio of tetrabutylammonium bromide to the product B is 1 g: 0.05mol) is PCT, m-CPBA is an oxidant (the mass molar ratio of tetrabutylammonium bromide to the product B is 4.78: 1), the reaction is stopped after reflux heating is carried out for 13h at 50 ℃, and sodium sulfite is added to consume the redundant oxidant; then dichloromethane is used for extracting the mixed solution, 10% NaOH solution is used for washing the extract liquor, the obtained aqueous solution is acidified by 50% sulfuric acid, finally, ether is used for extraction, and rotary evaporation is carried out to obtain phenylacetic acid.
Example 2:
a catalyst for phenylacetic acid production process was prepared in the same manner as in example 1.
A phenylacetic acid was prepared in the following manner, which was different from example 1 in that: in the Friedel-crafts alkylation reaction, the mass ratio of benzene, the product A and the catalyst is 1: 3.86: 0.43.
example 3:
a catalyst for phenylacetic acid production process was prepared in the same manner as in example 1.
A phenylacetic acid was prepared in the following manner, which was different from example 1 in that: in the Friedel-crafts alkylation reaction, the mass ratio of benzene, the product A and the catalyst is 1: 3.8: 0.3.
example 4:
a catalyst for phenylacetic acid production process was prepared in the same manner as in example 1.
A phenylacetic acid was prepared in the following manner, which was different from example 1 in that: in the Friedel-crafts alkylation reaction, the mass ratio of benzene, the product A and the catalyst is 1: 3.89: 0.48.
example 5:
a catalyst for phenylacetic acid production process was prepared in the same manner as in example 1.
A phenylacetic acid was prepared in the following manner, which was different from example 1 in that: and adding the azaperone into the alkyne for oxidation, wherein the adding amount is 8.41 percent of the mass of the tetrabutylammonium bromide.
Comparative example 1:
a phenylacetic acid was prepared in the following manner, which was different from example 1 in that: in Friedel-crafts alkylation reaction, AlCl is used as catalyst3The mass ratio of the ionic liquid, benzene, the product A and the catalyst is 1: 3.86: 3.39.
comparative example 2:
preparation of a catalyst for a phenylacetic acid production process:
dissolving N-vinylimidazole in ethanol (solid-to-liquid ratio is 1 g: 25mL), adding N-bromoheptane (the solid-to-liquid ratio of N-vinylimidazole is 1 g: 2.5mL) in a dark place, centrifuging after stirring for 12h under magnetic force, washing with a large amount of ethanol to remove redundant N-bromoheptane, and drying at 60 ℃ for 12 h; then putting the mixture into anhydrous toluene solution (the volume ratio of the two is 1: 8.5) containing trifluoromethanesulfonic acid for room temperature acidification, reacting for 24h, then centrifugally washing for 3 times by using diethyl ether, and then drying for 6h at 50 ℃ to obtain the catalyst.
A phenylacetic acid was prepared in the same manner as in example 1.
Test example 1:
catalyst characterization and Performance testing
1. Infrared Spectrometry (FT-IR)
After the samples are subjected to water removal treatment in a constant-temperature drying oven, a small amount of samples and potassium bromide are uniformly mixed in an agate mortar, ground and tabletted, and then the mixture is placed on a TENSOR 27 type infrared spectrometerPerforming a test, wherein the scanning wave number range is 4000-500 cm-1Scanning resolution of 6cm-1The number of scans was 18.
The catalyst obtained in example 1 was subjected to the above test, and the results are shown in FIG. 1. As can be seen in the figure, 1636cm-1And 1460cm-1The two characteristic peaks respectively correspond to the stretching vibration of C ═ C and C ═ N of the imidazole ring, and indicate the existence of the imidazole ring in the mesoporous and macroporous polymer; at 1267cm-1A strong characteristic peak appears, which is a vibration absorption peak of C-F and indicates the existence of the triflate; 703cm-1The strong absorption peak corresponds to the characteristic peak of long-chain alkane, 2930cm-1Has an absorption peak of CH2Stretching vibration of (2); 3040cm-1The nearby absorption peak is the stretching vibration of the unsaturated carbon-hydrogen bond; 1734cm-1The absorption peak is the stretching vibration of C ═ O in the ester group; 1230cm-1And 1060cm-1The absorption peaks at (a) are the stretching vibrations of P ═ O and P — O — C, respectively; 936cm-1The absorption peaks at the left and right are C-C-N+Characteristic peak of (2). The above results indicate that the polymeric acidic ionic liquid catalyst was successfully prepared.
2. Thermogravimetric analysis (TGA)
Thermogravimetric analysis of the sample the prepared sample was subjected to thermogravimetric analysis by a TG 8120 differential scanning calorimeter of Rigaku corporation. The analysis conditions are 10 ℃ and min in air atmosphere-1The analysis rate of (2).
The catalyst obtained in example 1 was subjected to the above test, and the results are shown in FIG. 2. It can be seen from the figure that the thermal decomposition of the catalyst is divided into three stages, the decrease in each stage of the curve corresponding to the decomposition of one of the monomers. Among them, it is to be specifically noted that the decrease in the curve at the initial stage is attributed to the residual solvent in the sample. Thereafter, around 200 ℃, the TGA curve has a downward trend, indicating that the polymer starts to decompose. There is a clear trend towards a decline at around 380 ℃ due to the cleavage of the main bond between N-vinylimidazole and L- α -phosphatidylcholine- β -arachidonoyl- γ -stearoyl. Finally, the sample was completely decomposed at around 630 ℃. As a whole, polymeric acidic ionic liquids formed by free radical polymerization have relative thermal stability over a range of temperatures: at the temperature lower than 380 ℃, the polymeric acidic ionic liquid structure can maintain certain stability, and then the structure collapses. The catalyst can be suitable for Friedel-crafts alkylation reaction in the process by combining the reaction condition requirement of the phenylacetic acid preparation process.
3. Evaluation of catalytic Properties
3.1 catalytic reaction
The alkylation reaction of o-xylene and styrene is carried out in a three-neck flask provided with a condenser tube, a thermometer and a constant pressure dropping funnel, and the mass ratio of the raw material benzene to the styrene is ensured to be 7.5: 1, a detailed test was carried out with the ortho-xylene (30g) and styrene (4g) being dosed. Firstly, 0.17g of catalyst (accounting for 0.5 percent of the total mass of reactants) and a part of o-xylene are added into a three-neck flask, the temperature is increased to 80 ℃, the rest o-xylene and styrene are mixed, the mixture is slowly dripped into the flask through a constant pressure dropping funnel, the dripping time is controlled within 2 hours, and then the reaction is continued for 1 hour. And after the reaction, carrying out vacuum filtration on the obtained product and collecting to obtain filtrate, washing the reacted catalyst with excessive absolute ethyl alcohol, drying and recovering. The filtrate was subjected to reduced pressure distillation to separate unreacted o-xylene and to give a crude diarylethane (PXE) product which was weighed and labeled for further gas chromatographic analysis.
3.2 analysis of the product
The product was analyzed by gas chromatography, model GC 9890A. The chromatographic conditions were: the chromatographic column is HPTNNOWAX, the capillary column is 60m multiplied by 0.53mm, the carrier gas is nitrogen, the sample injection amount is 0.4 mu L, the temperature of the sample injector is 250 ℃, the temperature of the detector is 250 ℃, a programmed heating mode is adopted, the initial temperature is set to be 150 ℃, the temperature is kept for 2min, and the heating rate is 5 ℃ min-1The termination temperature is 250 ℃, the holding time is 2min, and the total time is 30 min. And the N2000 type double-channel chromatographic workstation calculates the yield of the sample by adopting an area normalization method.
Actual yield/theoretical yield × 100%
Actual yield ═ total crude weight × product (chromatographic assay)%
The above tests were carried out on the catalyst obtained in example 1, and the calculated PXE yield was 99.48%, indicating that the catalyst obtained in the present invention has excellent catalytic activity.
3.3 cycle Performance test
In addition to thermal stability, the cycle performance of the catalyst is another important indicator for evaluating the performance of the catalyst. Samples were subjected to 6 cycles of catalysis and product analysis as described above. The catalyst obtained in example 1 was subjected to the above test, and the results are shown in FIG. 3. Analysis shows that the catalytic activity is not obviously reduced after 6 times of recycling, and PXE keeps higher yield, which shows that the catalyst prepared by the invention has better stability.
Test example 2:
1. yield analysis of intermediate B
The test method used a gas chromatograph, and the procedure was as shown in 3.2 in test example 1.
The results of the above tests on the product B obtained in the processes of preparation of phenylacetic acid according to comparative example 1, comparative example 2 and examples 1 to 4 are shown in FIG. 4. From the analysis in the figure, the yield of the product B prepared in example 1 is 98.4%, which is obviously higher than 64.3% of comparative example 1 and 81.9% of comparative example 2, and is slightly better than that of examples 2-4, and the yields of the products B prepared in examples 1-4 of the invention are all more than 95%, which shows that the catalyst prepared in the invention has higher catalytic activity, can better catalyze the reaction, and improves the yield of the product B. In addition, the amount of catalyst used in example 1 was significantly lower than in comparative example 1, further indicating that AlCl was used in comparison to the conventional catalyst3The catalyst prepared by the method has excellent catalytic activity, and the dosage of the catalyst in the reaction process is greatly reduced. Compared with the comparative example 2, the yield of the product B is obviously improved, which shows that the polymerized acidic ionic liquid prepared in the example 1 of the invention has higher catalytic activity as a catalyst.
2. Analysis of Phenylacetic acid yield
The test method is shown in 3.2 of test example 1.
The phenylacetic acids obtained in examples 1 and 5 were subjected to the above-described tests, and the results are shown in FIG. 5. As can be seen from the figure, the yield of the sample prepared in example 5 is 98.2%, which is obviously higher than 80.4% of that prepared in example 1, and the result shows that the yield of phenylacetic acid can be effectively improved by adding azaperone and tetrabutylammonium bromide in alkyne oxidation for compounding.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. The structural formula of the catalyst for the phenylacetic acid preparation process is shown as a formula I:
2. a method of preparing the catalyst of claim 1, comprising:
s1: weighing monomers N-vinylimidazole and L-alpha-phosphatidylcholine-beta-arachidonoyl-gamma-stearoyl, dissolving in DMF, adding AIBN, stirring, reacting at high pressure and high temperature, vacuum drying, and grinding to obtain a product M;
s2: dissolving the product M in ethanol, adding n-bromoheptane in a dark place, stirring, centrifuging, washing and drying; then acidizing by using trifluoromethanesulfonic acid, centrifugally washing, and drying to obtain the catalyst.
3. The method for preparing a catalyst according to claim 2, characterized in that: in the step S1, the mass ratio of the monomer N-vinyl imidazole to the monomer L-alpha-phosphatidylcholine-beta-arachidonoyl-gamma-stearoyl is 1: 1.8 to 2.5.
4. The method for preparing a catalyst according to claim 2, characterized in that: the solid-to-liquid ratio of the product M to the n-bromoheptane in the step S2 is 1 g: 2-3 mL.
5. A method for producing phenylacetic acid, comprising:
carrying out sulfoesterification reaction on alcohol, and carrying out sulfoesterification treatment on 2-butyne-1, 4-diol by using p-toluenesulfonyl chloride to obtain a product A;
friedel-crafts alkylation reaction, benzene and the product A react to obtain a product B under the catalysis of the catalyst of claim 1;
oxidizing alkyne, taking tetrabutylammonium bromide as PCT and m-CPBA as an oxidant, and treating the product B to obtain phenylacetic acid.
6. The method for producing phenylacetic acid according to claim 5, wherein: in the sulfoesterification reaction of the alcohol, the molar ratio of the 2-butyne-1, 4-diol to the p-toluenesulfonyl chloride is 1: 2.4 to 2.8.
7. The method for producing phenylacetic acid according to claim 5, wherein: the mass ratio of benzene, the product A and the catalyst in the Friedel-crafts alkylation reaction is 1: 3.8-3.9: 0.3 to 0.5.
8. The method for producing phenylacetic acid according to claim 5, wherein: the yield of the product B in the Friedel-crafts alkylation reaction is more than 95 percent.
9. The method for producing phenylacetic acid according to claim 5, wherein: the molar ratio of the product B to the m-CPBA in the alkyne oxidation is 1: 5.8-6.2; the mass mol ratio of the tetrabutylammonium bromide to the product B is 1 g: 0.04 to 0.06 mol.
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| CN107297222A (en) * | 2017-06-14 | 2017-10-27 | 东南大学 | A kind of preparation of poly ion liquid solid acid catalyst and its application process |
Non-Patent Citations (2)
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| LIU，YH ET AL.: "the catalytic performance study of polymerized ionic liquid synthesized in different conditions on alkylation of o-xylene with styrene", 《APPLIED ORGANOMETALLIC CHEMISTRY》 * |
| 武燕娟: "苯乙酸合成工艺的研究", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ⅰ辑》 * |
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