CN112479863A - Method for preparing 2-methyl-4-chlorophenoxyacetic acid by catalytic chlorination of 2-methylphenoxyacetic acid - Google Patents
Method for preparing 2-methyl-4-chlorophenoxyacetic acid by catalytic chlorination of 2-methylphenoxyacetic acid Download PDFInfo
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- CN112479863A CN112479863A CN202011353841.2A CN202011353841A CN112479863A CN 112479863 A CN112479863 A CN 112479863A CN 202011353841 A CN202011353841 A CN 202011353841A CN 112479863 A CN112479863 A CN 112479863A
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- QJVXBRUGKLCUMY-UHFFFAOYSA-N 2-(2-methylphenoxy)acetic acid Chemical compound CC1=CC=CC=C1OCC(O)=O QJVXBRUGKLCUMY-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000005574 MCPA Substances 0.000 title claims abstract description 34
- WHKUVVPPKQRRBV-UHFFFAOYSA-N Trasan Chemical compound CC1=CC(Cl)=CC=C1OCC(O)=O WHKUVVPPKQRRBV-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 18
- 239000000460 chlorine Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002608 ionic liquid Substances 0.000 claims abstract description 8
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 5
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- -1 2-n-pentyl Chemical group 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 229910006130 SO4 Inorganic materials 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims 1
- 150000002460 imidazoles Chemical class 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 11
- 239000012847 fine chemical Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxyacetic acid Chemical compound OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- QCYOIFVBYZNUNW-UHFFFAOYSA-N 2-(dimethylazaniumyl)propanoate Chemical compound CN(C)C(C)C(O)=O QCYOIFVBYZNUNW-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 241000234653 Cyperus Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention relates to a preparation method of 2-methyl-4-chlorophenoxyacetic acid, in particular to a method for preparing 2-methyl-4-chlorophenoxyacetic acid by catalyzing and chlorinating 2-methyl phenoxyacetic acid. Taking o-methylphenoxyacetic acid (MPA) as a raw material, reacting in the presence of chlorine through a catalyst, and filtering to obtain 2-methyl-4-chlorophenoxyacetic acid (MCPA); wherein, the catalyst is imidazole ionic liquid. The method uses the catalyst, has higher reaction activity, carries out catalytic chlorination reaction on the o-tolyloxy acetic acid, and prepares the 2-methyl-4-chlorophenoxyacetic acid with high yield; compared with the existing literature reports, the reaction system is simple and convenient to operate, does not generate wastewater in the chlorination step, can obtain products with higher quality, and is beneficial to large-scale production.
Description
Technical Field
The invention relates to a preparation method of 2-methyl-4-chlorophenoxyacetic acid, in particular to a method for preparing 2-methyl-4-chlorophenoxyacetic acid by catalyzing and chlorinating 2-methyl phenoxyacetic acid.
Background
2-methyl-4-chlorophenoxyacetic acid, 2-methyl-4-chlorine for short, is a phenoxyacetic acid selective systemic transfer hormone type herbicide, is used for preventing and killing annual or perennial broadleaf weeds and partial nutgrass flatsedge, and is an important herbicide product. The structure is as follows.
According to the structure of the compound, the synthesis method mainly comprises the steps of firstly chlorinating to generate chlorophenol, and then synthesizing a raw medicine; and a route of using phenoxyacetic acid as a raw material to obtain a raw pesticide through chlorination. The chlorination method has the problem of generating dioxin compounds through over-reaction, and has no advantages in the aspects of product purification, production operation and the like, so that more methods are adopted for obtaining raw Medicines (MCPA) by taking o-tolyloxy acetic acid (MPA) as a raw material through chlorination reaction. As follows.
It has been reported that the above reaction is mainly carried out using chlorine gas in the presence of water.
US4515985 reports that MPA is added into water as a raw material, then the temperature is kept at 60 ℃, chlorine is introduced, and after the reaction is completed, the product MCPA is obtained after filtration, the content is 96 percent, and the yield is 92 percent.
WO9201663 reports that MPA is used as a raw material, catalysts N, N-dimethyl-2-aminopropionic acid and N, N-dimethylformamide are added into an aqueous solution, the temperature is kept at 20 ℃, the pH is controlled to be 8.5, sodium hypochlorite is dropwise added, hydrochloric acid is added after the reaction is completed, and filtration is performed to obtain the product MCPA with a yield of 96.8%.
CN201010269440.9 reports that MPA is used as a raw material, dimethylaminopyridine and N, N-dimethylformamide with catalytic amount are added into an alkaline aqueous solution, then chlorine is introduced at the temperature of 20-25 ℃, hydrochloric acid is added after the reaction is completed, and the product MCPA is obtained after filtration, wherein the content is 97.4% and the yield is 95.5%.
In the above reports, the raw material MPA reacts with chlorine or sodium hypochlorite in an aqueous solution, and a large amount of chlorinated wastewater is generated after the reaction, which generates a large pressure on subsequent environmental-friendly treatment and maintenance and operation of production equipment.
CN201810825161.2 reports that MPA is added into methyl ethyl carbonate, the temperature is kept at 50 ℃, chlorine is introduced, after the reaction is completed, water washing and filtration are carried out, and the product MCPA is obtained with the yield of 77.3 percent (calculated by o-cresol).
CN201110320431.2 reports that MPA is added into dichloromethane, the temperature is kept at 30 ℃, chlorine is introduced, and after the reaction is completed, filtration is carried out to obtain the product MCPA with the yield of 90 percent (calculated by MPA).
CN200310110175.X reports adding dichloroethane into MPA, maintaining at 75-80 deg.c, introducing chlorine gas to react completely to obtain coarse MCPA product with conversion rate of 90% and refining to obtain the product.
In the above report, the chlorination reaction is carried out using an organic solvent in the chlorination step, so that the problem of wastewater generated when water is used as a solvent is avoided, and good economy can be realized by recycling the organic solvent. However, in the above reports, the preparation of MPA requires post-treatment, i.e. the synthesized MPA needs to be purified, filtered, dried, etc. to achieve the corresponding yield.
Meanwhile, according to the guidance of the State safety administration on the enhancement of the work of evaluating the safety risk of the fine chemical reaction, the safety evaluation of the chlorination process reported in CN200310110175.X is 3 grade according to the specification of the third 2017 document No. 1 of the safety supervision general header.
In the research, the chlorination reaction is hoped to be carried out by adopting an organic solvent, the process simplicity is improved, and the MPA post-treatment is avoided. And by means of catalytic chlorination, the generation of three wastes is avoided, and meanwhile, higher yield and simplicity and convenience in process operation are realized. And reduces the risk of the process.
Disclosure of Invention
The invention aims to provide a method for preparing 2-methyl-4-chlorophenoxyacetic acid by catalyzing and chlorinating o-methylphenoxyacetic acid.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing 2-methyl-4-chlorophenoxyacetic acid by catalytic chlorination of o-tolyloxy acetic acid comprises the following steps: taking o-methylphenoxyacetic acid (MPA) as a raw material, reacting in the presence of chlorine through a catalyst, and filtering to obtain 2-methyl-4-chlorophenoxyacetic acid (MCPA); wherein, the catalyst is imidazole ionic liquid.
Dissolving the o-tolyloxy acetic acid in a solvent, adding a catalyst, introducing chlorine at 30-70 ℃, reacting until the analysis shows that the reaction is complete, about 3-7h, cooling to 0-5 ℃ after the reaction, and filtering to obtain the 2-methyl-4-chlorophenoxyacetic acid (MCPA).
The introduction amount of the chlorine is 1-2: 1(w/w, o-methylphenol/chlorine).
The catalyst is imidazole ionic liquid which can be in the form of solid, solution or aqueous solution, and has the following structural formula:
in the above formula:
R1、R2、R3、R4selected from H, C, which may be the same or different1-C5An alkyl group;
x is selected from halogen and SO4、HSO4、H2PO4、HPO4、PO4Or BF4；
The using amount of the catalyst is 30-300: 1(w/w, o-methyl phenol/pyridine ionic liquid).
Preferably in the formula:
R1、R2、R3、R4、R5may be the same or differentIs selected from H, methyl, ethyl, isopropyl, n-propyl, tert-butyl, n-butyl, isobutyl, n-pentyl, 2-n-pentyl, 3-methyl-2-butyl, tert-butyl or isobutyl;
x is selected from chlorine, bromine, iodine, SO4、HSO4、H2PO4、HPO4、PO4Or BF4。
Adding water and liquid caustic soda into o-methyl phenol serving as a raw material, mixing and stirring until the mixture is clear, heating to 100-130 ℃, dropwise adding sodium chloroacetate into the system at the temperature, finishing the addition within 2-4 hours, and keeping the same temperature to continuously react for 1-2 hours until the analysis shows that the reaction is complete; and adjusting the pH value of the system to be 0-2, adding an organic solvent for extraction, and separating a water layer to obtain an MPA solution.
The organic solvent is selected from 1, 2-dichloroethane, trichloromethane or halogenated alkane.
1: 6-9: 1-2; the addition amount of sodium chloroacetate is 1-2.
Extracting by 1, 2-dichloroethane or trichloromethane after the reaction, standing at 40-70 ℃ for layering, and collecting a lower organic phase which is MPA solution for MCPA synthesis.
The invention has the advantages that:
(1) compared with the prior literature report, the technical method avoids using water as a solvent, can reduce the generation of waste water and reduce the pressure of the production process on equipment corrosion and environmental protection treatment on the premise of realizing higher yield.
(2) According to the invention, by adding the catalyst, the production of a product with higher purity is realized and the generation of impurities is avoided on the premise of not carrying out MPA synthesis post-treatment.
(3) Compared with the prior literature report, the technical method of the invention adopts extraction and layering separation without purification processes such as filtration and drying, and the obtained MPA solution can be directly used for chlorination reaction, so that the method has better operation simplicity.
(4) According to the technical method, in the chlorination step, the imidazole ionic liquid is used as the catalyst, so that the high yield can be realized on the premise of obtaining qualified products. The overall yield of the two-step reaction of MPA and MCPA in this study can reach 90%, while the yield 90% is achieved when the comparative literature uses refined MPA to prepare MCPA.
(5) According to the technical method, the reaction temperature is reduced, the addition amount of raw materials and the introduction amount of chlorine are controlled by adding the catalyst, the process risk degree of the technical scheme is evaluated according to the specification of a file No. III (2017) 1 of safety supervision of the State safety administration for strengthening the safety risk evaluation work of the fine chemical reaction, the process risk degree is 1 grade, and compared with the process reported by the existing literature, the safety of the reaction process is better.
Drawings
FIG. 1 is a scheme showing the synthesis scheme of 2-methyl-4-chlorophenoxyacetic acid provided in the example of the present invention.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
In the preparation process, the catalyst is used, the reaction activity is higher, the catalytic chlorination reaction is carried out on the o-tolyloxy acetic acid, and the 2-methyl-4-chlorophenoxyacetic acid is prepared with high yield; compared with the existing literature reports, the reaction system is simple and convenient to operate, does not generate wastewater in the chlorination step, can obtain products with higher quality, and is beneficial to large-scale production.
Example 1
Adding 50g of raw material o-methylphenol and 200g of water into a reaction bottle, adding 62g of liquid alkali, stirring until the mixture is clear, heating to 120 ℃, controlling the same temperature, dropwise adding a prepared sodium chloroacetate aqueous solution (44 g of chloroacetic acid and 100g of water) for about 5 hours, and preserving the temperature for 2 hours until the reaction is complete; adding hydrochloric acid into a bottle until the pH value of the system is 1, then adding 700ml of dichloroethane for extraction, keeping the temperature at 50 ℃, standing for layering, and collecting the lower organic phase which is MPA feed liquid for the next step of reaction.
Adding the MPA feed liquid into a reaction bottle, adding 0.2g of catalyst 1-isopropyl-4-methylimidazole phosphate, starting stirring, keeping the temperature of the feed liquid at 70 ℃, keeping the temperature, starting introducing chlorine gas until the raw material is completely converted, stopping introducing the chlorine gas, consuming 35g of chlorine gas, cooling to 10 ℃, filtering, and drying to obtain a product MCPA77.8g, the purity of which is 95 percent and the yield of which is 79.8 percent (calculated by o-methylphenol).
Wherein, o-methyl phenol: the weight ratio of chlorine gas is 1.
Example 2
The difference from the embodiment 1 is that:
adding all MPA solution obtained in example 1 into a reaction bottle, adding 1g of catalyst 1,3, 4-tri-n-pentylimidazole tetrafluoroborate, starting stirring, keeping the temperature of the feed liquid at 30 ℃, keeping the temperature, starting introducing chlorine gas until the raw material is completely converted, stopping introducing the chlorine gas, consuming 47g of chlorine gas, cooling to 5 ℃, filtering, and drying to obtain a product MCPA84.3g, with the purity of 96% and the yield of 87.3% (calculated on o-methylphenol).
Wherein, o-methyl phenol: the weight ratio of chlorine gas is 1.5.
The embodiment evaluates the reaction process risk degree according to a fine chemical reaction safety risk evaluation guide rule (trial) in the guidance opinions of the State safety administration on strengthening the fine chemical reaction safety risk evaluation work, and the evaluation is grade 1.
Example 3
The difference from the embodiment 1 is that:
adding all MPA solution obtained in example 1 into a reaction bottle, adding 0.7g of catalyst 2-ethyl-4-isopropyl imidazole bromide, starting stirring, keeping the temperature of the feed liquid at 58 ℃, keeping the temperature, starting introducing chlorine gas until the raw material is completely converted, stopping introducing the chlorine gas, consuming 40g of chlorine gas, cooling to 0 ℃, filtering, and drying to obtain a product MCPA85.1g with the purity of 96% and the yield of 90.1% (calculated by o-methylphenol).
Wherein, o-methyl phenol: the weight ratio of chlorine gas is 1.2.
The embodiment evaluates the reaction process risk degree according to a fine chemical reaction safety risk evaluation guide rule (trial) in the guidance opinions of the State safety administration on strengthening the fine chemical reaction safety risk evaluation work, and the evaluation is grade 1.
Example 4
The difference from the embodiment 1 is that:
adding all MPA solution obtained in the example 1 into a reaction bottle, starting stirring, keeping the temperature of the feed liquid at 72 ℃, keeping the temperature, starting introducing chlorine gas until the raw material is completely converted, stopping introducing the chlorine gas, consuming 52g of the chlorine gas, cooling to 0 ℃, filtering, and drying to obtain a product MCPA67.9g, wherein the purity is 95 percent, and the yield is 69.5 percent (calculated by o-methylphenol).
Wherein, o-methyl phenol: the weight ratio of chlorine gas is 1.5.
The embodiment evaluates the reaction process risk degree according to a fine chemical reaction safety risk evaluation guide rule (trial) in the guidance opinions of the State safety administration on strengthening the fine chemical reaction safety risk evaluation work, and the evaluation is grade 3.
According to the embodiments, the process flow can be simplified through a catalytic chlorination mode, high reaction yield can be achieved, waste water generation is reduced, and corrosion hazard of equipment is reduced. In addition, the reduction of the chlorination temperature improves the safety of the synthesis process.
Claims (9)
1. A method for preparing 2-methyl-4-chlorophenoxyacetic acid by catalytic chlorination of o-tolyloxy acetic acid is characterized by comprising the following steps: taking o-methylphenoxyacetic acid (MPA) as a raw material, reacting in the presence of chlorine through a catalyst, and filtering to obtain 2-methyl-4-chlorophenoxyacetic acid (MCPA); wherein, the catalyst is imidazole ionic liquid.
2. The method of claim 1, wherein: dissolving the o-tolyloxy acetic acid in a solvent, adding a catalyst, introducing chlorine at 30-70 ℃, reacting for 3-7h, cooling to 0-5 ℃, and filtering to obtain 2-methyl-4-chlorophenoxyacetic acid (MCPA).
3. A method according to claim 1 or 2, characterized in that: the introduction amount of the chlorine is 1-2: 1(w/w, o-methylphenol/chlorine).
4. The method of claim 1, wherein: the catalyst is imidazole ionic liquid, and the structural formula of the catalyst is as follows:
in the above formula:
R1、R2、R3、R4may be the same or different and is selected from the group consisting of H, C1-C5 alkyl;
x is selected from halogen and SO4、HSO4、H2PO4、HPO4、PO4Or BF4；
The using amount of the catalyst is 30-300: 1(w/w, o-methylphenol/imidazole ionic liquid).
5. The method of claim 4, wherein: in the formula: r1、R2、R3、R4Which may be identical or different, are selected from H, methyl, ethyl, isopropyl, n-propyl, tert-butyl, n-butyl, isobutyl, n-pentyl, 2-n-pentyl, 3-methyl-2-butyl, tert-butyl, isobutyl;
x is selected from chlorine, bromine, iodine, SO4、HSO4、H2PO4、HPO4、PO4Or BF4。
6. The method of claim 1, wherein: adding water and liquid caustic soda into o-methyl phenol serving as a raw material, mixing and stirring until the mixture is clear, heating to 100-130 ℃, dropwise adding sodium chloroacetate into the system at the temperature, finishing the addition within 2-4 hours, and keeping the same temperature to continuously react for 1-2 hours until the analysis shows that the reaction is complete; and adjusting the pH value of the system to be 0-2, adding an organic solvent for extraction, and separating a water layer to obtain an MPA solution.
7. The method of claim 6, wherein: the organic solvent is selected from 1, 2-dichloroethane, trichloromethane or halogenated alkane.
8. The method of claim 6, wherein: 1 of o-methyl phenol, water and base: 6-9: 1-2; the addition amount of sodium chloroacetate is 1-2.
9. The method of claim 6, wherein: extracting by 1, 2-dichloroethane or trichloromethane after the reaction, standing at 40-70 ℃ for layering, and collecting a lower organic phase which is MPA solution for MCPA synthesis.
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