CN112479863B - Method for preparing 2-methyl-4-chlorophenoxyacetic acid by catalyzing and chlorinating 2-methylphenoxy acetic acid - Google Patents
Method for preparing 2-methyl-4-chlorophenoxyacetic acid by catalyzing and chlorinating 2-methylphenoxy acetic acid Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- 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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- 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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- 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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- C07—ORGANIC CHEMISTRY
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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-methylphenoxy acetic acid. O-Methyl Phenoxyacetic Acid (MPA) is used as a raw material, reacts in the presence of chlorine through a catalyst, and is filtered to obtain 2-methyl-4-chlorophenoxyacetic acid (MCPA); wherein the catalyst is imidazole ionic liquid. The catalyst has higher reaction activity, and the o-methyl phenoxyacetic acid is subjected to catalytic chlorination reaction to prepare the 2-methyl-4-chlorophenoxyacetic acid with high yield; compared with the prior literature reports, the reaction system is simple and convenient to operate, does not generate waste water in the chlorination step, can obtain a product with higher quality, and is beneficial to amplified 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-methylphenoxy acetic acid.
Background
2-methyl-4-chlorophenoxyacetic acid, namely 2-methyl-4-chlorine, is a phenoxyacetic acid selective systemic transfer hormone herbicide, is used for preventing and killing annual or perennial broadleaf weeds and part of 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 the original drug; and a route for obtaining the original medicine by chloridizing the phenoxyacetic acid serving as a raw material. Because the method of chlorination first has the problem of excessive reaction to generate dioxin compounds, and has no advantages in the aspects of product purification, production operation and the like, more methods of taking o-Methyl Phenoxyacetic Acid (MPA) as a raw material and obtaining crude drug (MCPA) through chlorination reaction are adopted. The following is provided.
It has been reported that chlorine is mainly used to carry out the above reaction in the presence of water.
US4515985 reports that adding MPA as a raw material into water, then maintaining 60 ℃, introducing chlorine, and filtering after the reaction is complete, to obtain the product MCPA, the content of which is 96%, and the yield of which is 92%.
WO9201663 reports that using MPA as a raw material, adding catalysts N, N-dimethyl-2-aminopropionic acid and N, N-dimethylformamide into an aqueous solution, maintaining the temperature at 20 ℃, controlling the ph=8.5, adding sodium hypochlorite dropwise, adding hydrochloric acid after the reaction is complete, and filtering to obtain the product MCPA with a yield of 96.8%.
CN201010269440.9 reports that taking MPA as raw material, adding catalyst amount of dimethylaminopyridine and N, N-dimethylformamide into alkaline aqueous solution, then keeping 20-25 ℃, introducing chlorine, adding hydrochloric acid after the reaction is complete, filtering to obtain the product MCPA, the content is 97.4%, and the yield is 95.5%.
In the report, raw material MPA reacts with chlorine or sodium hypochlorite in aqueous solution, a large amount of chlorinated wastewater is generated after the reaction, and a large pressure is generated for subsequent environmental protection treatment and maintenance and operation of production equipment.
CN201810825161.2 reports that MPA is added to ethyl methyl carbonate, the temperature is kept at 50 ℃, chlorine is introduced, after the reaction is complete, water is washed, and filtration is carried out, so that the product MCPA is obtained, the yield is 77.3% (calculated as o-methylphenol).
CN201110320431.2 reports that MPA is added to dichloromethane, maintained at 30 ℃, and after the reaction is complete, filtered to obtain the product MCPA in 90% (calculated as MPA).
CN200310110175.X reports that adding dichloroethane into MPA, maintaining 75-80 deg.C, introducing chlorine gas, obtaining crude MCPA after the reaction is completed, the conversion rate is 90%, and obtaining the product after refining.
The above report has been made to solve the problem of wastewater generation in the case of using water as a solvent by using an organic solvent for the chlorination reaction in the chlorination step, and can realize good economical efficiency by recycling the organic solvent. However, in the above reports, post-treatment is required for preparing MPA, that is, the synthetic MPA needs to be purified, filtered, dried, etc. to achieve the corresponding yield.
Meanwhile, according to the guidance opinion of the national security administration on strengthening the security risk assessment work of the fine chemical reaction, the security assessment is carried out on the chlorination process reported by CN200310110175.X according to the specification of the security administration three [ 2017 ] No. 1 document, and the security assessment is grade 3.
The present study is expected to improve the process simplicity and avoid post-treatment of MPA while using an organic solvent for the chlorination reaction. And by means of catalytic chlorination, the three wastes are avoided, and simultaneously, higher yield and simplicity of 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-methylphenoxy acetic acid.
In order to achieve the above purpose, the invention adopts the technical scheme that:
a method for preparing 2-methyl-4-chlorophenoxyacetic acid by catalyzing and chlorinating o-methylphenoxy acetic acid comprises the following steps: O-Methyl Phenoxyacetic Acid (MPA) is used as a raw material, reacts in the presence of chlorine through a catalyst, and is filtered to obtain 2-methyl-4-chlorophenoxyacetic acid (MCPA); wherein the catalyst is imidazole ionic liquid.
The o-methyl phenoxyacetic acid is dissolved in a solvent, a catalyst is added, chlorine is introduced at the temperature of 30-70 ℃ to react until analysis shows that the reaction is complete, the reaction time is about 3-7 hours, the temperature is reduced to 0-5 ℃ after the reaction, and the 2-methyl-4-chlorophenoxyacetic acid (MCPA) is obtained after filtration.
The introducing 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:
R 1 、R 2 、R 3 、R 4 may be the same or different selected from H, C 1 -C 5 An alkyl group;
x is selected from halogen, SO 4 、HSO 4 、H 2 PO 4 、HPO 4 、PO 4 Or BF 4 ；
The usage amount of the catalyst is 30-300:1 (w/w, o-methylphenol/pyridine ionic liquid).
Preferably, in the formula:
R 1 、R 2 、R 3 、R 4 、R 5 which may be the same or different, are selected from H, methyl, ethyl, isopropyl, n-propyl, t-butyl, n-butyl, isobutyl, n-pentyl, 2-n-pentyl, 3-methyl-2-butyl, t-butyl or isobutyl;
x is selected from chlorine, bromine, iodine, SO 4 、HSO 4 、H 2 PO 4 、HPO 4 、PO 4 Or BF 4 。
The o-Methyl Phenoxyacetic Acid (MPA) is prepared by adding water and liquid alkali into o-methyl phenol as raw materials, mixing and stirring until the mixture is clear, heating to 100-130 ℃, dropwise adding sodium chloroacetate into a system at the temperature for 2-4 hours, and keeping the same temperature for continuous reaction for 1-2 hours until analysis shows that the reaction is complete; adjusting the pH value of the system to be between 0 and 2, adding an organic solvent for extraction, and separating a water layer to obtain the MPA solution.
The organic solvent is selected from 1, 2-dichloroethane, chloroform or halogenated alkane.
O-methylphenol, water and base 1: 6-9:1-2; the adding amount of the sodium chloroacetate is 1-2.
Extracting the reaction product with 1, 2-dichloroethane or chloroform, standing at 40-70deg.C for layering, and collecting lower organic phase as MPA solution for MCPA synthesis.
The invention has the advantages that:
(1) Compared with the prior art, the technical method avoids using water as a solvent, can reduce the generation of wastewater and lighten 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 on the premise of not carrying out MPA post-synthesis treatment, and the generation of impurities is avoided.
(3) Compared with the prior art, the technical method of the invention adopts extraction and layering to separate without filtering, drying and other purification processes, and the obtained MPA solution can be directly used for chlorination reaction, thus having better operation simplicity.
(4) According to the technical method, in the chlorination step, imidazole ionic liquid is used as a catalyst, and on the premise of obtaining a qualified product, higher yield can be realized. The overall yield of the two-step reaction of MPA and MCPA in this study was 90%, whereas the comparison document achieved a yield of 90% when purified MPA was used to prepare MCPA.
(5) According to the technical method, the reaction temperature is reduced and the addition amount of raw materials and the introduction amount of chlorine are controlled by adding the catalyst, and the technical scheme is evaluated for the process risk degree according to the guidelines of the national security administration on the work of reinforcing the security risk assessment of the fine chemical reaction, and the security of the reaction process is better compared with the process reported in the prior document, wherein the specification of the security administration No. three 2017 No. 1 document is used for evaluating the process risk degree of the technical scheme.
Drawings
FIG. 1 is a diagram of a synthetic route for 2-methyl-4-chlorophenoxyacetic acid provided by an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention is further provided in connection with the accompanying examples, and it should be noted that the embodiments described herein are for the purpose of illustration and explanation only, and are not limiting of the invention.
The catalyst used in the preparation process has higher reaction activity, and the o-methyl phenoxyacetic acid is subjected to catalytic chlorination reaction to prepare the 2-methyl-4-chlorophenoxyacetic acid with high yield; compared with the prior literature reports, the reaction system is simple and convenient to operate, does not generate waste water in the chlorination step, can obtain a product with higher quality, and is beneficial to amplified 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 pre-prepared sodium chloroacetate aqueous solution (44 g of chloroacetic acid and 100g of water) for about 5 hours, and preserving the heat for 2 hours until the reaction is complete after the addition; hydrochloric acid was added to the flask until the pH of the system was=1, then 700ml of dichloroethane was added for extraction, and the mixture was kept at 50 ℃, allowed to stand for delamination, and the lower organic phase was collected as MPA feed liquid for the next reaction.
Adding the MPA feed liquid obtained above into a reaction bottle, adding 0.2g of catalyst 1-isopropyl-4-methylimidazole phosphate, starting stirring, maintaining the temperature of the feed liquid at 70 ℃, keeping the temperature, starting to introduce chlorine, stopping introducing the chlorine after the raw material is completely converted, consuming 35g of chlorine, cooling to 10 ℃, filtering, and drying to obtain the product MCPA77.8g with the purity of 95% and the yield of 79.8% (calculated by o-methylphenol).
Wherein, o-methylphenol: the weight ratio of chlorine is 1.
Example 2
The difference from example 1 is that:
adding all MPA solution obtained in example 1 into a reaction bottle, adding 1g of catalyst 1,3, 4-tri-n-pentane imidazole tetrafluoroborate, starting stirring, keeping the temperature of the feed liquid at 30 ℃, keeping the temperature, starting to introduce chlorine, stopping introducing the chlorine until the raw material is completely converted, consuming 47g of chlorine, cooling to 5 ℃, filtering, and drying to obtain the product MCPA84.3g with the purity of 96% and the yield of 87.3% (calculated by o-methylphenol).
Wherein, o-methylphenol: the weight ratio of the chlorine is 1.5.
The embodiment evaluates the risk of the reaction process according to the fine chemical reaction safety risk evaluation guideline (trial) in the national security administration guidance opinion about reinforcing fine chemical reaction safety risk evaluation work, which is 1 grade.
Example 3
The difference from example 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 feed liquid at 58 ℃, keeping the temperature, starting to introduce chlorine, stopping introducing the chlorine until the raw material is completely converted, consuming 40g of chlorine, cooling to 0 ℃, filtering, and drying to obtain the product MCPA85.1g with the purity of 96% and the yield of 90.1% (calculated by o-methylphenol).
Wherein, o-methylphenol: the weight ratio of the chlorine is 1.2.
The embodiment evaluates the risk of the reaction process according to the fine chemical reaction safety risk evaluation guideline (trial) in the national security administration guidance opinion about reinforcing fine chemical reaction safety risk evaluation work, which is 1 grade.
Example 4
The difference from example 1 is that:
adding all MPA solution obtained in example 1 into a reaction bottle, starting stirring, maintaining the temperature of feed liquid at 72 ℃, keeping the temperature, starting to introduce chlorine, stopping introducing the chlorine until the raw material is completely converted, consuming 52g of chlorine, cooling to 0 ℃, filtering, and drying to obtain the product MCPA67.9g with the purity of 95% and the yield of 69.5% (calculated by o-methylphenol).
Wherein, o-methylphenol: the weight ratio of the chlorine is 1.5.
The embodiment evaluates the risk of the reaction process according to the fine chemical reaction safety risk evaluation guideline (trial) in the national safety supervision administration's guidance opinion about reinforcing fine chemical reaction safety risk evaluation work, which is grade 3.
The method can simplify the process flow in a catalytic chlorination mode, realize higher reaction yield, reduce the generation of wastewater and reduce the corrosion hazard of equipment. In addition, the reduction of the chlorination temperature improves the safety of the synthesis process.
Claims (5)
1. A method for preparing 2-methyl-4-chlorophenoxyacetic acid by catalyzing and chlorinating o-methylphenoxy acetic acid is characterized by comprising the following steps: o-methyl phenoxyacetic acid is used as a raw material, reacts in the presence of chlorine through a catalyst, and is filtered to obtain 2-methyl-4-phenoxyacetic acid; wherein the catalyst is imidazole ionic liquid;
dissolving o-methyl phenoxyacetic acid in a solvent, adding a catalyst, introducing chlorine at 30-70 ℃, reacting for 3-7h, reducing the temperature to 0-5 ℃, and filtering to obtain 2-methyl-4-chlorophenoxyacetic acid;
the catalyst is imidazole ionic liquid, and the structural formula is as follows:
in the above formula:
R 1 、R 2 、R 3 、R 4 may be the same or different and are selected from H, C1-C5 alkyl groups;
x is selected from halogen, HSO 4 、H 2 PO 4 Or BF 4 ；
The o-methyl phenoxyacetic acid is prepared by adding water and liquid alkali into o-methyl phenol serving as raw materials, mixing and stirring until the mixture is clear, heating to 100-130 ℃, dropwise adding sodium chloroacetate into a system at the temperature, after 2-4 hours of addition, keeping the same temperature for continuous reaction for 1-2 hours until analysis and display of complete reaction; adjusting the pH value of the system to be between 0 and 2, adding an organic solvent for extraction, and separating a water layer to obtain an o-methyl phenoxyacetic acid solution;
the catalyst is used in the mass ratio of o-methylphenol/imidazole ionic liquid of 30-300:1.
2. The method of claim 1, wherein: the chlorine gas is introduced into the reactor in a mass ratio of o-methyl phenol to chlorine gas of 1-2:1.
3. The method of claim 1, wherein: in the formula:
R 1 、R 2 、R 3 、R 4 which may be the same or different, are selected from H, methyl, ethyl, isopropyl, n-propyl, t-butyl, n-butyl, isobutyl, n-pentyl, 2-n-pentyl, 3-methyl-2-butyl;
x is selected from chlorine, bromine, iodine, HSO 4 、H 2 PO 4 Or BF 4 。
4. The method of claim 1, wherein: the organic solvent is selected from 1, 2-dichloroethane or chloroform.
5. The method of claim 1, wherein: extracting the reaction product with 1, 2-dichloroethane or chloroform, standing at 40-70 ℃ for layering, and collecting the lower organic phase which is o-methyl phenoxyacetic acid solution for synthesizing 2-methyl-4-chlorophenoxyacetic acid.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336654A (en) * | 2011-07-14 | 2012-02-01 | 大连化工研究设计院 | Chlorination method of phenoxyacetic acid and its derivatives |
| CN103058855A (en) * | 2011-10-20 | 2013-04-24 | 上海泰禾化工有限公司 | Method for synthesizing phenoxyacetic acid derivative |
| RU2563831C1 (en) * | 2014-10-13 | 2015-09-20 | Федеральное государственное бюджетное учреждение науки Иркутский институт химии им. А.Е. Фаворского Сибирского отделения Российской академии наук | Using protatran 4-chlor-2-methylphenoxyacetate (chlorcresacin) for arrest of cholesterolesterase activity |
| CN104945240A (en) * | 2015-06-01 | 2015-09-30 | 安徽华星化工有限公司 | Synthetic method of 2-methyl-4-chlorophenoxyacetic acid |
| CN106632014A (en) * | 2016-12-21 | 2017-05-10 | 嘉兴学院 | Preparation of 2-amino-5-chloropyridine |
| CN108727196A (en) * | 2018-07-23 | 2018-11-02 | 安徽华星化工有限公司 | A method of producing the esters of 2-methyl-4-chlorophenoxyacetic acid |
| CN108774126A (en) * | 2018-06-29 | 2018-11-09 | 江苏健谷化工有限公司 | 2-methyl-4-chlorophenoxyacetic acid production technology |
| CN110028399A (en) * | 2018-01-11 | 2019-07-19 | 上海泰禾国际贸易有限公司 | A kind of preparation method of 2-methyl-4-chlorophenoxyacetic acid |
-
2020
- 2020-11-27 CN CN202011353841.2A patent/CN112479863B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336654A (en) * | 2011-07-14 | 2012-02-01 | 大连化工研究设计院 | Chlorination method of phenoxyacetic acid and its derivatives |
| CN103058855A (en) * | 2011-10-20 | 2013-04-24 | 上海泰禾化工有限公司 | Method for synthesizing phenoxyacetic acid derivative |
| RU2563831C1 (en) * | 2014-10-13 | 2015-09-20 | Федеральное государственное бюджетное учреждение науки Иркутский институт химии им. А.Е. Фаворского Сибирского отделения Российской академии наук | Using protatran 4-chlor-2-methylphenoxyacetate (chlorcresacin) for arrest of cholesterolesterase activity |
| CN104945240A (en) * | 2015-06-01 | 2015-09-30 | 安徽华星化工有限公司 | Synthetic method of 2-methyl-4-chlorophenoxyacetic acid |
| CN106632014A (en) * | 2016-12-21 | 2017-05-10 | 嘉兴学院 | Preparation of 2-amino-5-chloropyridine |
| CN110028399A (en) * | 2018-01-11 | 2019-07-19 | 上海泰禾国际贸易有限公司 | A kind of preparation method of 2-methyl-4-chlorophenoxyacetic acid |
| CN108774126A (en) * | 2018-06-29 | 2018-11-09 | 江苏健谷化工有限公司 | 2-methyl-4-chlorophenoxyacetic acid production technology |
| CN108727196A (en) * | 2018-07-23 | 2018-11-02 | 安徽华星化工有限公司 | A method of producing the esters of 2-methyl-4-chlorophenoxyacetic acid |
Non-Patent Citations (1)
| Title |
|---|
| 氯化烷基咪唑:一种氯气吸收及氯化反应的媒介;施沈一等;《有机化学》;20110215(第02期);227-230 * |
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