CN113896714A - Method for synthesizing chlorantraniliprole - Google Patents
Method for synthesizing chlorantraniliprole Download PDFInfo
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- CN113896714A CN113896714A CN202111391383.6A CN202111391383A CN113896714A CN 113896714 A CN113896714 A CN 113896714A CN 202111391383 A CN202111391383 A CN 202111391383A CN 113896714 A CN113896714 A CN 113896714A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
The invention discloses a synthesis method of chlorantraniliprole, which relates to the field of pesticide chlorantraniliprole synthesis and comprises the following steps of firstly, preparing a four-neck flask, adding 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formic acid, and uniformly stirring; the method takes 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formic acid as a starting material, adopts an acyl chlorination reagent, takes toluene, acetonitrile or dichloroethane (preferably toluene) as a solvent, synthesizes an acyl chloride toluene solution of the acid through acyl chlorination reaction, does not separate, adds 2-amino-5-chloro-N, 3-dimethyl benzamide into the acyl chloride toluene solution, and performs reflux reaction to obtain a chlorantraniliprole product.
Description
Technical Field
The invention relates to the field of synthesizing pesticide chlorantraniliprole, in particular to a method for synthesizing chlorantraniliprole.
Background
The problems of pesticide residue in agricultural products and toxicity to animals are always the focus of attention of people, in recent years, DuPont companies of various high-efficiency and low-toxicity pesticides are successfully developed, the influence of the pesticides on the environment is changed, the pesticides in the world are successfully researched and developed, chlorantraniliprole has strong permeability and systemic conductivity, and the pesticide entering the plants is conducted to other parts without being applied along xylem, so that the neogenetic tissue is protected; stomach toxicity is the main component, and contact killing is the secondary component; long lasting period and rain wash resistance.
According to the search, Chinese patent No. CN _101072767_ A discloses a method for preparing N-phenylpyrazole-1-formamide, which synthesizes chlorantraniliprole (3-bromo-N- [ 4-chloro-2-methyl-6- (methylcarbamoyl) benzene ] -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-formamide) by condensing 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-carboxylic acid with 2-amino-5-chloro-N, 3-methylbenzamide, uses pyridine, methylsulfonyl chloride, acetonitrile and other reagents, generates a large amount of pyridine and sodium chloride, the sodium methanesulfonate produces high-salt waste water, and the cost of pyridine recovery and waste water treatment is very high.
Disclosure of Invention
The invention aims to: in order to solve the technical problem, a synthesis method of chlorantraniliprole is provided.
In order to achieve the purpose, the invention provides the following technical scheme: a method for synthesizing chlorantraniliprole comprises the following steps,
firstly, preparing a four-neck flask, adding 3-bromo-1- (3-chloro-2-pyridyl) -1-hydrogen-pyrazole-5-formic acid, and uniformly stirring;
adding an acyl chlorination reagent in the stirring process, heating to 70-110 ℃, and carrying out heat preservation reaction until the system is clear, so as to obtain a 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formyl chloride toluene solution;
adding 2-amino-5-chloro-N, 3-dimethylbenzamide (purity 97.0%, 63.9g and 0.313mol) into the 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formyl chlorotoluene solution, heating to reflux, finishing the reaction, and cooling in an ice-water bath;
and step four, carrying out vacuum filtration, washing the filter cake with a small amount of toluene, and after pumping, carrying out vacuum drying on the filter cake at 80 ℃ to obtain chlorantraniliprole (the content is 98%, the yield is 126.3g, and the yield is 86%) which is a white powdery solid.
Further, the flask which can be described in the first step was equipped with a mechanical stirrer, a thermometer and a condenser and had a volume of 1000 ml.
Further, the acyl chlorination reagent in the second step is one or more of thionyl chloride, triphosgene, diphosgene, phosgene and oxalyl chloride, and the triphosgene is preferred.
Furthermore, the reflux reaction time in the third step is controlled to be 5 to 6 hours, and the temperature is reduced to be below 10 ℃.
Further, the synthetic route of the chlorantraniliprole is as follows:
compared with the prior art, the invention has the beneficial effects that:
1. the method takes 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formic acid as a starting material, adopts an acyl chlorination reagent, takes toluene, acetonitrile or dichloroethane (preferably toluene) as a solvent, synthesizes an acyl chloride toluene solution of the acid through acyl chlorination reaction, does not separate, adds 2-amino-5-chloro-N, 3-dimethyl benzamide into the acyl chloride toluene solution, and performs reflux reaction to obtain a chlorantraniliprole product.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of examples.
Example (b): a method for synthesizing chlorantraniliprole comprises the following steps,
firstly, preparing a 1000ml four-mouth flask provided with a mechanical stirrer, a thermometer and a condenser, adding 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formic acid (purity 98.5%, 100g, 0.298mol), 600ml of toluene and DMF (purity 99%, 0.5g, 0.007mol), and uniformly stirring;
adding triphosgene (with the purity of 99 percent, 100g and 0.334mol) in the stirring process, heating to 70-110 ℃, generating a large amount of gas, and carrying out heat preservation reaction until the system is clear, so as to obtain a 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formyl chloride toluene solution;
adding 2-amino-5-chloro-N, 3-methylbenzamide (purity 97.0%, 63.9g and 0.313mol) into the 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formyl chlorotoluene solution, heating to reflux, carrying out reflux reaction for 5 hours, finishing the reaction, cooling in an ice water bath, and cooling to below 10 ℃;
and step four, carrying out vacuum filtration, washing the filter cake with a small amount of toluene, and after pumping, carrying out vacuum drying on the filter cake at 80 ℃ to obtain chlorantraniliprole (the content is 98%, the yield is 126.3g, and the yield is 86%) which is a white powdery solid.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (5)
1. A method for synthesizing chlorantraniliprole is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
firstly, preparing a four-neck flask, adding 3-bromo-1- (3-chloro-2-pyridyl) -1-hydrogen-pyrazole-5-formic acid, and uniformly stirring;
adding an acyl chlorination reagent in the stirring process, heating to 70-110 ℃, and carrying out heat preservation reaction until the system is clear, so as to obtain a 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formyl chloride toluene solution;
adding 2-amino-5-chloro-N, 3-dimethylbenzamide (purity 97.0%, 63.9g and 0.313mol) into the 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formyl chlorotoluene solution, heating to reflux, finishing the reaction, and cooling in an ice-water bath;
and step four, carrying out vacuum filtration, washing the filter cake with a small amount of toluene, and after pumping, carrying out vacuum drying on the filter cake at 80 ℃ to obtain chlorantraniliprole (the content is 98%, the yield is 126.3g, and the yield is 86%) which is a white powdery solid.
2. The method for synthesizing chlorantraniliprole according to claim 1, which is characterized in that: the flask that can be described in step one was equipped with a mechanical stirrer, thermometer and condenser, and had a volume of 1000 ml.
3. The method for synthesizing chlorantraniliprole according to claim 1, which is characterized in that: and the acyl chlorination reagent in the step two is one or more of thionyl chloride, triphosgene, diphosgene, phosgene and oxalyl chloride, and the triphosgene is preferred.
4. The method for synthesizing chlorantraniliprole according to claim 1, which is characterized in that: in the third step, the reflux reaction time is controlled to be 5-6 hours, and the temperature is reduced to be below 10 ℃.
5. The method for synthesizing chlorantraniliprole according to claim 1, which is characterized in that: the synthetic route of the chlorantraniliprole is as follows:
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| CN202111391383.6A CN113896714A (en) | 2021-11-23 | 2021-11-23 | Method for synthesizing chlorantraniliprole |
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| CN202111391383.6A CN113896714A (en) | 2021-11-23 | 2021-11-23 | Method for synthesizing chlorantraniliprole |
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2021
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Application publication date: 20220107 |