CN111517975A - Preparation method of 2-amino-5-chloro-N, 3-dimethylbenzamide - Google Patents
Preparation method of 2-amino-5-chloro-N, 3-dimethylbenzamide Download PDFInfo
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- CN111517975A CN111517975A CN202010459411.2A CN202010459411A CN111517975A CN 111517975 A CN111517975 A CN 111517975A CN 202010459411 A CN202010459411 A CN 202010459411A CN 111517975 A CN111517975 A CN 111517975A
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- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
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- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
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- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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Abstract
The invention relates to a preparation method of 2-amino-5-chloro-N, 3-dimethylbenzamide. The preparation method comprises the following steps: 2-nitro-3-methyl benzoic acid is taken as an initial raw material, and the 2-amino-5-chloro-N, 3-dimethyl benzamide is obtained by reduction reaction, chlorination reaction, esterification reaction and ammonolysis reaction in sequence. The preparation method provides a new path for synthesizing the 2-amino-5-chloro-N, 3-dimethylbenzamide, the yield of the whole route can reach more than 80%, the cost is obviously reduced, the reaction conditions of each step are mild, the quantity of three wastes is small, and the preparation method is suitable for industrial production.
Description
Technical Field
The invention relates to a preparation method of 2-amino-5-chloro-N, 3-dimethylbenzamide.
Background
Chlorantraniliprole, the common name of which is Chlorantranilprole, is an anthranilamide pesticide successfully developed by DuPont in 2000, the trade names of which are Altaco, Coragen, Rynaxypyr, KANGWI and KK technical products, and the chemical name of which is: 3-bromo-N- { 4-chloro-2-methyl-6- [ (methylamino) carbonyl]Phenyl } -1- (3-chloro-2-pyridines)Pyridyl) -1H-pyrazole-5-amide with CAS registry number of 500008-45-7 and molecular formula of C18H14BrCl2N5O2The chemical structural formula is as follows:
2-amino-5-chloro-N, 3-dimethyl benzamide is an important intermediate for synthesizing chlorantraniliprole, and the existing 2-amino-5-chloro-N, 3-dimethyl benzamide synthesis methods mainly comprise two methods. The first method comprises the following steps: o-toluidine is used as a raw material, the o-toluidine is condensed with chloral hydrate and hydroxylamine hydrochloride to generate oxime, the oxime is dehydrated and subjected to ring closing under the action of concentrated sulfuric acid to obtain isatin, then the isatin anhydride is oxidized by hydrogen peroxide to generate isatoic anhydride, the isatoic anhydride is subjected to ring opening by methylamine gas to obtain 2-amino-N, 3-dimethylbenzamide, and finally the 2-amino-5-chloro-N, 3-dimethylbenzamide is obtained by chlorination of sulfuryl chloride. The whole route has the advantages that the starting material o-toluidine is cheaper, and the disadvantages that the total yield is lower and is only about 30 percent, and the total raw material cost is higher. And a large amount of Na is used in the reaction process2SO4And concentrated sulfuric acid, the three wastes are large. A specific synthetic route of the method is as follows:
the second method comprises the following steps: 2-amino-3-methylbenzoic acid is taken as a raw material, NCS chlorination is firstly carried out to obtain 2-amino-5-chloro-3-methylbenzoic acid, then solid phosgene cyclization is carried out to obtain a compound 11, and finally ring opening is carried out by methylamine gas to obtain an intermediate 2-amino-5-chloro-N, 3-dimethylbenzamide. The whole route has the advantage of high total yield of about 70%. Disadvantages are that the starting material 2-amino-3-methylbenzoic acid is expensive, the chlorination reaction uses expensive and atom-uneconomical NCS, the cyclization uses solid phosgene, the atom is uneconomical, and a large amount of HCl is generated and needs to be neutralized by adding alkali, so that a large amount of solid waste is generated. The specific synthetic route of the second method is as follows:
the method I is used for preparing the 2-amino-5-chloro-N, 3-dimethylbenzamide, and has the advantages of lower total yield, higher total raw material cost and more three wastes; the preparation of 2-amino-5-chloro-N, 3-dimethylbenzamide by the second method has higher total cost and more solid wastes due to the more expensive starting materials and used reagents. Therefore, the development of a synthetic method which has high yield, low cost, high atom economy and environmental friendliness is of great significance for the industrialization of the 2-amino-5-chloro-N, 3-dimethylbenzamide.
Disclosure of Invention
The invention aims to provide a novel preparation method of 2-amino-5-chloro-N, 3-dimethylbenzamide, which has high yield, low cost, high atom economy and less three wastes.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of 2-amino-5-chloro-N, 3-dimethylbenzamide, which comprises the following steps:
K1. 2-nitro-3-methylbenzoic acid is used as an initial raw material to carry out reduction reaction to obtain 2-amino-3-methylbenzoic acid;
K2. performing chlorination reaction on 2-amino-3-methylbenzoic acid to obtain 2-amino-5-chloro-3-methylbenzoic acid;
K3. carrying out esterification reaction on 2-amino-5-chloro-3-methylbenzoic acid to obtain 2-amino-5-chloro-3-methylbenzoate;
K4. 2-amino-5-chloro-3-methylbenzoate is subjected to ammonolysis reaction to obtain 2-amino-5-chloro-N, 3-dimethylbenzoyl.
Preferably, the 2-nitro-3-methylbenzoic acid described in K1 is subjected to the reduction reaction with hydrogen in ethanol under the presence of a catalyst.
In the invention, the specific operation steps of the reduction reaction are as follows: dissolving 2-nitro-3-methylbenzoic acid in ethanol, placing the solution in a hydrogenation kettle, adding a catalyst, closing the hydrogenation kettle, introducing hydrogen, heating for reaction, filtering while the solution is hot after the reaction is finished, recovering the catalyst, and distilling the filtrate under reduced pressure to remove the solvent to obtain the 2-amino-3-methylbenzoic acid.
Preferably, the feeding mass ratio of the 2-nitro-3-methylbenzoic acid to the ethanol in the reduction reaction is 1: 4-6, preferably 1: 5.
Preferably, nitrogen is used for 1 to 3 times before the introduction of hydrogen.
Preferably, the catalyst is raney nickel.
Further preferably, the feeding mass ratio of the 2-nitro-3-methylbenzoic acid to the raney nickel is 1: 0.01-0.05.
More preferably, the hydrogen pressure is 0.1 to 1.5 MPa.
Further preferably, the reaction temperature of the reduction reaction is 20 ℃ to 80 ℃.
More preferably, the reaction temperature of the reduction reaction is 50 ℃ to 70 ℃.
More preferably, the reaction time of the reduction reaction is 3 to 8 hours.
More preferably, the reaction time of the reduction reaction is 4 to 6 hours.
Preferably, the 2-amino-3-methylbenzoic acid described in K2 is subjected to the chlorination reaction with chlorine in an organic solvent.
In the invention, the specific operation steps of the chlorination reaction are as follows: placing 2-amino-3-methylbenzoic acid into a reaction container, adding an organic solvent, stirring and heating, introducing chlorine gas for reaction, cooling to room temperature after the reaction is finished, and filtering to obtain 2-amino-5-chloro-3-methylbenzoic acid.
The feeding mass ratio of the 2-amino-3-methylbenzoic acid to the organic solvent in the chlorination reaction is 1: 4-6, and preferably 1: 5.
Further preferably, the organic solvent includes but is not limited to one or more of chloroform, dichloroethane, acetonitrile, tetrahydrofuran.
More preferably, the solvent is dichloroethane.
Further preferably, the feeding molar ratio of the 2-amino-3-methylbenzoic acid to the chlorine gas is 1: 1-1.5.
Further preferably, the reaction temperature of the chlorination reaction is 20-80 ℃.
More preferably, the reaction temperature of the chlorination reaction is 50 ℃ to 60 ℃.
More preferably, the reaction time of the chlorination reaction is 2 to 4 hours.
Preferably, the esterification of 2-amino-5-chloro-3-methylbenzoic acid described in K3 with an alcohol is carried out in the presence of concentrated sulfuric acid.
In the invention, the esterification reaction comprises the following specific operation steps: placing 2-amino-5-chloro-3-methylbenzoic acid into a reaction container, adding alcohol, cooling in an ice water bath, dropwise adding concentrated sulfuric acid, heating for reflux reaction after dropwise adding, distilling to remove alcohol after reaction, adding water, pulping at room temperature, and filtering to obtain 2-amino-5-chloro-3-methylbenzoic acid methyl ester.
The feeding mass ratio of the 2-amino-5-chloro-3-methylbenzoic acid to the alcohol in the esterification reaction is 1: 4-6, and preferably 1: 5.
Further preferably, the alcohol includes but is not limited to one or more of methanol, ethanol, isopropanol and n-butanol.
Further preferably, the feeding molar ratio of the 2-amino-5-chloro-3-methylbenzoic acid to the concentrated sulfuric acid is 1: 0.1-0.5.
Further preferably, the reaction time of the chlorination reaction is 4 to 10 hours.
Preferably, the 2-amino-5-chloro-3-methylbenzoate described in K4 is subjected to the aminolysis reaction with methylamine in an alcohol.
In the invention, the specific operation steps of the ammonolysis reaction are as follows: adding 2-amino-5-chloro-3-methyl benzoate and alcohol into a reaction container, stirring and heating, introducing methylamine gas for reaction, and distilling to remove the alcohol after the reaction is finished to obtain the 2-amino-5-chloro-N, 3-dimethyl benzamide.
The feeding mass ratio of the methyl 2-amino-5-chloro-3-methylbenzoate to the alcohol in the ammonolysis reaction is 1: 3-5, and preferably 1: 4.
Further preferably, the alcohol is one or more of methanol, ethanol, isopropanol and n-butanol.
Further preferably, the feeding molar ratio of the 2-amino-5-chloro-3-methylbenzoate to the methylamine is 1: 1-1.5.
Further preferably, the reaction temperature of the ammonolysis reaction is 20 ℃ to 60 ℃.
More preferably, the reaction temperature of the ammonolysis reaction is 45-60 ℃.
Further preferably, the reaction time of the ammonolysis reaction is 2 to 8 hours.
The reaction formula of the invention is as follows:
the preparation method provides a new path for the synthesis of the 2-amino-5-chloro-N, 3-dimethylbenzamide, the reaction conditions of the steps in the preparation method are mild, the yield is high, the total yield is more than 80%, the quantity of three wastes is small, no solid waste is generated, the preparation method is environment-friendly and suitable for industrial production, the problems of low reaction yield, high cost, poor atom economy and more three wastes in the prior art are solved, and the production cost of the intermediate 2-amino-5-chloro-N, 3-dimethylbenzamide is greatly reduced, so that the production cost of the chlorantraniliprole is reduced, and convenience is provided for the industrial production of the chlorantraniliprole.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
the new preparation method of the 2-amino-5-chloro-N, 3-dimethylbenzamide has the advantages of high yield, low cost, high atom economy and less three wastes, and is suitable for industrial production.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments, but the present invention is not limited to the following embodiments. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
Example 1
Preparation of K1, 2-amino-3-methylbenzoic acid
Dissolving 10g (55.2mmol) of 2-nitro-3-methylbenzoic acid in 50g of ethanol, placing the mixture in a hydrogenation kettle, adding 0.4g of Raney nickel, closing the hydrogenation kettle, replacing with nitrogen for 3 times, introducing 0.2MPa hydrogen, starting stirring, heating to 50 ℃ and reacting for 4 hours. After the reaction, raney nickel was recovered by hot filtration, and the solvent was removed from the filtrate by distillation under reduced pressure to obtain 8.2g of 2-amino-3-methylbenzoic acid with a yield of 98.3%.
Preparation of K2, 2-amino-5-chloro-3-methylbenzoic acid
8g (53mmol) of 2-amino-3-methylbenzoic acid are placed in a flask, 40g of dichloroethane are added, stirring is switched on, the temperature is raised to 50 ℃ and 4.5g (63.4mmol) of chlorine are slowly passed through for reaction for 3 h. After the reaction, the temperature was decreased to room temperature and filtration was conducted to obtain 9.6g of 2-amino-5-chloro-3-methylbenzoic acid (3) in 98.1% yield.
Preparation of K3.2-amino-5-chloro-3-methylbenzoic acid methyl ester
9g (48.6mmol) of 2-amino-5-chloro-3-methylbenzoic acid is placed in a flask, 45g of methanol is added, stirring is started, an ice water bath is cooled to 5 ℃, 0.95g (9.7mmol) of concentrated sulfuric acid is added dropwise, and after the dropwise addition is finished, the temperature is increased for reflux reaction for 8 hours. After the reaction, methanol was distilled off, 10g of water was added, and after beating at room temperature for 0.5 hour, methyl 2-amino-5-chloro-3-methylbenzoate was obtained by filtration in a yield of 95%.
Preparation of K4.2-amino-5-chloro-N, 3-dimethylbenzamide
After 9g (45.1mmol) of methyl 2-amino-5-chloro-3-methylbenzoate was dissolved in 36g of methanol, the mixture was placed in a flask, stirred, heated to 45 ℃ and slowly charged with 1.7g (54.8mmol) of methylamine gas to react for 6 hours. After the completion of the reaction, methanol was distilled off to obtain 8.7g of 2-amino-5-chloro-N, 3-dimethylbenzamide in a yield of 97.2%.
Example 2
Preparation of K1, 2-amino-3-methylbenzoic acid
40g (221mmol) of 2-nitro-3-methylbenzoic acid is dissolved in 200g of ethanol and then placed in a hydrogenation kettle, 1.2g of Raney nickel is added, then the hydrogenation kettle is closed, nitrogen is replaced for 3 times, then 0.3MPa hydrogen is introduced, stirring is started, and the temperature is raised to 60 ℃ for reaction for 6 hours. After the reaction, Raney nickel is recovered by hot filtration, and the filtrate is subjected to reduced pressure distillation to remove the solvent, so that 32g of 2-amino-3-methylbenzoic acid is obtained, and the yield is 95.9%.
Preparation of K2, 2-amino-5-chloro-3-methylbenzoic acid
30g (198.7mmol) of 2-amino-3-methylbenzoic acid are placed in a flask, 150g of acetonitrile are added, stirring is started, the temperature is raised to 60 ℃, 20.5g (288.7mmol) of chlorine gas is slowly introduced and the reaction is carried out for 4 h. After the reaction, the temperature was decreased to room temperature and filtration was carried out to obtain 35.4g of 2-amino-5-chloro-3-methylbenzoic acid in a yield of 96%.
Preparation of K3.2-amino-5-chloro-3-methylbenzoic acid ethyl ester
Placing 30g (161.7mmol) of 2-amino-5-chloro-3-methylbenzoic acid into a flask, adding 150g of ethanol, starting stirring, cooling to 5 ℃ in an ice water bath, dropwise adding 4.75g (48.5mmol) of concentrated sulfuric acid, and heating to reflux for 6 hours after dropwise adding. After the reaction is finished, ethanol is removed by reduced pressure distillation, 30g of water is added, pulping is carried out for 0.5h at room temperature, and then filtration is carried out to obtain 31.8g of ethyl 2-amino-5-chloro-3-methylbenzoate, wherein the yield is 92.1%.
Preparation of K4.2-amino-5-chloro-N, 3-dimethylbenzamide
30g (140.5mmol) of ethyl 2-amino-5-chloro-3-methylbenzoate are dissolved in 120g of methanol and placed in a flask, stirring is started, the temperature is raised to 50 ℃, and then 5.7g (182.6mmol) of methylamine gas is slowly introduced for reaction for 6 h. After the reaction, ethanol was distilled off to obtain 26.6g of 2-amino-5-chloro-N, 3-dimethylbenzamide with a yield of 95.4%.
Example 3
Preparation of K1, 2-amino-3-methylbenzoic acid
Dissolving 90g (497.2mmol) of 2-nitro-3-methylbenzoic acid in 450g of ethanol, placing the mixture in a hydrogenation kettle, adding 1.8g of Raney nickel, closing the hydrogenation kettle, replacing with nitrogen for 3 times, introducing 0.5MPa hydrogen, stirring, heating to 70 ℃, and reacting for 5 hours. And after the reaction is finished, filtering while the reaction is hot to recover raney nickel, and distilling the filtrate under reduced pressure to remove the solvent to obtain 73g of 2-amino-3-methylbenzoic acid with the yield of 97.2 percent.
Preparation of K2, 2-amino-5-chloro-3-methylbenzoic acid
70g (463.6mmol) of 2-amino-3-methylbenzoic acid are dissolved in 350g of tetrahydrofuran and placed in a flask, stirring is started, the temperature is raised to 50 ℃ and 46.1g (649.3mmol) of chlorine are slowly introduced and the reaction is carried out for 2 h. After the reaction, the temperature was decreased to room temperature and filtration was carried out to obtain 82g of 2-amino-5-chloro-3-methylbenzoic acid in a yield of 95.4%.
Preparation of isopropyl K3.2-amino-5-chloro-3-methylbenzoate
Placing 80g (431.3mmol) of 2-amino-5-chloro-3-methylbenzoic acid in a flask, adding 400g of isopropanol, starting stirring, cooling to 5 ℃ in an ice water bath, dropwise adding 10.6g (108mmol) of concentrated sulfuric acid, and heating to carry out reflux reaction for 6 hours after dropwise adding. After the reaction is finished, the isopropanol is removed by reduced pressure distillation, 80g of water is added, pulping is carried out for 0.5h at room temperature, and then filtration is carried out to obtain 93g of isopropyl 2-amino-5-chloro-3-methylbenzoate, wherein the yield is 94.8%.
Preparation of K4.2-amino-5-chloro-N, 3-dimethylbenzamide
90g (395.6mmol) of isopropyl 2-amino-5-chloro-3-methylbenzoate are dissolved in 360g of isopropanol and placed in a flask, stirring is started, the temperature is raised to 60 ℃, and then 17.2g (554.8mmol) of methylamine gas is slowly introduced for reaction for 7 h. After the reaction, isopropanol was distilled off under reduced pressure to obtain 76g of 2-amino-5-chloro-N, 3-dimethylbenzamide with a yield of 96.8%.
The present invention is described in detail in order to make those skilled in the art understand the content and practice the present invention, and the present invention is not limited to the above embodiments, and all equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. A preparation method of 2-amino-5-chloro-N, 3-dimethyl benzamide is characterized in that: the method comprises the following steps:
K1. 2-nitro-3-methylbenzoic acid is used as an initial raw material to carry out reduction reaction to obtain 2-amino-3-methylbenzoic acid;
K2. performing chlorination reaction on 2-amino-3-methylbenzoic acid to obtain 2-amino-5-chloro-3-methylbenzoic acid;
K3. carrying out esterification reaction on 2-amino-5-chloro-3-methylbenzoic acid to obtain 2-amino-5-chloro-3-methylbenzoate;
K4. 2-amino-5-chloro-3-methylbenzoate is subjected to ammonolysis reaction to obtain 2-amino-5-chloro-N, 3-dimethylbenzamide.
2. The method of claim 1, wherein: the 2-nitro-3-methyl benzoic acid in K1 and hydrogen are subjected to reduction reaction in ethanol under the condition of a catalyst, and the catalyst is Raney nickel.
3. The method of claim 2, wherein: the feeding mass ratio of the 2-nitro-3-methylbenzoic acid to the Raney nickel is 1: 0.01-0.05; the hydrogen pressure is 0.1MPa to 1.5 MPa; the reaction temperature of the reduction reaction is 20-80 ℃; the reaction time of the reduction reaction is 3-8 h.
4. The method of claim 1, wherein: the chlorination is carried out with 2-amino-3-methylbenzoic acid as described in K2 and chlorine in an organic solvent.
5. The method of claim 4, wherein: the organic solvent is one or more of chloroform, dichloroethane, acetonitrile and tetrahydrofuran; the feeding molar ratio of the 2-amino-3-methylbenzoic acid to the chlorine gas is 1:1 to 1.5; the reaction temperature of the chlorination reaction is 20-80 ℃; the reaction time of the chlorination reaction is 2-4 h.
6. The method of claim 1, wherein: the esterification of 2-amino-5-chloro-3-methylbenzoic acid described in K3 with alcohols is carried out under the action of concentrated sulfuric acid.
7. The method of claim 6, wherein: the alcohol is one or more of methanol, ethanol, isopropanol and n-butanol; the feeding molar ratio of the 2-amino-5-chloro-3-methylbenzoic acid to the concentrated sulfuric acid is 1: 0.1 to 0.5; the reaction time of the chlorination reaction is 4-10 h.
8. The method of claim 1, wherein: the 2-amino-5-chloro-3-methylbenzoate described in K4 was subjected to the aminolysis reaction with methylamine in an alcohol.
9. The method of claim 8, wherein: the alcohol is one or more of methanol, ethanol, isopropanol and n-butanol; the feeding molar ratio of the 2-amino-5-chloro-3-methylbenzoate to the methylamine is 1: 1-1.5; the reaction temperature of the ammonolysis reaction is 20-60 ℃; the reaction time of the ammonolysis reaction is 2-8 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115417781A (en) * | 2022-09-30 | 2022-12-02 | 西安凯立新材料股份有限公司 | Method for preparing chlorantraniliprole intermediate K amine |
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| CN105859574A (en) * | 2016-04-26 | 2016-08-17 | 常州市阿曼特化工有限公司 | Synthesis method of 2-amino-5-chloro-N,3-dimethylbenzamide |
| CN110845341A (en) * | 2019-11-08 | 2020-02-28 | 苏州开元民生科技股份有限公司 | Preparation method of 2-amino-5-chloro-N, 3-dimethylbenzamide |
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| CN105859574A (en) * | 2016-04-26 | 2016-08-17 | 常州市阿曼特化工有限公司 | Synthesis method of 2-amino-5-chloro-N,3-dimethylbenzamide |
| CN110845341A (en) * | 2019-11-08 | 2020-02-28 | 苏州开元民生科技股份有限公司 | Preparation method of 2-amino-5-chloro-N, 3-dimethylbenzamide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115417781A (en) * | 2022-09-30 | 2022-12-02 | 西安凯立新材料股份有限公司 | Method for preparing chlorantraniliprole intermediate K amine |
| CN115417781B (en) * | 2022-09-30 | 2023-08-29 | 西安凯立新材料股份有限公司 | Method for preparing chlorantraniliprole intermediate K amine |
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