CN117186060A

CN117186060A - Production method of o-carboxamido benzamide compound

Info

Publication number: CN117186060A
Application number: CN202210609153.0A
Authority: CN
Inventors: 陈达; 孙克娜; 郑思佳; 祝钰涛; 朱海峰
Original assignee: Shandong Youdao Chemical Co ltd
Current assignee: Shandong Youdao Chemical Co ltd
Priority date: 2022-05-31
Filing date: 2022-05-31
Publication date: 2023-12-08

Abstract

The invention provides a production method of an o-carboxamido benzamide compound, which adopts substituted pyrazole formic acid as a raw material to prepare substituted pyrazole formyl chloride through acylation reaction and then to synthesize the o-carboxamido benzamide compound through condensation reaction with the o-carboxamido benzamide, so that the use of dehydration coupling agents such as methanesulfonyl chloride and the like is avoided, and the problems of three wastes difficult to treat and cost caused by using methanesulfonyl chloride are avoided. In addition, the concentration process is arranged at the rear end of the acylation and condensation reaction stage, so that the content of the acyl chloride reagent in the acylation reaction liquid can be reduced, the side reaction of excessive acyl chloride reagent and o-aminobenzamide is avoided, and the potential safety hazard caused by evaporating the solvent is avoided; the precipitation rate of the product can be increased, the product loss is reduced, the refining processes and equipment such as multi-stage washing and recrystallization which are matched due to the recovery and separation of the product in the mother liquor are omitted, the process can be simplified, the yield and purity of the product are improved, and the product with better appearance quality is obtained.

Description

Production method of o-carboxamido benzamide compound

Technical Field

The invention relates to the technical field of pesticide production, in particular to a production method of o-formamido benzamide compounds.

Background

The o-formamido benzamide compounds such as chlorantraniliprole, cyantraniliprole, tetrachlorantraniliprole, cycloartemia, flucyantraniliprole and the like are low-toxicity and high-efficiency novel pesticides, and are widely applied to prevention and control of lepidoptera pests.

At present, a plurality of documents report a synthesis method of an o-carboxamido benzamide compound, for example, patent CN100422177C discloses that 3-halogeno-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formic acid and substituted o-aminobenzoic acid are taken as raw materials to prepare a benzoxazinone intermediate under the action of methanesulfonyl chloride and an acid binding agent, and then the benzoxazinone intermediate is reacted with a methylamine aqueous solution to obtain the o-carboxamido benzamide compound.

Patent CN101072767B discloses a method for preparing an anthranilamide compound from 3-halo-1- (3-chloro-2-pyridinyl) -1H-pyrazole-5-carboxylic acid and substituted anthranilamide as raw materials under the action of methanesulfonyl chloride and an acid binding agent, which reduces the usage amount of methanesulfonyl chloride but generates an iminobenzoxazine as a dehydration cyclization byproduct, and in order to reduce product loss, the reaction mixture needs to be treated with an aqueous acid in the production process to convert the byproduct into a product, thereby generating a large amount of mixed salt wastewater containing pyridine, sodium chloride and sodium methanesulfonate, and the treatment cost is high.

Patent CN101945861B and CN110028489B disclose that 3-halo-1- (3-chloro-2-pyridyl) -4, 5-dihydro-1H-pyrazole-5-carboxylic acid is used as a raw material, and is subjected to acyl halogenation and oxidation to prepare 3-halo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formylhalide, and the substituted pyrazole formylhalide and substituted aniline are subjected to the action of an acid binding agent to prepare an o-carboxamido benzamide compound, so that the traditional oxidation reaction by using an oxidant is replaced, the use of methanesulfonyl chloride is avoided, the reaction step is simplified, the reaction yield is improved, but after the acyl halogenation and oxidation reaction is finished, a solvent is required to be evaporated to dryness.

Patent CN113896714a discloses that 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-carboxylic acid is acylated to prepare 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-carboxamide, and then chlorantraniliprole is prepared with 2-amino-5-chloro-N, 3-dimethylbenzamide under reflux conditions, so that the problem of waste salt caused by using methanesulfonyl chloride is avoided and the influence of reduction products of acyl halogenating reagent on product quality is avoided, but in order to improve the conversion rate of substituted pyrazole-carboxylic acid, excessive acyl chlorination reagent is used in the acylation reaction stage, and the acyl chloride solution obtained by the acylation reaction is directly added with 2-amino-5-chloro-N, 3-dimethylbenzamide for reflux reaction, so that the yield of high-purity product is lower although the reaction operation is simplified.

Disclosure of Invention

In view of the above, the technical problem to be solved by the invention is to provide a production method of o-carboxamido benzamide compounds, which has higher yield and purity.

The invention provides a production method of an o-formamido benzamide compound, which comprises the following steps:

s1: adding substituted pyrazole formic acid and a first solvent into an acylation reaction kettle, dropwise adding an acyl chloride reagent or a mixed solution of the acyl chloride reagent and a second solvent, and carrying out acylation reaction at a temperature of 20-reflux to obtain an acylation reaction solution containing substituted pyrazole formyl chloride;

s2: distilling the acylation reaction liquid containing the substituted pyrazole formyl chloride in the step S1, distilling out part of the solvent, and adding a third solvent to obtain an acylation liquid containing the substituted pyrazole formyl chloride;

s3: adding o-aminobenzamide, a fourth solvent and the acylation liquid containing the substituted pyrazole formyl chloride obtained in the step S2 into a condensation reaction kettle, and carrying out condensation reaction at a temperature of 20-reflux to obtain a condensation reaction liquid;

s4: distilling and concentrating the condensation reaction liquid in the step S3, and evaporating part of the solvent to obtain a reaction concentrated liquid;

s5: and mixing and washing the reaction concentrated solution with a washing reagent, and then carrying out solid-liquid separation and drying to obtain the product o-formamidobenzamide compound.

Optionally, the substituted pyrazole carboxylic acid is selected from one of 3-bromo-1- (3-chloro-2-pyridinyl) -1H-pyrazole-5-carboxylic acid, 3-bromo-1- (3, 5-dichloro-2-pyridinyl) -1H-pyrazole-5-carboxylic acid. Correspondingly, the prepared substituted pyrazole formyl chloride is 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formyl chloride or 3-bromo-1- (3, 5-dichloro-2-pyridyl) -1H-pyrazole-5-formyl chloride.

Alternatively, the anthranilamide is selected from one of 2-amino-5-chloro-N, 3-dimethylbenzamide, 2-amino-5-cyano-N, 3-dimethylbenzamide, 2-amino-3, 5-dichloro-N-methylbenzamide, 2-amino-3-bromo-5-chloro-N- (1-cyclopropylethyl) benzamide.

Researches show that the acylating and chlorinating agent can carry out side reactions such as acylation and cyclization with the anthranilamide, a small amount of the acylating agent which does not participate in the reaction is doped in the acylating reaction liquid obtained in the step S1, the acylating reaction liquid is directly used for the next condensation reaction, the acylating and chlorinating agent consumes raw material anthranilamide, impurities are introduced, and the utilization rate of the raw material and the content of products are reduced. The invention creatively discovers that the acyl chloride reagent which does not participate in the reaction can be carried out in the process of evaporating the solvent, the distillation operation is added at the rear end of the step S1, and the content of the acyl chloride reagent in the acylation reaction liquid is reduced by evaporating part of the solvent, so that the consumption of the acyl chloride reagent on raw material anthranilamide and the generation of impurities are reduced.

The conventional production method adopts the modes of direct cooling, filtering and drying after the condensation reaction is finished, but a small amount of product is dissolved in the filtering mother liquor, so that the yield of the product is improved, the treatment burden of organic wastewater is reduced, the filtering mother liquor is rectified to recover the solvent, the heavy component is recovered, the heavy component is repeatedly washed and separated to recover the product, but the product obtained by the mode is often doped with more impurities, the product content is lower, and the product is further refined by recrystallization.

In order to ensure the conversion rate of the raw materials in the acylation reaction stage and to consider the solubility of the materials and improve the convenience of the post-treatment operation of the acylation reaction and the condensation reaction, as a preferable technical scheme of the invention, the acylating agent adopted in the step S1 is selected from thionyl chloride, oxalyl chloride or triphosgene, and the first solvent, the second solvent, the third solvent and the fourth solvent adopted in the step S1 and the steps S2 and S3 are independently selected from dichloromethane, dichloropropane, dichloroethane, acetonitrile or toluene, preferably dichloroethane, acetonitrile or toluene.

In order to balance the relation between the yield, purity and production efficiency of the product, as a preferable technical scheme of the invention, the first solvent in the step S1 is used in an amount which is 1.5 to 8 times, preferably 2 to 6 times, the mass of the substituted pyrazole formic acid, and when the acylation reaction liquid is distilled in the step S2, the distilled solvent accounts for 50 to 90 percent of the total solvent in the acylation reaction stage.

In order to further improve the yield and purity of the product, as a preferred technical scheme of the present disclosure, the total solvent amount of the condensation reaction in step S3 is 3 to 20 times, preferably 4 to 16 times, the mass of the substituted pyrazole carboxylic acid, and when the condensation reaction liquid is distilled and concentrated in step S4, the distilled solvent amount accounts for 50 to 90% of the total solvent amount in the condensation reaction stage.

In the acylation reaction stage and the condensation reaction stage, the use amount of the solvent is too small, so that the mixing effect and the heat transfer efficiency in the reaction process are affected, the industrial production is not facilitated, the production efficiency of equipment is reduced, and the equipment cost and the operation cost are increased. If the distilled solvent is too small after the acylation reaction is finished, the carried-out acid chloride reagent is less, the residual acid chloride reagent in the acylation reaction liquid enters a condensation reaction stage to generate impurities with the anthranilamide, so that the content of products is reduced, if the distilled solvent is too small after the condensation reaction is finished, a small amount of products are still dissolved in the condensed reaction liquid after condensation, the products in the solvents are not recovered, the products are lost, a series of product refining equipment is required to be matched for the products in the recovered solvents, and the investment cost is high; if the solvent evaporated after the two reaction stages are over, the kettle bottom liquid is easy to be coked to generate high-boiling-point impurities, thereby reducing the yield and purity of the final product and easily generating safety accidents.

In the step S2, the acylation reaction liquid is distilled and concentrated, and then the solvent distilled out is dissolved with an acyl chloride reagent, so that the effective utilization of materials, the reduction of wastes and the reduction of material cost are realized, and the solvent distilled out in the step S2 is applied to the step S1 acylation reaction stage as a preferable technical scheme of the invention.

Because the raw material substituted pyrazole carboxylic acid has longer synthetic process flow and higher material cost than the raw material o-aminobenzamide, the molar ratio of the substituted pyrazole acyl chloride to the o-aminobenzamide in the step S3 is 1:1-1.2, preferably 1:1.03-1.15, as a preferable technical scheme of the invention for reducing the material cost.

In the step S1, in the acylation reaction stage of substituted pyrazole carboxylic acid, in order to improve the conversion rate of the substituted pyrazole carboxylic acid, and consider that a small amount of acyl chloride reagent is lost in the reaction process, the usage amount of the acyl chloride reagent is slightly excessive compared with that of the substituted pyrazole carboxylic acid, and when the acyl chloride reagent is thionyl chloride or oxalyl chloride, the molar ratio of the substituted pyrazole carboxylic acid to the acyl chloride reagent is 1:1.05-1.8; when the acyl chloride reagent is triphosgene, the molar ratio of the substituted pyrazole formic acid to the acyl chloride reagent is 1:0.35-0.6.

The reaction time and the reaction temperature of the acyl chlorination reaction stage and the condensation reaction stage of the step S1 and the step S3, the addition amount of materials and other factors are related, and the acylation reaction liquid containing substituted pyrazole formyl chloride and the condensation reaction liquid containing o-formamido benzamide can be obtained after the reaction for 0.5 to 10 hours at the temperature of 20 to reflux, wherein the conversion rate of substituted pyrazole formic acid in the acylation reaction stage and the conversion rate of substituted pyrazole formyl chloride in the condensation reaction stage can reach more than 99 percent. The reflux temperature refers to the boiling point of the solvent used at normal pressure, such as acetonitrile at normal pressure having a boiling point of 81-82 ℃, methylene chloride having a boiling point of 40 ℃, toluene having a boiling point of 111 ℃, and dichloroethane having a boiling point of 82-84 ℃.

In order to increase the reaction rate of the acylation reaction in the step S1, as a preferable technical scheme of the invention, when the substituted pyrazole carboxylic acid and the first solvent are added into the acylation reaction kettle in the step S1, a catalyst DMF is also added, and preferably, the molar ratio of the DMF to the substituted pyrazole carboxylic acid is 0.01-0.15:1.

In the step S3, hydrogen chloride is generated in the process of carrying out condensation reaction between substituted pyrazole acyl chloride and anthranilamide, and in order to promote the condensation reaction, as a preferable technical scheme of the invention, when the anthranilamide and the fourth solvent are added into the condensation reaction kettle in the step S3, an acid-binding agent is also added, wherein the acid-binding agent is preferably one of 3-methylpyridine, pyridine, 2-methylpyridine and triethylamine.

In order to realize effective utilization of materials, reduce waste and material cost, the invention adopts a preferable technical scheme that the solvent distilled in the step S4 is applied to the condensation reaction stage of the step S3. When the acid binding agent is added in the condensation reaction stage, the solvent distilled in the step S4 can be directly applied to the condensation reaction stage, can also be applied to the acylation reaction stage in the step S1, and when the acid binding agent is not added in the condensation reaction stage, a small amount of hydrogen chloride gas is contained in the solvent distilled in the step S4, and can be directly applied to the condensation reaction stage after dehydrochlorination treatment, and can also be directly applied to the condensation reaction stage.

In the step S4, a small amount of impurities are precipitated and attached to the surface of the product along with the product in the condensation reaction liquid containing the product o-formamidobenzamide in the concentration process, and in order to improve the purity of the product, the reaction concentrated liquid obtained after distillation and concentration is firstly mixed with a washing reagent before solid-liquid separation, and the impurities attached to the surface of the product are brought into a liquid phase and then separated from the impurities through solid-liquid separation. As a preferred embodiment of the present invention, the washing reagent in step S5 is selected from one or more of water, sodium carbonate solution, sodium bicarbonate solution, sodium hydroxide solution, methanol, ethanol, ethyl acetate, and acetonitrile.

In the step S5, the reaction concentrated solution and the washing reagent are mixed and washed and then subjected to solid-liquid separation, wet materials of the separated products are dried to obtain the o-carboxamido benzamide, and in order to further improve the purity of the products and reduce the impurity content in the products, the method also comprises the following steps of: and adding a washing reagent to wash and separate the solid crude product, and drying the wet product obtained by separation to obtain the o-formamidobenzamide, wherein the washing reagent is preferably one or more of water, methanol, ethanol and acetonitrile.

As a specific embodiment of the invention, a first solvent of substituted pyrazole formic acid and 1.5-8 times of substituted pyrazole formic acid is added into an acylation reaction kettle, then an acyl chloride reagent is dripped at 20 ℃, the reaction is stopped when the dripping is completed and the conversion rate of the substituted pyrazole formic acid reaches over 99 percent at 20-reflux temperature, an acylation reaction liquid containing substituted pyrazole formyl chloride is obtained, the acylation reaction liquid is transferred into a distillation kettle to distill 50-90 percent of the solvent, then fresh third solvent is added into the kettle to obtain the acylation liquid, the acylation liquid is added into a condensation reaction kettle added with o-aminobenzamide and a fourth solvent, wherein the total solvent amount is 3-20 times of the mass of the substituted pyrazole formic acid, the substituted pyrazole formyl chloride and the o-aminobenzamide are subjected to condensation reaction at 20-reflux temperature, the condensation reaction liquid is obtained, then the condensation reaction liquid is transferred into the distillation kettle to distill 50-90 percent of the solvent, then a washing reagent is added into the distillation kettle to wash the reaction liquid, and the condensation reaction liquid is subjected to solid-liquid separation, and the o-aminobenzamide is obtained after drying.

As another specific embodiment of the invention, adding a first solvent with the mass of substituted pyrazole formic acid, DMF and 1.5-8 times of substituted pyrazole formic acid into an acylation reaction kettle, then dropwise adding an acyl chloride reagent at 20 ℃, reacting at 20-reflux temperature after the dropwise adding until the conversion rate of the substituted pyrazole formic acid reaches more than 99%, stopping the reaction to obtain an acylation reaction liquid containing substituted pyrazole formyl chloride, transferring the acylation reaction liquid into a distillation kettle to distill 50-90% of the solvent, then adding a fresh third solvent into the kettle to obtain an acylation liquid, adding the acylation liquid into a condensation reaction kettle with the o-aminobenzamide, an acid binding agent and a fourth solvent, wherein the total solvent amount is 3-20 times of the mass of the substituted pyrazole formic acid, condensing the substituted pyrazole formyl chloride and the o-aminobenzamide at 20-reflux temperature, obtaining a condensation reaction liquid, transferring the condensation reaction liquid into the distillation kettle to distill 50-90% of the solvent, then adding a washing reagent into the distillation kettle to wash the reaction concentrated liquid, and obtaining the o-aminobenzamide product through solid-liquid separation, washing and drying.

Compared with the prior art, the invention provides a production method of an o-formamido benzamide compound, which comprises the following steps: s1: adding substituted pyrazole formic acid and a first solvent into an acylation reaction kettle, dropwise adding an acyl chloride reagent or a mixed solution of the acyl chloride reagent and a second solvent, and carrying out acylation reaction at a temperature of 20-reflux to obtain an acylation reaction solution containing substituted pyrazole formyl chloride; s2: distilling the acylation reaction liquid containing the substituted pyrazole formyl chloride in the step S1, distilling out part of the solvent, and adding a third solvent to obtain an acylation liquid containing the substituted pyrazole formyl chloride; s3: adding o-aminobenzamide, a fourth solvent and the acylation liquid containing the substituted pyrazole formyl chloride obtained in the step S2 into a condensation reaction kettle, and carrying out condensation reaction at a temperature of 20-reflux to obtain a condensation reaction liquid; s4: distilling and concentrating the condensation reaction liquid in the step S3, and evaporating part of the solvent to obtain a reaction concentrated liquid; s5: and mixing and washing the reaction concentrated solution with a washing reagent, and then carrying out solid-liquid separation and drying to obtain the product o-formamidobenzamide compound.

The invention adopts substituted pyrazole formic acid as raw material to prepare substituted pyrazole formyl chloride through acylation reaction and then to synthesize o-carboxamido benzamide compound through condensation reaction with o-amino benzamide, thus avoiding the use of dehydration coupling agents such as methanesulfonyl chloride and the like, and avoiding the problems of three wastes difficult to treat and cost caused by using methanesulfonyl chloride.

In addition, the production method of the o-carboxamido benzamide compound provided by the invention is characterized in that the rear ends of the acylation and condensation reaction stages are provided with concentration processes. After the acylation reaction is finished, the acylation reaction liquid is concentrated, and part of solvent is distilled off, so that the content of an acyl chloride reagent in the acylation reaction liquid can be reduced, the side reaction of excessive acyl chloride reagent and o-aminobenzamide is avoided, and the potential safety hazard of more impurities caused by evaporating the solvent is avoided; after the condensation reaction is finished, the condensation reaction liquid is concentrated, part of solvent is distilled off, the precipitation rate of the product can be increased, the product loss is reduced, the refining processes and equipment such as multistage washing, recrystallization and the like matched with the recovery and separation of the product in the mother liquor are omitted, the process can be simplified, the yield and purity of the product are improved, and the product with better appearance quality is obtained.

Detailed Description

In order to further illustrate the present invention, the following describes in detail the production method of the anthranilamide compound provided by the present invention with reference to examples.

Example 1

Adding 242g of 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-carboxylic acid and 363g of dichloromethane into an acylation reaction kettle, uniformly mixing, dropwise adding 100g of thionyl chloride at 20 ℃, continuously stirring for 10 hours after the dropwise addition, stopping the reaction to obtain an acylation reaction solution containing substituted pyrazole formyl chloride, transferring the acylation reaction solution into a distillation kettle to distill 50% of solvent, adding 181.5g of dichloromethane into the kettle to obtain an acylation solution, adding the acylation solution into a condensation reaction kettle with 1599 g of 2-amino-5-chloro-N, 3-dimethylbenzamide and 363g of dichloromethane, heating to reflux temperature for reaction for 6 hours to obtain a condensation reaction solution, transferring the condensation reaction solution into the distillation kettle to distill 50% of solvent, adding 2% of sodium hydroxide solution into the distillation kettle for washing the reaction concentrated solution, performing solid-liquid separation and drying to obtain 364 g of chlorantraniliprole, and obtaining 94.2% of chlorantraniliprole with 98.3% of liquid phase detection content.

Example 2

Adding 197g of 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formic acid, 0.9g of DMF and 393.3g of dichloropropane into an acylation reaction kettle, uniformly mixing, then dropwise adding 94.9g of oxalyl chloride at 20 ℃, heating to 40 ℃ after the dropwise addition, continuously stirring for 8 hours to stop the reaction to obtain an acylation reaction liquid containing substituted pyrazole formyl chloride, transferring the acylation reaction liquid into a distillation kettle to evaporate 60% of solvent, then adding 236g of dichloropropane into the kettle to obtain an acylation liquid, adding 126.7g of 2-amino-5-cyano-N, 3-dimethylbenzamide, 393.3g of dichloropropane and 51.4g of pyridine into the condensation reaction kettle, heating to 50 ℃ to obtain a condensation reaction liquid, transferring the condensation reaction liquid into the distillation kettle to evaporate 60% of solvent, adding water into the distillation kettle to wash the reaction liquid, and obtaining 291.6g of cyantranilide with a content of 94.7% of cyantranilide after solid-liquid separation and drying, and detecting the liquid phase content of cyantranilide to be 94.5%.

Example 3

Adding 139g of 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formic acid, 2g of DMF and 487g of dichloroethane into an acylation reaction kettle, uniformly mixing, dropwise adding 71.2g of thionyl chloride at 20 ℃, heating to 60 ℃ after the dropwise addition, continuously stirring for 6.5H, stopping the reaction to obtain an acylation reaction liquid containing substituted pyrazole acyl chloride, transferring the acylation reaction liquid into a distillation kettle to evaporate 70% of solvent, adding 341g of dichloroethane into the kettle to obtain an acylation liquid, adding the acylation liquid into a condensation reaction kettle with 96.9g of 2-amino-5-chloro-N, 3-dimethylbenzamide, 626.2g of dichloroethane and 42.8g of 3-methylpyridine, heating to 60 ℃ to obtain a condensation reaction liquid, transferring the condensation reaction liquid into the distillation kettle to obtain 80% of solvent, adding a mixed liquid of methanol water into the distillation kettle, washing the reaction concentrate, separating solid from the solid, washing the solid, and drying to obtain the final product, wherein the solid is separated from the solid, and the final product is dried to obtain the benzamide with the liquid phase of 99.5%, and the liquid phase content of the benzamide is detected to be 9.95%.

Example 4

108g of 3-bromo-1- (3, 5-dichloro-2-pyridinyl) -1H-pyrazole-5-carboxylic acid, 2.7g of DMF and 300g of acetonitrile are added into an acylation reaction kettle, after uniform mixing, an acetonitrile solution of triphosgene is dropwise added at 20 ℃, wherein 33.2g of triphosgene and 241.6g of acetonitrile are dropwise added, the temperature is raised to 70 ℃ after the completion of the dropwise addition, stirring is continued for 5 hours to stop the reaction, an acylation reaction liquid containing substituted pyrazole formyl chloride is obtained, the acylation reaction liquid is transferred into a distillation kettle to distill 80% of solvent, 433g of acetonitrile is added into the kettle to obtain an acylation liquid, the acylation liquid is added into a condensation reaction kettle with 77.2g of 2-amino-3, 5-dichloro-N-methylbenzamide, 541.6g of acetonitrile and 29.8g of 2-methylpyridine, the condensation reaction liquid is obtained after stirring and reacting for 10 hours at 20 ℃, then the condensation reaction liquid is transferred into the distillation kettle to 70% of solvent, water is added into the distillation kettle to wash the reaction liquid, then the condensation liquid is separated, solid is separated, the solid is separated, and the solid is washed with 9.95% of liquid phase, and the final yield is 9.95% of the obtained.

Example 5

94.8g of 3-bromo-1- (3, 5-dichloro-2-pyridinyl) -1H-pyrazole-5-carboxylic acid, 3.6g of DMF and 300g of toluene are added into an acylation reaction kettle, a toluene solution of triphosgene is dropwise added at 20 ℃ after uniform mixing, wherein 37.4g of triphosgene and 268.7g of toluene are dropwise added, the temperature is raised to 80 ℃ after the dropwise addition, stirring is continued for 3 hours to stop the reaction, an acylation reaction liquid containing substituted pyrazole formyl chloride is obtained, the acylation reaction liquid is transferred into a distillation kettle to distill 50% of solvent, 284g of toluene is added into the kettle to obtain an acylation liquid, the acylation liquid is added into a condensation reaction kettle, 93.4g of 2-amino-3-bromo-5-chloro-N- (1-cyclopropylethyl) benzamide, 568.7g of toluene and 28.3g of triethylamine are added into the condensation reaction kettle, the condensation reaction liquid is obtained after stirring and reacting for 2 hours at 80 ℃, then 60% of solvent is distilled out, water is added into the distillation kettle, the distillation kettle is used for washing the concentrated reaction liquid, the concentrated solution is separated, and then the solid phase is separated, the solid phase is washed with 99.5% of the obtained, and finally, the solid phase is separated, and the solid phase is washed, and the solid phase is obtained, and the solid phase is separated, and the solid phase and the product is separated from the solid phase and the product.

Example 6

81.7g of 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-carboxylic acid, 4.6g of DMF and 271.7g of dichloroethane are added into an acylation reaction kettle, a dichloroethane solution of triphosgene is dropwise added at 20 ℃ after uniform mixing, wherein 48.1g of triphosgene and 300g of dichloroethane are dropwise added, the temperature is raised to a reflux temperature after the completion of the dropwise addition and stirring is continued for 2 hours to stop the reaction, an acylation reaction liquid containing substituted pyrazole formyl chloride is obtained, the acylation reaction liquid is transferred into a distillation kettle to distill 90% of solvent, 514.6g of dichloroethane is added into the kettle to obtain an acylation liquid, the acylation liquid is added into a condensation reaction kettle with 55.2g of 2-amino-5-cyano-N, 3-dimethylbenzamide, 735.1g of dichloroethane and 21.4g of pyridine, the condensation reaction liquid is obtained after stirring reaction for 1.5 hours at the reflux temperature, then the condensation reaction liquid is transferred into the distillation kettle to distill 60% of solvent, then the mixed liquid containing ethanol water is added into the distillation kettle to wash the reaction liquid, then the reaction liquid concentrate is separated, the solid phase is separated, and the 2.121.95% of bromine is obtained, and the solid phase is separated, and the 2.95% of the solid phase is obtained, and the 2.95% of bromine is finally separated.

Example 7

69.6g of 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-carboxylic acid, 4.9g of DMF and 556.6g of toluene are added into an acylation reaction kettle, 41g of thionyl chloride is dropwise added at 20 ℃ after uniform mixing, the temperature is raised to reflux temperature after the dropwise addition, stirring is continued for 0.5H, the reaction is stopped to obtain an acylation reaction liquid containing substituted pyrazole formyl chloride, the acylation reaction liquid is transferred into a distillation kettle to evaporate 60% of solvent, 334g of toluene is added into the kettle to obtain an acylation liquid, the acylation liquid is added into a condensation reaction kettle with 52.6g of 2-amino-5-chloro-N, 3-dimethylbenzamide, 834.9g of toluene and 21.4g of 3-methylpyridine, the condensation reaction liquid is obtained after stirring for 0.5H at reflux temperature, then the condensation reaction liquid is transferred into the distillation kettle to obtain 90% of solvent, the mixed liquid containing methanol and water is added into the distillation kettle to wash the reaction liquid, then the reaction liquid is subjected to solid-liquid separation, the crude product is washed, and finally the solid-liquid phase is separated, and the solid-phase is separated, and the 3.8% of benzamide is obtained, and the yield is detected, and the final solid-phase is separated, and the 3.8% of the 3-methyl chloride is obtained.

Example 8

103g of 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-formic acid, 2.4g of DMF and 462.8g of acetonitrile are added into an acylation reaction kettle, after uniform mixing, 77.7g of oxalyl chloride is dropwise added at 20 ℃, the temperature is raised to reflux temperature after the dropwise addition, stirring is continued for 2 hours, the reaction is stopped to obtain an acylation reaction liquid containing substituted pyrazole formyl chloride, the acylation reaction liquid is transferred into a distillation kettle to evaporate 70% of solvent, then 324g of acetonitrile is added into the kettle to obtain an acylation liquid, the acylation liquid is added into a condensation reaction kettle with 81.1g of 2-amino-5-chloro-N, 3-dimethylbenzamide, 462.8g of acetonitrile and 31.7g of 2-methylpyridine, the condensation reaction liquid is obtained after stirring reaction for 1 hour at reflux temperature, then the condensation reaction liquid is transferred into the distillation kettle to obtain 80% of solvent, water is added into the distillation kettle to stop the reaction concentrate for washing, then solid crude product is subjected to solid-liquid separation, 157% of washing separation is carried out, finally, and the 3.95% of benzamide is obtained, and the 3.95% of liquid phase is detected after the final drying.

Comparative example 1

103g of 3-bromo-1- (3-chloro-2-pyridyl) -1H-pyrazole-5-carboxylic acid, 2.4g of DMF and 462.8g of acetonitrile are added into an acylation reaction kettle, after uniform mixing, 77.7g of oxalyl chloride is dropwise added at 20 ℃, the temperature is raised to a reflux temperature after the dropwise addition, stirring is continued for 2 hours, the reaction is stopped to obtain an acylation reaction liquid containing substituted pyrazole formyl chloride, the acylation reaction liquid is added into a condensation reaction kettle added with 81.1g of 2-amino-5-chloro-N, 3-dimethylbenzamide, 462.8g of acetonitrile and 31.7g of 2-methylpyridine, the condensation reaction liquid is obtained after stirring for 1 hour at the reflux temperature, then the condensation reaction liquid is cooled to normal temperature, solid-liquid separation and drying are carried out to obtain 138.8g of chlorantraniliprole, the yield is 84.5%, and the liquid phase detection content is 97.8%.

The results of comparative example 1 show that the acylation reaction and the condensation reaction are not followed by a concentration step, the side reaction of the reaction is increased, and the yield and the purity are reduced.

The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.

Claims

1. A method for producing an o-carboxamido benzamide compound comprises the following steps:

2. The method for producing an anthranilamide compound according to claim 1, characterized in that the substituted pyrazole carboxylic acid is one selected from 3-bromo-1- (3-chloro-2-pyridinyl) -1H-pyrazole-5-carboxylic acid, 3-bromo-1- (3, 5-dichloro-2-pyridinyl) -1H-pyrazole-5-carboxylic acid;

the anthranilamide is selected from one of 2-amino-5-chloro-N, 3-dimethylbenzamide, 2-amino-5-cyano-N, 3-dimethylbenzamide, 2-amino-3, 5-dichloro-N-methylbenzamide and 2-amino-3-bromo-5-chloro-N- (1-cyclopropylethyl) benzamide;

the acyl chloride reagent in the step S1 is selected from thionyl chloride, oxalyl chloride or triphosgene;

the first solvent, the second solvent, the third solvent and the fourth solvent are independently selected from dichloromethane, dichloropropane, dichloroethane, acetonitrile or toluene.

3. The method for producing an anthranilamide compound according to claim 2, characterized in that when the acid chloride reagent is thionyl chloride or oxalyl chloride, the molar ratio of the substituted pyrazole carboxylic acid to the acid chloride reagent is 1:1.05 to 1.8;

when the acyl chloride reagent is triphosgene, the molar ratio of the substituted pyrazole formic acid to the acyl chloride reagent is 1:0.35-0.6.

4. The method for producing an anthranilamide compound according to claim 1 or 2, characterized in that the sum of the addition amounts of the first solvent and the second solvent in the step S1 is 1.5 to 8 times the mass of the substituted pyrazole carboxylic acid;

the amount of the part of solvent distilled in the step S2 is 50% -90% of the total solvent amount in the acylation reaction stage;

the total solvent amount of the condensation reaction in the step S3 is 3-20 times of the mass of the substituted pyrazole carboxylic acid;

the amount of the part of solvent distilled in the step S4 is 50% -90% of the total solvent amount in the condensation reaction stage.

5. The method for producing an anthranilamide compound according to claim 1, characterized in that the solvent distilled off in step S2 is applied to the step S1 acylation reaction stage.

6. The method for producing an anthranilamide compound according to claim 1, characterized in that in the step S3, the molar ratio of the substituted pyrazole formyl chloride to the anthranilamide is 1: (1-1.2).

7. The method for producing an anthranilamide compound according to claim 1, characterized in that a catalyst DMF is further added when the substituted pyrazole carboxylic acid and the first solvent are added to the acylation reaction vessel in the step S1;

the molar ratio of DMF to substituted pyrazole formic acid is 0.01-0.15:1.

8. The method for producing an anthranilamide compound according to claim 1, characterized in that an acid-binding agent is further added when the anthranilamide and the fourth solvent are added to the condensation reaction vessel in the step S3;

the acid binding agent is one or more selected from 3-picoline, pyridine, 2-picoline and triethylamine.

9. The method for producing an anthranilamide compound according to claim 1, wherein the washing reagent in step S5 is one or more selected from the group consisting of water, sodium carbonate solution, sodium bicarbonate solution, sodium hydroxide solution, methanol, ethanol, ethyl acetate, and acetonitrile.

10. The method for producing an anthranilamide compound according to claim 1, characterized in that the step S5 further comprises, after solid-liquid separation:

adding a washing reagent to wash the solid crude product;

the washing reagent is selected from one or more of water, methanol, ethanol and acetonitrile.