CN113480518A - Method for synthesizing chlorantraniliprole - Google Patents
Method for synthesizing chlorantraniliprole Download PDFInfo
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- CN113480518A CN113480518A CN202110771013.9A CN202110771013A CN113480518A CN 113480518 A CN113480518 A CN 113480518A CN 202110771013 A CN202110771013 A CN 202110771013A CN 113480518 A CN113480518 A CN 113480518A
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- 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 method for synthesizing chlorantraniliprole, which comprises the steps of stirring a solvent containing 2-amino-3-methylbenzoic acid, dropwise adding a methylamine solution in the stirring reaction process, dissolving N-methyl-3-methyl-2-amino-benzamide in an alkali liquor, carrying out a halogenation reaction with NCS after the reaction is finished to obtain N-methyl-3-methyl-2-amino-5-chloro-benzamide, and carrying out a subsequent ring closing reaction, a bromination reaction, an oxidation reaction and a condensation reaction by using a catalyst for an amide reaction in a matching way, thus obtaining the chlorantraniliprole. According to the invention, by optimizing the preparation steps of chlorantraniliprole, the steps of the whole process flow are more, but the post-treatment is simpler, an intermediate product can be directly obtained after the single step is finished, and the whole synthesis step does not need higher environmental control requirements, so that the industrialization can be conveniently realized.
Description
Technical Field
The invention belongs to the technical field of chlorantraniliprole synthesis, and particularly relates to a method for synthesizing chlorantraniliprole.
Background
The chlorantraniliprole is a broad-spectrum pesticide with a novel structure, has good control effect on noctuidae, snout moth family, moth-eating family, leaf roller moth family, pink moth family, plutella family, wheat moth family, fine moth family and the like of lepidoptera, and can also control various non-lepidoptera pests such as coleoptera curculigo family, phyllocreaceae family, diptera agromyzidae, bemisia tabaci and the like.
At present, the common chlorantraniliprole synthesis method is single, the requirement on the whole synthesis step is high, the reaction environments such as high vacuum, high refrigeration, high temperature, high pressure and the like are frequently used, different equipment is required for treatment, and the industrialization difficulty is high.
Disclosure of Invention
The invention aims to solve the defects in the prior art, the steps of the whole process flow are more but the post-treatment is simpler by optimizing the preparation steps of chlorantraniliprole, an intermediate product can be directly obtained after the single step is finished, and the whole synthesis step does not need higher environmental control requirements and can be convenient for realizing industrialization.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for synthesizing chlorantraniliprole, which comprises the following steps:
s1, stirring a solvent containing 2-amino-3-methylbenzoic acid, dropwise adding a methylamine solution in the stirring reaction process, heating and refluxing, extracting, and drying to obtain N-methyl-3-methyl-2-amino-benzamide;
s2, dissolving N-methyl-3-methyl-2-amino-benzamide in alkali liquor, stirring for 5-10 min, dropwise adding hydrogen peroxide with the mass concentration of 30%, controlling the temperature to be 12-28 ℃, and performing a halogenation reaction with NCS after the reaction is finished to obtain N-methyl-3-methyl-2-amino-5-chloro-benzamide;
s3, selecting 3-aminocrotonitrile to stir, adding hydrazine hydrate to mix during stirring, performing cyclization reaction, naturally heating to room temperature to react for 3-4 hours to obtain 3-amino-5-methylpyrazole;
s4, carrying out bromination reaction on 3-amino-5-methylpyrazole, adding 3-methyl-2-methyl aminobenzoate, chlorinating with NCS, adding 3-methyl-2-methyl aminobenzoate, and chlorinating with sulfuryl chloride SO2Cl2 to obtain 3-methyl-5-bromopyrazole;
s5, adding 5-chloro-3-methyl-2-aminobenzoic acid methyl ester into 3-methyl-5-bromopyrazole to perform oxidation reaction by matching with an oxidant to obtain 5-bromo-1H-3-pyrazolecarboxylic acid;
s6, dissolving 5-bromo-1H-3-pyrazolecarboxylic acid and 2, 3-dichloropyridine in an ethanol solution, adding a potassium carbonate solid, and heating and refluxing to obtain 1- (3-chloro-2-pyridyl) -3-bromo-1H-5-pyrazolecarboxylic acid;
s7, carrying out amide reaction on 1- (3-chloro-2-pyridyl) -3-bromo-1H-5-pyrazolecarboxylic acid and N-methyl-3-methyl-2-amino-5-chloro-benzamide by using a catalyst, so as to obtain chlorantraniliprole.
Preferably, the solvent in S1 is glacial acetic acid, an aromatic hydrocarbon compound, an alicyclic hydrocarbon compound, a halogenated hydrocarbon compound, a ketone compound or an ether compound.
Preferably, the alkali solution in S2 is an aqueous solution of potassium hydroxide, calcium hydroxide, sodium ethoxide, sodium butoxide or potassium tert-butoxide.
Preferably, in the S3, the pH value of the 3-aminocrotonitrile and the hydrazine hydrate is adjusted to 2-3 during stirring, and the mixture is stirred in an ice bath or at 50 ℃ at the stirring speed of 200-250 rpm.
Preferably, the catalyst in S7 is one or more of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, 3, 5-dimethylpyridine and 3-chloro-2-methylpyridine.
Preferably, in the bromination reaction in S4, 3-amino-5-methylpyrazole, concentrated hydrobromic acid and cuprous bromide are mixed, then heated to 60-80 ℃, added with a sodium nitrite aqueous solution, and continuously stirred for reaction for 20-60 min.
Preferably, the oxidation reaction in the S5 needs to be controlled at a reaction temperature of 60-80 ℃, and the stirring reaction time is controlled at 30-35 min.
Preferably, the heating reflux reaction time length in the condensation reaction in the S6 needs to be controlled to be 12-15 h.
The invention has the technical effects and advantages that:
according to the invention, by optimizing the preparation steps of chlorantraniliprole, the reaction steps such as the cyclization reaction, the chlorination reaction, the oxidation reaction, the bromination reaction and the like in the steps are simple and easy to implement, the whole process flow has more steps but simpler post-treatment, an intermediate product can be directly obtained after the single step is finished, and the whole synthesis step does not need higher environmental control requirements and can be convenient for realizing industrialization.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
S1, stirring a solvent containing 2-amino-3-methylbenzoic acid, wherein the solvent is an ether compound, dropwise adding a methylamine solution in the stirring reaction process, heating and refluxing, and then extracting and drying to obtain N-methyl-3-methyl-2-amino-benzamide;
s2, dissolving N-methyl-3-methyl-2-amino-benzamide in an alkali liquor, wherein the alkali liquor is an aqueous solution of potassium tert-butoxide, continuously stirring for 5min, dropwise adding hydrogen peroxide with the mass concentration of 30%, controlling the temperature to be 12 ℃, and performing a halogenation reaction with NCS after the reaction is finished to obtain N-methyl-3-methyl-2-amino-5-chloro-benzamide;
s3, selecting 3-aminocrotonic nitrile to stir, adding hydrazine hydrate to mix during stirring, performing cyclization reaction, naturally heating to room temperature to react for 3 hours to obtain 3-amino-5-methylpyrazole, adjusting the pH value to 2 during stirring the 3-aminocrotonic nitrile and the hydrazine hydrate, performing ice bath or stirring at 50 ℃, and stirring at the speed of 200 rpm;
s4, carrying out bromination reaction on 3-amino-5-methylpyrazole, mixing the 3-amino-5-methylpyrazole, concentrated hydrobromic acid and cuprous bromide, heating to 60-80 ℃, adding a sodium nitrite aqueous solution, continuously stirring for reaction for 30min, adding 3-methyl-2-methyl aminobenzoate, chlorinating with NCS, adding 3-methyl-2-methyl aminobenzoate, and chlorinating with sulfuryl chloride SO2Cl2 to obtain 3-methyl-5-bromopyrazole;
s5, adding 5-chloro-3-methyl-2-methyl aminobenzoate into 3-methyl-5-bromopyrazole to perform oxidation reaction by matching with an oxidant, controlling the reaction temperature to be 80 ℃, and controlling the stirring reaction time to be 35min to obtain 5-bromo-1H-3-pyrazolecarboxylic acid;
s6, dissolving 5-bromo-1H-3-pyrazolecarboxylic acid and 2, 3-dichloropyridine in an ethanol solution, adding a potassium carbonate solid, heating and refluxing to obtain 1- (3-chloro-2-pyridyl) -3-bromo-1H-5-pyrazolecarboxylic acid, and controlling the heating and refluxing reaction time in the condensation reaction to be 12 hours;
s7, carrying out amide reaction on 1- (3-chloro-2-pyridyl) -3-bromo-1H-5-pyrazolecarboxylic acid and N-methyl-3-methyl-2-amino-5-chloro-benzamide by using a catalyst in a matching manner, wherein the catalyst is dimethylformamide, so as to obtain chlorantraniliprole.
Example 2
S1, stirring a solvent containing 2-amino-3-methylbenzoic acid, wherein the solvent is an ether compound, dropwise adding a methylamine solution in the stirring reaction process, heating and refluxing, and then extracting and drying to obtain N-methyl-3-methyl-2-amino-benzamide;
s2, dissolving N-methyl-3-methyl-2-amino-benzamide in an alkali liquor, wherein the alkali liquor is a potassium tert-butoxide aqueous solution, continuously stirring for 10min, dropwise adding 30% hydrogen peroxide, controlling the temperature to be 28 ℃, and performing a halogenation reaction with NCS after the reaction is finished to obtain N-methyl-3-methyl-2-amino-5-chloro-benzamide;
s3, selecting 3-aminocrotonic nitrile to stir, adding hydrazine hydrate to mix during stirring, performing cyclization reaction, naturally heating to room temperature to react for 4 hours to obtain 3-amino-5-methylpyrazole, adjusting the pH value to 3 during stirring the 3-aminocrotonic nitrile and the hydrazine hydrate, performing ice bath or stirring at 50 ℃, and stirring at the speed of 250 rpm;
s4, carrying out bromination reaction on 3-amino-5-methylpyrazole, namely mixing the 3-amino-5-methylpyrazole with concentrated hydrobromic acid and cuprous bromide, heating to 80 ℃, adding a sodium nitrite aqueous solution, continuously stirring for reaction for 60min, adding methyl 3-methyl-2-aminobenzoate, chlorinating with NCS, adding methyl 3-methyl-2-aminobenzoate, and chlorinating with sulfuryl chloride SO2Cl2 to obtain 3-methyl-5-bromopyrazole;
s5, adding 5-chloro-3-methyl-2-methyl aminobenzoate into 3-methyl-5-bromopyrazole to perform oxidation reaction by matching with an oxidant, controlling the reaction temperature to be 80 ℃, and controlling the stirring reaction time to be 35min to obtain 5-bromo-1H-3-pyrazolecarboxylic acid;
s6, dissolving 5-bromo-1H-3-pyrazolecarboxylic acid and 2, 3-dichloropyridine in an ethanol solution, adding a potassium carbonate solid, heating and refluxing to obtain 1- (3-chloro-2-pyridyl) -3-bromo-1H-5-pyrazolecarboxylic acid, and controlling the heating and refluxing reaction time in the condensation reaction to be 14H;
s7, carrying out amide reaction on 1- (3-chloro-2-pyridyl) -3-bromo-1H-5-pyrazolecarboxylic acid and N-methyl-3-methyl-2-amino-5-chloro-benzamide by using a catalyst in a matching manner, wherein the catalyst is dimethylformamide, so as to obtain chlorantraniliprole.
Example 3
S1, stirring a solvent containing 2-amino-3-methylbenzoic acid, wherein the solvent is an ether compound, dropwise adding a methylamine solution in the stirring reaction process, heating and refluxing, and then extracting and drying to obtain N-methyl-3-methyl-2-amino-benzamide;
s2, dissolving N-methyl-3-methyl-2-amino-benzamide in an alkali liquor, wherein the alkali liquor is a potassium tert-butoxide aqueous solution, continuously stirring for 8min, dropwise adding 30% hydrogen peroxide, controlling the temperature to be 25 ℃, and performing a halogenation reaction with NCS after the reaction is finished to obtain N-methyl-3-methyl-2-amino-5-chloro-benzamide;
s3, selecting 3-aminocrotonic nitrile to stir, adding hydrazine hydrate to mix during stirring, performing cyclization reaction, naturally heating to room temperature to react for 4 hours to obtain 3-amino-5-methylpyrazole, adjusting the pH value to 3 during stirring the 3-aminocrotonic nitrile and the hydrazine hydrate, performing ice bath or stirring at 50 ℃, and controlling the stirring speed to be 230 rpm;
s4, carrying out bromination reaction on 3-amino-5-methylpyrazole, namely mixing the 3-amino-5-methylpyrazole with concentrated hydrobromic acid and cuprous bromide, heating to 70 ℃, adding a sodium nitrite aqueous solution, continuously stirring for reaction for 50min, adding methyl 3-methyl-2-aminobenzoate, chlorinating with NCS, adding methyl 3-methyl-2-aminobenzoate, and chlorinating with sulfuryl chloride SO2Cl2 to obtain 3-methyl-5-bromopyrazole;
s5, adding 5-chloro-3-methyl-2-methyl aminobenzoate into 3-methyl-5-bromopyrazole to perform oxidation reaction by matching with an oxidant, controlling the reaction temperature to be 80 ℃, and controlling the stirring reaction time to be 32min to obtain 5-bromo-1H-3-pyrazolecarboxylic acid;
s6, dissolving 5-bromo-1H-3-pyrazolecarboxylic acid and 2, 3-dichloropyridine in an ethanol solution, adding a potassium carbonate solid, heating and refluxing to obtain 1- (3-chloro-2-pyridyl) -3-bromo-1H-5-pyrazolecarboxylic acid, and controlling the heating and refluxing reaction time to be 15 hours in the condensation reaction;
s7, carrying out amide reaction on 1- (3-chloro-2-pyridyl) -3-bromo-1H-5-pyrazolecarboxylic acid and N-methyl-3-methyl-2-amino-5-chloro-benzamide by using a catalyst in a matching manner, wherein the catalyst is dimethylformamide, so as to obtain chlorantraniliprole.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (8)
1. The method for synthesizing chlorantraniliprole is characterized by comprising the following steps:
s1, stirring a solvent containing 2-amino-3-methylbenzoic acid, dropwise adding a methylamine solution in the stirring reaction process, heating and refluxing, extracting, and drying to obtain N-methyl-3-methyl-2-amino-benzamide;
s2, dissolving N-methyl-3-methyl-2-amino-benzamide in alkali liquor, stirring for 5-10 min, dropwise adding hydrogen peroxide with the mass concentration of 30%, controlling the temperature to be 12-28 ℃, and performing a halogenation reaction with NCS after the reaction is finished to obtain N-methyl-3-methyl-2-amino-5-chloro-benzamide;
s3, selecting 3-aminocrotonitrile to stir, adding hydrazine hydrate to mix during stirring, performing cyclization reaction, naturally heating to room temperature to react for 3-4 hours to obtain 3-amino-5-methylpyrazole;
s4, carrying out bromination reaction on 3-amino-5-methylpyrazole, adding 3-methyl-2-methyl aminobenzoate, chlorinating with NCS, adding 3-methyl-2-methyl aminobenzoate, and chlorinating with sulfuryl chloride SO2Cl2 to obtain 3-methyl-5-bromopyrazole;
s5, adding 5-chloro-3-methyl-2-aminobenzoic acid methyl ester into 3-methyl-5-bromopyrazole to perform oxidation reaction by matching with an oxidant to obtain 5-bromo-1H-3-pyrazolecarboxylic acid;
s6, dissolving 5-bromo-1H-3-pyrazolecarboxylic acid and 2, 3-dichloropyridine in an ethanol solution, adding a potassium carbonate solid, and heating and refluxing to obtain 1- (3-chloro-2-pyridyl) -3-bromo-1H-5-pyrazolecarboxylic acid;
s7, carrying out amide reaction on 1- (3-chloro-2-pyridyl) -3-bromo-1H-5-pyrazolecarboxylic acid and N-methyl-3-methyl-2-amino-5-chloro-benzamide by using a catalyst, so as to obtain chlorantraniliprole.
2. The method for synthesizing chlorantraniliprole according to claim 1, wherein the method comprises the following steps: the solvent in the S1 is glacial acetic acid, aromatic hydrocarbon compounds, alicyclic hydrocarbon compounds, halogenated hydrocarbon compounds, ketone compounds or ether compounds.
3. The method for synthesizing chlorantraniliprole according to claim 1, wherein the method comprises the following steps: the alkali liquor in the S2 is an aqueous solution of potassium hydroxide, calcium hydroxide, sodium ethoxide, sodium butoxide or potassium tert-butoxide.
4. The method for synthesizing chlorantraniliprole according to claim 1, wherein the method comprises the following steps: and in the S3, the pH value of the 3-aminocrotonitrile and hydrazine hydrate is adjusted to 2-3 in the stirring process, and the mixture is subjected to ice bath or stirring at 50 ℃ at the stirring speed of 200-250 rpm.
5. The method for synthesizing chlorantraniliprole according to claim 1, wherein the method comprises the following steps: the catalyst in the S7 is one or more than two of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, 3, 5-dimethylpyridine and 3-chloro-2-methylpyridine.
6. The method for synthesizing chlorantraniliprole according to claim 1, wherein the method comprises the following steps: in the bromination reaction in the S4, 3-amino-5-methylpyrazole, concentrated hydrobromic acid and cuprous bromide need to be mixed, then heated to 60-80 ℃, added with a sodium nitrite aqueous solution, and continuously stirred for reaction for 20-60 min.
7. The method for synthesizing chlorantraniliprole according to claim 1, wherein the method comprises the following steps: the oxidation reaction in the S5 needs to control the reaction temperature to be 60-80 ℃, and the stirring reaction time to be 30-35 min.
8. The method for synthesizing chlorantraniliprole according to claim 1, wherein the method comprises the following steps: the heating reflux reaction time length in the condensation reaction in the S6 needs to be controlled to be 12-15 h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191822A (en) * | 2017-12-06 | 2018-06-22 | 广东丸美生物技术股份有限公司 | A kind of synthetic method of Rynaxypyr |
| WO2021033172A1 (en) * | 2019-08-20 | 2021-02-25 | Eurofins Advinus Limited | Process for the preparation of chlorantraniliprole |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191822A (en) * | 2017-12-06 | 2018-06-22 | 广东丸美生物技术股份有限公司 | A kind of synthetic method of Rynaxypyr |
| WO2021033172A1 (en) * | 2019-08-20 | 2021-02-25 | Eurofins Advinus Limited | Process for the preparation of chlorantraniliprole |
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