CN114478264B - Synthesis method of intermediate of bisamide pesticide - Google Patents

Abstract

The invention relates to an intermediate synthesis method of bisamide pesticides, which includes the following steps: the compound of the formula (1) and the compound of the formula (2) are reacted in a solvent under the action of an amine catalyst, and the reaction is completed After post-treatment, the compound of formula (4) above is obtained. In the present invention, an amine catalyst is added to the reaction system to activate the halogen bond and reduce the reaction temperature, and then the compound of formula (1) that forms a perfluoropropyl radical is used to intercept the para carbon on the phenyl group of the compound of formula (2). Hydrogen atoms generate carbon free radicals, and finally realize C—C bonding reaction. The yield of the compound of formula (4) is ≥70% and the GC purity is ≥99%, achieving the improvement of 2-trifluoromethyl-4- The yield and purity of heptafluoroisopropylaniline are suitable for industrial production and has great implementation value and social and economic benefits.

Description

An intermediate synthesis method of bisamide pesticides

Technical field

The present invention relates to the technical field of organic synthesis, and in particular to an intermediate synthesis method of bisamide pesticides.

Background technique

Bisamide insecticides have been a hot topic in the field of insecticide research in recent years. They act on insects like fish nitin. They have a novel mechanism of action, are highly efficient, have no cross-resistance with traditional pesticides, are safe to non-target organisms and are harmful to the environment. The characteristics of good compatibility have attracted people's attention. Some large foreign pesticide companies have successively entered the research field of bisamide pesticides and participated in the synthesis research of such compounds, thus making them become the first choice for pesticide research and development. A big hotspot. Since the advent of flubendiamide, eight products have been commercialized or are about to be commercialized, making it the insecticide variety with the most market potential.

At present, the new insecticides flubendiamide and 2-bromiflubendiamide are pesticides with important market value. Among them, 2-methyl-4-heptafluoroisopropylaniline is the key intermediate of flubendiamide, and 2-trifluoromethyl-4-heptafluoroisopropylaniline is the intermediate of 2-bromoflubendiamide. Key intermediates. 2-Trifluoromethyl-4-heptafluoroisopropylaniline has low activity due to the introduction of ortho-trifluoromethylaniline, so 2-trifluoromethylaniline is directly synthesized from 2-trifluoromethylaniline. The yields of base-4-heptafluoroisopropylaniline are relatively low.

The existing synthesis methods of 2-trifluoromethyl-4-heptafluoroisopropylaniline mainly include the following two methods: 1) synthesis of 2-trifluoromethylaniline through the reaction of 2-trifluoromethylaniline and heptafluoroiodopropane -4-Heptafluoroisopropylaniline. In this method, the cost of the raw material heptafluoroiodopropane is high, and the yield is too low. The yield does not match the economic benefits, resulting in the lack of market competitiveness of the process; 2) Through 2-three Fluoromethylaniline and heptafluorobromopropane are reacted to synthesize 2-trifluoromethyl-4-heptafluoroisopropylaniline. This method uses heptafluorobromopropane as raw material. The production cost can be reduced, but the reactivity of heptafluorobromopropane is relatively low. Low. In order to increase the reaction yield, the reaction needs to be carried out at a higher temperature. The boiling point of heptafluorobromopropane is only 14°C, so the reaction needs to be carried out in closed equipment, and the maximum reaction conversion rate is only 70%. The actual yield It is far less than 70%, which is not conducive to reducing production costs.

Therefore, there is an urgent need to develop a synthesis method for the intermediate (2-trifluoromethyl-4-heptafluoroisopropylaniline) of bisamide pesticides, so as to increase the 2 -The yield and purity of trifluoromethyl-4-heptafluoroisopropylaniline are suitable for industrial production and have important economic value.

Contents of the invention

The problem to be solved by the present invention is to provide an intermediate synthesis method of bisamide pesticides in view of the above-mentioned deficiencies in the prior art, which solves the problems of high cost and low yield of the existing synthesis methods, and achieves In order to improve the yield and purity of 2-trifluoromethyl-4-heptafluoroisopropylaniline.

The above-mentioned invention objects of the present invention are achieved through the following technical solutions:

An intermediate synthesis method for bisamide insecticides. The route of the synthesis method is as follows:

;

The synthesis method includes the following steps: the compound of the above formula (1) and the compound of the above formula (2) are reacted in a solvent under the action of an amine catalyst; after the reaction is completed, the compound of the above formula (4) is obtained by post-processing;

Among them, X is selected from halogen.

By adopting the above technical solution, an amine catalyst is added to the above reaction system, the compound of formula (1) and the amine catalyst form an N...X halogen bond complex, and then under the action of the compound of formula (2), the compound of formula (1) The C—X bond of the compound is broken to form a perfluoropropyl radical, which intercepts the hydrogen atom on the para carbon on the phenyl group of the compound of formula (2) to generate a carbon radical, ultimately achieving C—C bond formation. reaction, the specific reaction process is as follows,

;

During the reaction process, after the amine catalyst is added to the reaction system, the reaction temperature is reduced, the volatile consumption of the compound of formula (1) is controlled, the yield is effectively improved compared to the existing synthesis method, and the impurities are controlled, and the obtained formula (4) The yield of the compound is ≥70% and the GC purity is ≥99%, which achieves the purpose of improving the yield and purity of 2-trifluoromethyl-4-heptafluoroisopropylaniline, and can be suitable for industrial production. Greater implementation value and social and economic benefits.

Specifically, in the compound of the above formula of the present invention, the meaning of "halogen" refers to a halogen element, which may be, without limitation, F, Cl, Br or I.

Further, the amine catalyst is one or a combination of several compounds of the following formulas (31) to (35),

.

Preferably, the molar ratio of the compound of the above formula (1), the compound of the above formula (2) and the amine catalyst is 1.00: (1.00~1.50): (0.01~0.80). More preferably, the molar ratio of the compound of the above formula (1), the compound of the above formula (2) and the amine catalyst is 1.00:1.20:0.10, which is beneficial to increasing the yield of the compound of the above formula (4).

Further, the synthesis method also includes the step of adding one or more combinations of an initiator, a basic compound and a surfactant into the mixed solvent. Specifically, the initiator, alkaline compound and surfactant are put into the solvent before the reaction starts, and some alkaline compounds are put into the solvent after the reaction is completed to promote the reaction and neutralize the acid generated by the reaction.

Preferably, the initiator is sodium dithionite, potassium dithionite, zinc dithionite or zinc sulfite, the alkaline compound is an inorganic base or an organic base, and the surfactant is a quaternary ammonium salt type. Surfactants, phosphate ester salt type surfactants or crown ether type surfactants. More preferably, the inorganic base is sodium carbonate, sodium bicarbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate or hydrogen phosphate. Dipotassium, surfactants are tetrabutylammonium bisulfate, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, trioctylmethylammonium chloride, dodecyl Trimethylammonium chloride or tetradecyltrimethylammonium chloride.

Preferably, the molar ratio of the compound of formula (1), basic compound, surfactant and initiator is 1.00: (1.00~1.50): (0.01~0.10): (1.00~1.50). More preferably, the molar ratio of the compound of formula (1), basic compound, surfactant and initiator is 1.00:1.20:0.01:1.20, which is beneficial to increasing the yield of the compound of formula (4).

Furthermore, the reaction temperature of the reaction is -20~100°C, and the reaction time is 10~12h. Preferably, the reaction is carried out in a closed or non-closed system, and before the reaction, the reaction vessel is cooled to -5~5°C in advance, and the compound of formula (1) is stored in an environment of -5~5°C in advance.

Furthermore, the solvent includes one or two mixtures of organic solvent and water; in the mixture of solvents, the volume ratio of organic solvent and water is 1.00: (0.75~1.00). Among them, the organic solvent is first used as a solvent for the compound of formula (1) above to obtain the compound of formula (1)/organic solvent. After adding the compound of formula (2) and the amine catalyst, the remaining water is added for mixing and stirring; or during the reaction After completion, evaporate the organic solvent and add water to dilute it.

Preferably, the organic solvent is a halogenated alkane solvent, an ether solvent, an alcohol solvent, a ketone solvent, an amide solvent, an ester solvent or a nitrile solvent. More preferably, the halogenated alkane solvent is selected from dichloroethane or methylene chloride, the ether solvent is selected from diethyl ether or methyl tert-butyl ether, the alcohol solvent is selected from methanol or ethanol, and the ketone solvent is selected from acetone or butyl ether. The ketone and amide solvents are selected from N,N-dimethylformamide, the ester solvent is selected from ethyl acetate, and the nitrile solvent is selected from acetonitrile.

Preferably, the mass ratio of the compound of formula (2) above and the organic solvent is 1:(2~20). By adopting the above ratio, the compound of the above formula (2) can be fully dissolved.

Furthermore, the synthesis method includes the following steps: first, add the compound of the formula (1)/organic solvent, the compound of the formula (2) and water to the reaction vessel in sequence, stir and mix, and then add the alkaline compound, surface The activator and amine catalyst are stirred and mixed, and then an initiator is added to react. After the reaction is completed, the reaction product is extracted and separated, washed, dried, filtered and distilled under reduced pressure to obtain the compound of formula (4) above.

Furthermore, the synthesis method includes the following steps: first, add the compound of the formula (1)/organic solvent, the compound of the formula (2) and the amine catalyst to the reaction vessel in sequence, stir and mix, and then add the first portion in sequence. Alkaline compounds and surfactants are stirred and mixed, and then an initiator is added to react. After the reaction is completed, the reaction product is distilled and the organic solvent is recovered. The distillation residue is diluted with water, and after the second portion of the alkaline compound is added, the reaction product is Extraction, liquid separation, washing, drying, filtration and vacuum distillation are performed to obtain the compound of formula (4) above; the molar ratio of the first basic compound to the second basic compound is 0.20: (0.80~1.30).

Preferably, the extraction agent for extraction and liquid separation is selected from ethyl acetate or dichloroethane, the detergent for washing is selected from water and/or sodium carbonate, and the drying desiccant is selected from anhydrous sodium sulfate.

To sum up, the beneficial technical effects of the present invention are as follows: activating halogen bonds and lowering the reaction temperature by adding amine catalysts to the reaction system, and then supplementing the formula (1) with the formation of perfluoropropyl free radicals to intercept formula (2) ) The hydrogen atom on the para carbon on the phenyl group of the compound generates carbon free radicals, and finally realizes the C—C bonding reaction. The yield of the compound of formula (4) is ≥70%, and the GC purity is ≥99%, reaching In order to improve the yield and purity of 2-trifluoromethyl-4-heptafluoroisopropylaniline, it can be suitable for industrial production and has great implementation value and social and economic benefits.

Description of the drawings

Figure 1 is a nuclear magnetic resonance spectrum of the reaction product of Example 2 of the present invention;

Figure 2 is a nuclear magnetic resonance spectrum of the reaction product of Example 3 of the present invention;

Figure 3 is a nuclear magnetic resonance spectrum of the reaction product of Example 4 of the present invention;

Figure 4 is a nuclear magnetic resonance spectrum of the reaction product of Example 5 of the present invention;

Figure 5 is a nuclear magnetic resonance spectrum of the reaction product of Example 6 of the present invention;

Figure 6 is a nuclear magnetic resonance spectrum of the reaction product of Example 7 of the present invention;

Figure 7 is a nuclear magnetic resonance spectrum of the reaction product of Example 8 of the present invention;

Figure 8 is a nuclear magnetic resonance spectrum of the reaction product of Example 9 of the present invention.

Detailed ways

In order to make the technical means, creative features, objectives and effects achieved by the present invention clearer and easier to understand, the present invention will be further elaborated below in conjunction with the accompanying drawings and specific implementation modes.

Example

Example 1: This is an intermediate synthesis method of a bisamide pesticide disclosed in the present invention. The route of the synthesis method is as follows:

;

The synthesis method includes the following steps. The compound of the above formula (1) and the compound of the above formula (2) are reacted in a solvent under the action of an amine catalyst, an initiator, an alkaline compound and a surfactant. After the reaction is completed, post-treatment is performed. Obtain the compound of formula (4) above;

Among them, X is selected from halogen.

After adding an amine catalyst to the above reaction system, the compound of formula (1) and the amine catalyst form an N...X halogen bond complex, and then under the action of the compound of formula (2), the C—X bond of the compound of formula (1) is Break to form a perfluoropropyl free radical, which intercepts the hydrogen atom on the para carbon on the phenyl group of the compound of formula (2) to generate a carbon free radical, and finally achieves a C—C bonding reaction. The specific reaction process is as follows ,

;

During the reaction process, after the amine catalyst is added to the reaction system, the reaction temperature is reduced, the volatile consumption of the compound of formula (1) is controlled, the yield is effectively improved compared to the existing synthesis method, and the impurities are controlled, and the obtained formula (4) The yield of the compound is ≥70% and the GC purity is ≥99%, which achieves the purpose of improving the yield and purity of 2-trifluoromethyl-4-heptafluoroisopropylaniline, and can be suitable for industrial production. Greater implementation value and social and economic benefits.

Preferably, the reaction temperature is -20~100°C, and the reaction time is 10~12h.

The amine catalyst is any one of the compounds of the following formulas (31) to (35),

.

The alkaline compound is an inorganic base or an organic base. The inorganic base is preferably sodium carbonate, sodium bicarbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate, Disodium hydrogen phosphate or dipotassium hydrogen phosphate.

The surfactant is a quaternary ammonium salt type surfactant, a phosphate ester salt type surfactant or a crown ether type surfactant, preferably tetrabutylammonium bisulfate, benzyltriethylammonium chloride, or tetrabutylammonium bromide. Ammonium, tetrabutylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride.

The initiator is sodium dithionite, potassium dithionite, zinc dithionite or zinc sulfite.

The molar ratio of the compound of the above formula (1), the compound of the above formula (2), amine catalyst, basic compound, surfactant and initiator is 1.00: (1.00~1.50): (0.01~0.80): (1.00~1.50 ): (0.01~0.10): (1.00~1.50).

The solvent includes one or two mixtures of organic solvent and water; in the solvent mixture, the volume ratio of organic solvent and water is 1.00: (0.75~1.00). The mass ratio of the compound of formula (2) above and the organic solvent is 1: (2~20). The organic solvent is a halogenated alkane solvent, an ether solvent, an alcohol solvent, a ketone solvent, an amide solvent, an ester solvent or a nitrile solvent. Wherein, the halogenated alkane solvent is selected from dichloroethane or methylene chloride, the ether solvent is selected from diethyl ether or methyl tert-butyl ether, the alcohol solvent is selected from methanol or ethanol, and the ketone solvent is selected from acetone or butanone, The amide solvent is selected from N,N-dimethylformamide, the ester solvent is selected from ethyl acetate, and the nitrile solvent is selected from acetonitrile.

Example 2: An intermediate synthesis method for bisamide pesticides disclosed in the present invention. The difference from Example 1 is that it includes the following steps:

S1: First cool the reaction vessel to 0°C, and store the compound of formula (1) in a 0°C environment in advance;

S2: Add 200 mL of 0.5 mol/L acetonitrile solution of the compound of formula (1), the compound of formula (2) and the compound of formula (31) (amine catalyst) to the reaction vessel in sequence, stir and mix, and then add sulfuric acid in sequence Stir and mix sodium bisulfite (the first alkaline compound) and tetrabutylammonium bisulfate (surfactant), then add sodium dithionite (initiator) to react, control the reaction temperature to 10°C, and the reaction time to 12 hours , obtain the reaction product;

After the S3 reaction is completed, distill the reaction product and recover the organic solvent. Dilute the distillation residue with 150 mL of water, add sodium bicarbonate (the second portion of basic compound), and extract three times with 100 mL of dichloroethane. Combine the organic phases. , after washing the organic phase with water and 5% sodium carbonate in sequence, drying with anhydrous sodium sulfate, filtering, steaming off the organic solvent, and distilling under reduced pressure to obtain the compound of formula (4) above;

Among them, the molar ratio of the compound of the above formula (1), the compound of the above formula (2), amine catalyst, basic compound, surfactant and initiator is 1.00:1.20:0.10:1.20:0.01:1.20, the first alkali The molar ratio of the basic compound to the second basic compound is 0.20:1.00.

Referring to Figure 1, the reaction product contains the compound of formula (4) above, and the yield of 2-trifluoromethyl-4-heptafluoroisopropylaniline is 76%, and the GC purity is ≥99%.

Example 3: This is an intermediate synthesis method for bisamide pesticides disclosed in the present invention. The difference from Example 1 is that it includes the following steps:

S1: First cool the reaction vessel to 0°C, and store the compound of formula (1) in a 0°C environment in advance;

S2: Add 200 mL of 0.5 mol/L acetonitrile solution of the compound of formula (1), the compound of formula (2) and the compound of formula (31) (amine catalyst) to the reaction vessel in sequence, stir and mix, and then add carbonic acid in sequence Potassium (the first basic compound) and benzyltriethylammonium chloride (surfactant), stir and mix, then add sodium dithionite (initiator) to react, control the reaction temperature to -20°C, and the reaction time For 10h, the reaction product is obtained;

After the S3 reaction is completed, distill the reaction product and recover the organic solvent. Dilute the distillation residue with 150 mL of water, add sodium bicarbonate (the second portion of basic compound), and extract three times with 100 mL of dichloroethane. Combine the organic phases. , after washing the organic phase with water and 5% sodium carbonate in sequence, drying with anhydrous sodium sulfate, filtering, steaming off the organic solvent, and distilling under reduced pressure to obtain the compound of formula (4) above;

Among them, the molar ratio of the compound of the above formula (1), the compound of the above formula (2), amine catalyst, basic compound, surfactant and initiator is 1.00:1.00:0.01:1.50:0.80:1.00, the first part of alkali The molar ratio of the basic compound to the second basic compound is 0.20:1.30.

Referring to Figure 2, the reaction product contains the compound of formula (4) above, and the yield of 2-trifluoromethyl-4-heptafluoroisopropylaniline is 80%, and the GC purity is ≥99%.

Example 4: This is an intermediate synthesis method for bisamide pesticides disclosed in the present invention. The difference from Example 1 is that it includes the following steps:

S1: First cool the reaction vessel to 0°C, and store the compound of formula (1) in a 0°C environment in advance;

S2: Add 200 mL of 0.5 mol/L acetonitrile solution of the compound of formula (1), the compound of formula (2) and the compound of formula (31) (amine catalyst) to the reaction vessel in sequence, stir and mix, and then add carbonic acid in sequence Stir and mix lithium (the first basic compound) and tetrabutylammonium bromide (surfactant), then add potassium dithionite (initiator) to react, control the reaction temperature to -10°C, and the reaction time For 11h, the reaction product is obtained;

After the S3 reaction is completed, distill the reaction product and recover the organic solvent. Dilute the distillation residue with 150 mL of water, add sodium bicarbonate (the second portion of basic compound), and extract three times with 100 mL of dichloroethane. Combine the organic phases. , after washing the organic phase with water and 5% sodium carbonate in sequence, drying with anhydrous sodium sulfate, filtering, steaming off the organic solvent, and distilling under reduced pressure to obtain the compound of formula (4) above;

Among them, the molar ratio of the compound of the above formula (1), the compound of the above formula (2), amine catalyst, basic compound, surfactant and initiator is 1.00:1.50:0.50:1.20:1.00:1.50, the first alkali The molar ratio of the basic compound to the second basic compound is 0.20:1.00.

Referring to Figure 3, the reaction product contains the compound of formula (4) above, and the yield of 2-trifluoromethyl-4-heptafluoroisopropylaniline is 77%, and the GC purity is ≥99%.

Example 5: An intermediate synthesis method for bisamide pesticides disclosed in the present invention. The difference from Example 1 is that it includes the following steps:

S1: First cool the reaction vessel to 0°C, and store the compound of formula (1) in a 0°C environment in advance;

S2: Add 200 mL of 0.5 mol/L acetonitrile solution of the compound of formula (1), the compound of formula (2) and the compound of formula (32) (amine catalyst) to the reaction vessel in sequence, stir and mix, and then add hydrogen in sequence Stir and mix sodium oxide (the first alkaline compound) and tetrabutylammonium chloride (surfactant), then add sodium dithionite (initiator) to react, control the reaction temperature to 0°C, and the reaction time to 12 hours , obtain the reaction product;

After the S3 reaction is completed, distill the reaction product and recover the organic solvent. Dilute the distillation residue with 150 mL of water, add sodium bicarbonate (the second portion of basic compound), and extract three times with 100 mL of dichloroethane. Combine the organic phases. , after washing the organic phase with water and 5% sodium carbonate in sequence, drying with anhydrous sodium sulfate, filtering, steaming off the organic solvent, and distilling under reduced pressure to obtain the compound of formula (4) above;

Among them, the molar ratio of the compound of the above formula (1), the compound of the above formula (2), amine catalyst, alkaline compound, surfactant and initiator is 1.00:1.40:0.80:1.30:0.90:1.40, the first alkali The molar ratio of the basic compound to the second basic compound is 0.20:1.10.

Referring to Figure 4, the reaction product contains the compound of formula (4) above, and the yield of 2-trifluoromethyl-4-heptafluoroisopropylaniline is 73%, and the GC purity is ≥99%.

Example 6: An intermediate synthesis method for bisamide pesticides disclosed in the present invention. The difference from Example 1 is that it includes the following steps:

S1: First cool the reaction vessel to 0°C, and store the compound of formula (1) in a 0°C environment in advance;

S2: Add 200 mL of 0.5 mol/L acetonitrile solution of the compound of the above formula (1), the compound of the above formula (2) and the compound of the above formula (33) (amine catalyst) into the reaction vessel in sequence, stir and mix, and then add phosphoric acid in sequence Stir sodium dihydrogen (the first basic compound) and trioctylmethyl ammonium chloride (surfactant), then add zinc dithionite (initiator) to react, and control the reaction temperature to 60°C , the reaction time is 10h, and the reaction product is obtained;

After the S3 reaction is completed, distill the reaction product and recover the organic solvent. Dilute the distillation residue with 150 mL of water, add sodium bicarbonate (the second portion of basic compound), and extract three times with 100 mL of dichloroethane. Combine the organic phases. , after washing the organic phase with water and 5% sodium carbonate in sequence, drying with anhydrous sodium sulfate, filtering, steaming off the organic solvent, and distilling under reduced pressure to obtain the compound of formula (4) above;

Among them, the molar ratio of the compound of the above formula (1), the compound of the above formula (2), amine catalyst, basic compound, surfactant and initiator is 1.00:1.10:0.05:1.40:0.50:1.30, the first alkali The molar ratio of the basic compound to the second basic compound is 0.20:1.20.

Referring to Figure 5, the reaction product contains the compound of formula (4) above, and the yield of 2-trifluoromethyl-4-heptafluoroisopropylaniline is 75%, and the GC purity is ≥99%.

Example 7: An intermediate synthesis method for bisamide pesticides disclosed in the present invention. The difference from Example 1 is that it includes the following steps:

S1: First cool the reaction vessel to 0°C, and store the compound of formula (1) in a 0°C environment in advance;

S2: Add 200 mL of 0.5 mol/L acetonitrile solution of the compound of formula (1), the compound of formula (2) and the compound of formula (34) (amine catalyst) to the reaction vessel in sequence, stir and mix, and then add hydrogen in sequence Stir and mix lithium oxide (the first basic compound) and dodecyltrimethylammonium chloride (surfactant), then add sodium dithionite (initiator) to react, and control the reaction temperature to 100°C. The reaction time was 11h, and the reaction product was obtained;

After the S3 reaction is completed, distill the reaction product and recover the organic solvent. Dilute the distillation residue with 150 mL of water, add sodium bicarbonate (the second portion of basic compound), and extract three times with 100 mL of dichloroethane. Combine the organic phases. , after washing the organic phase with water and 5% sodium carbonate in sequence, drying with anhydrous sodium sulfate, filtering, steaming off the organic solvent, and distilling under reduced pressure to obtain the compound of formula (4) above;

Among them, the molar ratio of the compound of the above formula (1), the compound of the above formula (2), amine catalyst, alkaline compound, surfactant and initiator is 1.00:1.30:0.60:1.10:0.70:1.20, the first alkali The molar ratio of the basic compound to the second basic compound is 0.20:0.90.

Referring to Figure 6, the reaction product contains the compound of formula (4) above, and the yield of 2-trifluoromethyl-4-heptafluoroisopropylaniline is 78%, and the GC purity is ≥99%.

Example 8: An intermediate synthesis method for bisamide pesticides disclosed in the present invention. The difference from Example 1 is that it includes the following steps:

S1: First cool the reaction vessel to 0°C, and store the compound of formula (1) in a 0°C environment in advance;

S2: Add 200 mL of 0.5 mol/L acetonitrile solution of the compound of formula (1), the compound of formula (2) and the compound of formula (35) (amine catalyst) to the reaction vessel in sequence, stir and mix, and then add phosphoric acid in sequence Stir and mix dipotassium hydrogen (the first alkaline compound) and tetradecyltrimethylammonium chloride (surfactant), then add zinc sulfite (initiator) to react, and control the reaction temperature to 50°C , the reaction time is 12h, and the reaction product is obtained;

After the S3 reaction is completed, distill the reaction product and recover the organic solvent. Dilute the distillation residue with 150 mL of water, add sodium bicarbonate (the second portion of basic compound), and extract three times with 100 mL of dichloroethane. Combine the organic phases. , after washing the organic phase with water and 5% sodium carbonate in sequence, drying with anhydrous sodium sulfate, filtering, steaming off the organic solvent, and distilling under reduced pressure to obtain the compound of formula (4) above;

Among them, the molar ratio of the compound of the above formula (1), the compound of the above formula (2), amine catalyst, alkaline compound, surfactant and initiator is 1.00:1.20:0.10:1.20:0.60:1.10, the first alkali The molar ratio of the basic compound to the second basic compound is 0.20:1.00.

Referring to Figure 7, the reaction product contains the compound of formula (4) above, and the yield of 2-trifluoromethyl-4-heptafluoroisopropylaniline is 70%, and the GC purity is ≥99%.

Example 9: An intermediate synthesis method for bisamide pesticides disclosed in the present invention. The difference from Example 1 is that it includes the following steps:

S1: First cool the reaction vessel to 0°C, and store the compound of formula (1) in a 0°C environment in advance;

S2: Add 200 mL of the 0.5 mol/L ethyl acetate solution of the compound of the above formula (1), the compound of the above formula (2) and 200 mL of water into the reaction vessel in sequence, stir and mix, and then add sodium carbonate and tetrabutyl hydrogen sulfate in sequence. Stir and mix ammonium and amine catalysts, then add sodium dithionite to react, control the reaction temperature to 10°C, and the reaction time to 12 hours to obtain the reaction product;

After the S3 reaction is completed, separate the aqueous phase and organic phase of the reaction product. Extract the aqueous phase with 20 mL of ethyl acetate and separate the liquids. Combine the organic phases. Wash the organic phase with water and 5% sodium carbonate in sequence, and then dry with anhydrous sodium sulfate. Filter, evaporate the organic solvent, and distill under reduced pressure to obtain the compound of formula (4) above;

Among them, the molar ratio of the compound of the above formula (1), the compound of the above formula (2), amine catalyst, basic compound, surfactant and initiator is 1.00:1.20:0.10:1.20:0.01:1.20.

Referring to Figure 8, the reaction product contains the compound of formula (4) above, and the yield of 2-trifluoromethyl-4-heptafluoroisopropylaniline is 78%, and the GC purity is ≥99%.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not limiting. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified. Modifications or equivalent substitutions without departing from the spirit and scope of the technical solution of the present invention shall be included in the scope of the claims of the present invention.

Claims (5)

1. A synthesis method of an intermediate of a bisamide pesticide is characterized by comprising the following steps of: the route of the synthesis method is as follows,

；

the synthesis method comprises the following steps that the compound of the formula (1) and the compound of the formula (2) react in a solvent under the action of an amine catalyst, and after the reaction is finished, the compound of the formula (4) is obtained through post-treatment;

wherein X is selected from halogen;

the amine catalyst is one or a combination of more than one of the following compounds (31) - (35),

；

the molar ratio of the compound of formula (1), the compound of formula (2) and the amine catalyst is 1.00: 1.00-1.50: 0.01 to 0.80;

the synthesis method further comprises the step of adding one or a combination of more of an initiator, an alkaline compound and a surfactant to the mixed solvent;

the initiator is sodium dithionite, potassium dithionite, zinc dithionite or zinc sulfite, the alkaline compound is inorganic alkali or organic alkali, and the surfactant is a quaternary ammonium salt type surfactant, a phosphate type surfactant or a crown ether type surfactant;

the molar ratio of the compound of the formula (1), the alkaline compound, the surfactant and the initiator is 1.00: 1.00-1.50: 0.01 to 0.10: 1.00-1.50.

2. The method for synthesizing the intermediate of the bisamide insecticide, which is characterized by comprising the following steps of: the reaction temperature of the reaction is-20-100 ℃ and the reaction time is 10-12 h.

3. The method for synthesizing the intermediate of the bisamide insecticide, which is characterized by comprising the following steps of: the solvent comprises one or a mixture of two of an organic solvent and water; in the solvent mixture, the volume ratio of the organic solvent to water was 1.00:0.75 to 1.00.

4. A process for the synthesis of a bisamide insecticide intermediate according to claim 3, wherein: the organic solvent is halogenated hydrocarbon solvent, ether solvent, alcohol solvent, ketone solvent, amide solvent, ester solvent or nitrile solvent.

5. A process for the synthesis of a bisamide insecticide intermediate according to claim 3, wherein: the mass ratio of the compound of the formula (2) to the organic solvent is 1: 2-20.