CN114478264B - Synthesis method of intermediate of bisamide pesticide - Google Patents
Synthesis method of intermediate of bisamide pesticide Download PDFInfo
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Abstract
The invention relates to a synthesis method of an intermediate of a bisamide pesticide, which comprises the following steps of reacting a compound of the formula (1) and a compound of the formula (2) in a solvent under the action of an amine catalyst, and obtaining a compound of the formula (4) through post-treatment after the reaction is finished. According to the invention, an amine catalyst is added into a reaction system to activate halogen bonds, the reaction temperature is reduced, then a compound in the formula (1) which forms perfluoropropyl radicals is used for intercepting hydrogen atoms on para carbon on the phenyl of the compound in the formula (2) to generate carbon radicals, and finally, a C-C bonding reaction is realized, so that the yield of the prepared compound in the formula (4) is more than or equal to 70%, the GC purity is more than or equal to 99%, the purpose of improving the yield and purity of 2-trifluoromethyl-4-heptafluoroisopropylaniline is achieved, the method is suitable for industrial production, and the method has great implementation value and social and economic benefits.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing an intermediate of a bisamide pesticide.
Background
The bisamide pesticide is a hot spot in the field of pesticide research in recent years, and the ryanodine of the action field insect is portable, has the characteristics of novel and efficient action mechanism, no interactive resistance with the traditional pesticide, safety to non-target organisms and good environmental compatibility, attracts attention, and a plurality of large pesticide companies abroad enter the field of bisamide pesticide research successively and participate in the synthesis research of the compound, so that the bisamide pesticide becomes a big hot spot for pesticide research and development. From the advent of fipronil amide to date, 8 products have been commercialized or are about to be commercialized, and become the most potential pesticide variety at present.
At present, the novel pesticides fipronil diamide and 2-bromofluorobenzene diamide are pesticides with important market value. Wherein 2-methyl-4-heptafluoroisopropylaniline is a key intermediate of flubendiamide, and 2-trifluoromethyl-4-heptafluoroisopropylaniline is a key intermediate of 2-bromobendiamide. 2-trifluoromethyl-4-heptafluoroisopropylaniline is introduced by ortho-trifluoromethyl, the activity of 2-trifluoromethyl aniline is lower, and the yield of 2-trifluoromethyl-4-heptafluoroisopropylaniline directly synthesized from 2-trifluoromethyl aniline is lower.
The existing synthetic method of 2-trifluoromethyl-4-heptafluoroisopropyl aniline mainly comprises the following two steps of 1) synthesizing 2-trifluoromethyl-4-heptafluoroisopropyl aniline through the reaction of 2-trifluoromethyl aniline and heptafluoroiodopropane, wherein the raw material heptafluoroiodopropane is high in cost, and meanwhile, the yield is too low and is not matched with economic benefit, so that the process lacks market competitiveness; 2) The 2-trifluoromethyl-4-heptafluoroisopropyl aniline is synthesized by the reaction of 2-trifluoromethyl aniline and heptafluoro-bromopropane, wherein the method adopts heptafluoro-bromopropane as a raw material, so that the production cost can be reduced, but the heptafluoro-bromopropane has lower reaction activity, the reaction needs to be carried out at a higher temperature to improve the reaction yield, and the boiling point of the heptafluoro-bromopropane is only 14 ℃, so that the reaction needs to be carried out in closed equipment, the highest reaction conversion rate is only 70%, and the actual yield is far lower than 70%, thereby being unfavorable for reducing the production cost.
Therefore, there is a need to develop a method for synthesizing an intermediate (2-trifluoromethyl-4-heptafluoroisopropylaniline) of bisamide pesticides, so that the yield and purity of the 2-trifluoromethyl-4-heptafluoroisopropylaniline are improved on the basis of using perfluorinated compounds, and the method is suitable for industrial production and has important economic value.
Disclosure of Invention
The invention aims to solve the problems of the prior art, and provides a synthesis method of an intermediate of a bisamide pesticide, which solves the problems of high cost and low yield of the prior synthesis method and achieves the purpose of improving the yield and purity of 2-trifluoromethyl-4-heptafluoroisopropylaniline.
The above object of the present invention is achieved by the following technical solutions:
a synthetic method of an intermediate of a bisamide pesticide comprises the following steps of,
；
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.
By adopting the technical scheme, the amine catalyst is added in the reaction system, the compound of the formula (1) and the amine catalyst form N … X halogen bond complex, then under the action of the compound of the formula (2), the C-X bond of the compound of the formula (1) is broken to form perfluoropropyl free radical, the free radical intercepts the hydrogen atom on para carbon on phenyl of the compound of the formula (2) to generate carbon free radical, the C-C bond forming reaction is finally realized, the specific reaction process is as follows,
；
in the reaction process, after an amine catalyst is added into a reaction system, the reaction temperature is reduced, the volatile consumption of the compound of the formula (1) is controlled, the yield of the compound of the formula (4) is effectively improved, the impurity is controlled, the yield of the prepared compound of the formula (4) is more than or equal to 70%, the GC purity is more than or equal to 99%, the purpose of improving the yield and purity of 2-trifluoromethyl-4-heptafluoroisopropylaniline is achieved, the method is suitable for industrial production, and the method has great implementation value and social and economic benefits.
Specifically, in the compounds of the above formula of the present invention, the meaning of "halogen" means a halogen element, and may be, for example, F, cl, br or I without limitation.
Further, the amine catalyst is one or a combination of more than one of the compounds of the following formulas (31) - (35),
。
preferably, the molar ratio of the compound of formula (1) above, the compound of formula (2) above and the amine catalyst is 1.00: (1.00-1.50): (0.01 to 0.80). More preferably, the molar ratio of the compound of formula (1) above, the compound of formula (2) above and the amine catalyst is 1.00:1.20:0.10, which is advantageous in improving the yield of the compound of the above formula (4).
Further, the synthesis method further comprises the step of adding one or a combination of several of an initiator, a basic compound and a surfactant to the mixed solvent. Specifically, an initiator, a basic compound and a surfactant are put into a solvent before the start of the reaction, and a part of the basic compound is put into the solvent after the end of the reaction to promote the progress of 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 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. 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 dipotassium hydrogen phosphate, and the surfactant is tetrabutylammonium hydrogen sulfate, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride.
Preferably, the molar ratio of the compound of formula (1) above, the basic compound, the surfactant and the initiator is 1.00: (1.00-1.50): (0.01 to 0.10): (1.00-1.50). More preferably, the molar ratio of the compound of formula (1) above, the basic compound, the surfactant and the initiator is 1.00:1.20:0.01:1.20, which is advantageous in improving the yield of the compound of formula (4) above.
Further, the reaction temperature of the reaction is-20-100 ℃ and the reaction time is 10-12 hours. Preferably, the reaction is carried out in a closed or non-closed system, and before the reaction, the reaction vessel is cooled to-5 to 5 ℃ in advance, and the compound of the formula (1) is stored in an environment of-5 to 5 ℃ in advance.
Still further, 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). The method comprises the steps of (1) firstly, using an organic solvent as a solvent of a compound of the formula (1) to obtain a compound of the formula (1)/organic solvent, adding the compound of the formula (2) and an amine catalyst, and then adding the rest water for mixing and stirring; or after the reaction is finished, evaporating the organic solvent, and then adding water for dilution.
Preferably, the organic solvent is a halogenated hydrocarbon solvent, an ether solvent, an alcohol solvent, a ketone solvent, an amide solvent, an ester solvent, or a nitrile solvent. More preferably, the haloalkane solvent is selected from dichloroethane or dichloromethane, the ether solvent is selected from diethyl ether or methyl tert-butyl ether, the alcohol solvent is selected from methanol or ethanol, 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.
Preferably, the mass ratio of the compound of formula (2) and the organic solvent is 1: (2-20). By using the above ratio, the compound of the above formula (2) can be sufficiently dissolved.
Further, the synthesis method comprises the steps of sequentially adding the compound of the formula (1)/organic solvent, the compound of the formula (2) and water into a reaction container, stirring and mixing the mixture uniformly, sequentially adding the alkaline compound, the surfactant and the amine catalyst, stirring and mixing the mixture uniformly, adding the initiator to react, and obtaining the compound of the formula (4) through extraction and liquid separation, washing, drying, filtering and reduced pressure distillation of a reaction product after the reaction is finished.
Further, the synthesis method comprises the steps of sequentially adding the compound of the formula (1)/organic solvent, the compound of the formula (2) and amine catalyst into a reaction container, stirring and mixing uniformly, sequentially adding the first part of alkaline compound and surfactant, stirring and mixing uniformly, adding an initiator for reaction, distilling a reaction product after the reaction is finished, recycling the organic solvent, diluting distilled residues with water, adding the second part of alkaline compound, and obtaining the compound of the formula (4) through extraction and liquid separation, washing, drying, filtration and reduced pressure distillation of the reaction product; the molar ratio of the first part of basic compound to the second part of basic compound is 0.20: (0.80 to 1.30).
Preferably, the extractant of the extraction liquid is selected from ethyl acetate or dichloroethane, the washing detergent is selected from water and/or sodium carbonate, and the drying agent is selected from anhydrous sodium sulfate.
In summary, the beneficial technical effects of the invention are as follows: the amine catalyst is added into a reaction system to activate halogen bonds, the reaction temperature is reduced, then the compound of the formula (1) which forms perfluoropropyl radicals is used for intercepting hydrogen atoms on para carbon on phenyl of the compound of the formula (2) to generate carbon radicals, and finally, the C-C bonding reaction is realized, so that the yield of the prepared compound of the formula (4) is more than or equal to 70%, the GC purity is more than or equal to 99%, the purpose of improving the yield and purity of 2-trifluoromethyl-4-heptafluoroisopropylaniline is achieved, the method is suitable for industrial production, and the method has great implementation value and social and economic benefits.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the reaction product of example 2 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of the reaction product of example 3 of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of the reaction product of example 4 of the present invention;
FIG. 4 is a nuclear magnetic resonance spectrum of the reaction product of example 5 of the present invention;
FIG. 5 is a nuclear magnetic resonance spectrum of the reaction product of example 6 of the present invention;
FIG. 6 is a nuclear magnetic resonance spectrum of the reaction product of example 7 of the present invention;
FIG. 7 is a nuclear magnetic resonance spectrum of the reaction product of example 8 of the present invention;
FIG. 8 is a nuclear magnetic resonance spectrum of the reaction product of example 9 of the present invention.
Detailed Description
The invention will be further described with reference to the drawings and detailed description in order to make the technical means, the creation characteristics, the achievement of the objects and the functions of the invention more clear and easy to understand.
Examples
Example 1: the invention discloses a synthesis method of an intermediate of a bisamide pesticide, which comprises the following steps of,
；
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, an initiator, an alkaline compound and a surfactant, and after the reaction is finished, the compound of the formula (4) is obtained through post-treatment;
wherein X is selected from halogen.
Adding amine catalyst, forming N … X halogen bond complex by the compound of formula (1) and amine catalyst, then breaking C-X bond of the compound of formula (1) under the action of the compound of formula (2) to form perfluoropropyl free radical, intercepting hydrogen atom on para carbon on phenyl of the compound of formula (2) by the free radical to generate carbon free radical, finally realizing C-C bond reaction, wherein the specific reaction process is as follows,
；
in the reaction process, after an amine catalyst is added into a reaction system, the reaction temperature is reduced, the volatile consumption of the compound of the formula (1) is controlled, the yield of the compound of the formula (4) is effectively improved, the impurity is controlled, the yield of the prepared compound of the formula (4) is more than or equal to 70%, the GC purity is more than or equal to 99%, the purpose of improving the yield and purity of 2-trifluoromethyl-4-heptafluoroisopropylaniline is achieved, the method is suitable for industrial production, and the method has great implementation value and social and economic benefits.
Preferably, the reaction temperature of the reaction is-20-100 ℃ and the reaction time is 10-12 h.
The amine catalyst is any one of the compounds of the following formulas (31) - (35),
。
the basic compound is an inorganic base or an organic base, and 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 quaternary ammonium salt type surfactant, phosphate ester type surfactant or crown ether type surfactant, preferably tetrabutylammonium bisulfate, benzyltriethylammonium chloride, tetrabutylammonium bromide, 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 formula (1), the compound of formula (2), the amine catalyst, the basic compound, the surfactant and the initiator is 1.00: (1.00-1.50): (0.01 to 0.80): (1.00-1.50): (0.01 to 0.10): (1.00-1.50).
The solvent comprises one or 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). The mass ratio of the compound of the formula (2) to the organic solvent is 1: (2-20). The organic solvent is halogenated hydrocarbon solvent, ether solvent, alcohol solvent, ketone solvent, amide solvent, ester solvent or nitrile solvent. Wherein the halogenated alkane solvent is selected from dichloroethane or dichloromethane, the ether solvent is selected from diethyl ether or methyl tertiary butyl ether, the alcohol solvent is selected from methanol or ethanol, 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: the synthesis method of the intermediate of the bisamide pesticide disclosed by the invention is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling a reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment of 0 ℃ in advance;
s2, sequentially adding 200mL of 0.5mol/L acetonitrile solution of the compound of the formula (1), the compound of the formula (2) and the compound of the formula (31) (amine catalyst) into a reaction container, stirring and mixing uniformly, sequentially adding sodium bisulfate (first part of alkaline compound) and tetrabutylammonium bisulfate (surfactant), stirring and mixing uniformly, then adding sodium hydrosulfite (initiator) for reaction, and controlling the reaction temperature to be 10 ℃ and the reaction time to be 12 hours to obtain a reaction product;
s3, after the reaction is finished, distilling a reaction product, recovering an organic solvent, diluting a distillation residue by adding 150mL of water, adding sodium bicarbonate (second alkaline compound), extracting with 100mL of dichloroethane for 3 times respectively, merging organic phases, washing the organic phases with water and 5% sodium carbonate in sequence, drying the organic phases with anhydrous sodium sulfate, filtering, distilling the organic solvent, and distilling under reduced pressure to obtain a compound of the formula (4);
wherein the molar ratio of the compound of formula (1), the compound of formula (2), the amine catalyst, the basic compound, the surfactant and the initiator is 1.00:1.20: 0.10: 1.20:0.01:1.20 The molar ratio of the first part of basic compound to the second part of basic compound is 0.20: 1.00.
Referring to FIG. 1, the compound of formula (4) above was formed in the reaction product with a yield of 76% and a GC purity of 99% or more of 2-trifluoromethyl-4-heptafluoroisopropylaniline.
Example 3: the synthesis method of the intermediate of the bisamide pesticide disclosed by the invention is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling a reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment of 0 ℃ in advance;
s2, sequentially adding 200mL of 0.5mol/L acetonitrile solution of the compound of the formula (1), the compound of the formula (2) and the compound of the formula (31) (amine catalyst) into a reaction container, stirring and mixing uniformly, sequentially adding potassium carbonate (first part of alkaline compound) and benzyl triethyl ammonium chloride (surfactant), stirring and mixing uniformly, then adding sodium dithionite (initiator) for reaction, and controlling the reaction temperature to be minus 20 ℃ and the reaction time to be 10 hours to obtain a reaction product;
s3, after the reaction is finished, distilling a reaction product, recovering an organic solvent, diluting a distillation residue by adding 150mL of water, adding sodium bicarbonate (second alkaline compound), extracting with 100mL of dichloroethane for 3 times respectively, merging organic phases, washing the organic phases with water and 5% sodium carbonate in sequence, drying the organic phases with anhydrous sodium sulfate, filtering, distilling the organic solvent, and distilling under reduced pressure to obtain a compound of the formula (4);
wherein the molar ratio of the compound of formula (1), the compound of formula (2), the amine catalyst, the basic compound, the surfactant and the initiator is 1.00: 1.00: 0.01: 1.50: 0.80: 1.00 The molar ratio of the first part of basic compound to the second part of basic compound is 0.20: 1.30.
Referring to FIG. 2, the compound of formula (4) above was formed in the reaction product with a yield of 80% and a GC purity of 99% or more of 2-trifluoromethyl-4-heptafluoroisopropylaniline.
Example 4: the synthesis method of the intermediate of the bisamide pesticide disclosed by the invention is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling a reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment of 0 ℃ in advance;
s2, sequentially adding 200mL of 0.5mol/L acetonitrile solution of the compound of the formula (1), the compound of the formula (2) and the compound of the formula (31) (amine catalyst) into a reaction container, stirring and mixing uniformly, sequentially adding lithium carbonate (first part of alkaline compound) and tetrabutylammonium bromide (surfactant), stirring and mixing uniformly, then adding potassium dithionite (initiator) for reaction, controlling the reaction temperature to be-10 ℃ and the reaction time to be 11h, and obtaining a reaction product;
s3, after the reaction is finished, distilling a reaction product, recovering an organic solvent, diluting a distillation residue by adding 150mL of water, adding sodium bicarbonate (second alkaline compound), extracting with 100mL of dichloroethane for 3 times respectively, merging organic phases, washing the organic phases with water and 5% sodium carbonate in sequence, drying the organic phases with anhydrous sodium sulfate, filtering, distilling the organic solvent, and distilling under reduced pressure to obtain a compound of the formula (4);
wherein the molar ratio of the compound of formula (1), the compound of formula (2), the amine catalyst, the basic compound, the surfactant and the initiator is 1.00: 1.50: 0.50: 1.20: 1.00: 1.50 The molar ratio of the first part of basic compound to the second part of basic compound is 0.20: 1.00.
Referring to FIG. 3, the compound of formula (4) above was formed in the reaction product with a yield of 77% and a GC purity of 99% or more of 2-trifluoromethyl-4-heptafluoroisopropylaniline.
Example 5: the synthesis method of the intermediate of the bisamide pesticide disclosed by the invention is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling a reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment of 0 ℃ in advance;
s2, sequentially adding 200mL of 0.5mol/L acetonitrile solution of the compound of the formula (1), the compound of the formula (2) and the compound of the formula (32) (amine catalyst) into a reaction container, stirring and mixing uniformly, sequentially adding sodium hydroxide (first part of alkaline compound) and tetrabutylammonium chloride (surfactant), stirring and mixing uniformly, then adding sodium dithionite (initiator) for reaction, controlling the reaction temperature to be 0 ℃ and the reaction time to be 12 hours, and obtaining a reaction product;
s3, after the reaction is finished, distilling a reaction product, recovering an organic solvent, diluting a distillation residue by adding 150mL of water, adding sodium bicarbonate (second alkaline compound), extracting with 100mL of dichloroethane for 3 times respectively, merging organic phases, washing the organic phases with water and 5% sodium carbonate in sequence, drying the organic phases with anhydrous sodium sulfate, filtering, distilling the organic solvent, and distilling under reduced pressure to obtain a compound of the formula (4);
wherein the molar ratio of the compound of formula (1), the compound of formula (2), the amine catalyst, the basic compound, the surfactant and the initiator is 1.00: 1.40: 0.80: 1.30: 0.90: 1.40 The molar ratio of the first part of basic compound to the second part of basic compound is 0.20: 1.10.
Referring to FIG. 4, the compound of formula (4) above was formed in the reaction product with a yield of 73% 2-trifluoromethyl-4-heptafluoroisopropylaniline and a GC purity of 99% or more.
Example 6: the synthesis method of the intermediate of the bisamide pesticide disclosed by the invention is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling a reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment of 0 ℃ in advance;
s2, sequentially adding 200mL of 0.5mol/L acetonitrile solution of the compound of the formula (1), the compound of the formula (2) and the compound of the formula (33) (amine catalyst) into a reaction container, stirring and mixing uniformly, sequentially adding sodium dihydrogen phosphate (first part of alkaline compound) and trioctylmethyl ammonium chloride (surfactant), stirring and mixing uniformly, then adding zinc dithionite (initiator) for reaction, controlling the reaction temperature to be 60 ℃ and the reaction time to be 10 hours, and obtaining a reaction product;
s3, after the reaction is finished, distilling a reaction product, recovering an organic solvent, diluting a distillation residue by adding 150mL of water, adding sodium bicarbonate (second alkaline compound), extracting with 100mL of dichloroethane for 3 times respectively, merging organic phases, washing the organic phases with water and 5% sodium carbonate in sequence, drying the organic phases with anhydrous sodium sulfate, filtering, distilling the organic solvent, and distilling under reduced pressure to obtain a compound of the formula (4);
wherein the molar ratio of the compound of formula (1), the compound of formula (2), the amine catalyst, the basic compound, the surfactant and the initiator is 1.00: 1.10: 0.05: 1.40: 0.50: 1.30 The molar ratio of the first part of basic compound to the second part of basic compound is 0.20: 1.20.
Referring to FIG. 5, the compound of formula (4) above was formed in the reaction product with a yield of 75% 2-trifluoromethyl-4-heptafluoroisopropylaniline and a GC purity of 99% or more.
Example 7: the synthesis method of the intermediate of the bisamide pesticide disclosed by the invention is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling a reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment of 0 ℃ in advance;
s2, sequentially adding 200mL of 0.5mol/L acetonitrile solution of the compound of the formula (1), the compound of the formula (2) and the compound of the formula (34) (amine catalyst) into a reaction container, stirring and mixing uniformly, sequentially adding lithium hydroxide (first part of alkaline compound) and dodecyl trimethyl ammonium chloride (surfactant), stirring and mixing uniformly, then adding sodium hydrosulfite (initiator) for reaction, and controlling the reaction temperature to be 100 ℃ and the reaction time to be 11 hours to obtain a reaction product;
s3, after the reaction is finished, distilling a reaction product, recovering an organic solvent, diluting a distillation residue by adding 150mL of water, adding sodium bicarbonate (second alkaline compound), extracting with 100mL of dichloroethane for 3 times respectively, merging organic phases, washing the organic phases with water and 5% sodium carbonate in sequence, drying the organic phases with anhydrous sodium sulfate, filtering, distilling the organic solvent, and distilling under reduced pressure to obtain a compound of the formula (4);
wherein the molar ratio of the compound of formula (1), the compound of formula (2), the amine catalyst, the basic compound, the surfactant and the initiator is 1.00: 1.30: 0.60: 1.10: 0.70: 1.20 The molar ratio of the first part of basic compound to the second part of basic compound is 0.20: 0.90.
Referring to FIG. 6, the compound of formula (4) above was formed in the reaction product with a yield of 78% and a GC purity of 99% or more of 2-trifluoromethyl-4-heptafluoroisopropylaniline.
Example 8: the synthesis method of the intermediate of the bisamide pesticide disclosed by the invention is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling a reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment of 0 ℃ in advance;
s2, sequentially adding 200mL of 0.5mol/L acetonitrile solution of the compound of the formula (1), the compound of the formula (2) and the compound of the formula (35) (amine catalyst) into a reaction container, stirring and mixing uniformly, sequentially adding dipotassium hydrogen phosphate (first part of alkaline compound) and tetradecyl trimethyl ammonium chloride (surfactant), stirring and mixing uniformly, then adding zinc sulfite (initiator) for reaction, controlling the reaction temperature to be 50 ℃ and the reaction time to be 12 hours, and obtaining a reaction product;
s3, after the reaction is finished, distilling a reaction product, recovering an organic solvent, diluting a distillation residue by adding 150mL of water, adding sodium bicarbonate (second alkaline compound), extracting with 100mL of dichloroethane for 3 times respectively, merging organic phases, washing the organic phases with water and 5% sodium carbonate in sequence, drying the organic phases with anhydrous sodium sulfate, filtering, distilling the organic solvent, and distilling under reduced pressure to obtain a compound of the formula (4);
wherein the molar ratio of the compound of formula (1), the compound of formula (2), the amine catalyst, the basic compound, the surfactant and the initiator is 1.00:1.20: 0.10: 1.20: 0.60: 1.10 The molar ratio of the first part of basic compound to the second part of basic compound is 0.20: 1.00.
Referring to FIG. 7, the compound of formula (4) above was formed in the reaction product with a yield of 70% and a GC purity of 99% or more of 2-trifluoromethyl-4-heptafluoroisopropylaniline.
Example 9: the synthesis method of the intermediate of the bisamide pesticide disclosed by the invention is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling a reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment of 0 ℃ in advance;
s2, sequentially adding 200mL of 0.5mol/L ethyl acetate solution of the compound of the formula (1), the compound of the formula (2) and 200mL of water into a reaction container, stirring and mixing uniformly, sequentially adding sodium carbonate, tetrabutylammonium bisulfate and an amine catalyst, stirring and mixing uniformly, then adding sodium dithionite for reaction, controlling the reaction temperature to be 10 ℃ and the reaction time to be 12 hours, and obtaining a reaction product;
s3, after the reaction is finished, separating an aqueous phase and an organic phase of a reaction product, extracting the aqueous phase with 20mL of ethyl acetate, separating liquid, merging the organic phases, washing the organic phase with water and 5% sodium carbonate in sequence, drying the organic phase with anhydrous sodium sulfate, filtering, distilling the organic solvent, and distilling under reduced pressure to obtain the compound of the formula (4);
wherein the molar ratio of the compound of formula (1), the compound of formula (2), the amine catalyst, the basic compound, the surfactant and the initiator is 1.00:1.20: 0.10: 1.20:0.01: 1.20.
Referring to FIG. 8, the compound of formula (4) above was formed in the reaction product with a yield of 78% and a GC purity of 99% or more of 2-trifluoromethyl-4-heptafluoroisopropylaniline.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by 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.
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