CN114478264A - Synthesis method of intermediate of bisamide insecticide - Google Patents
Synthesis method of intermediate of bisamide insecticide Download PDFInfo
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Abstract
The invention relates to a synthesis method of an intermediate of a bisamide insecticide, which comprises the following steps of reacting a compound of a formula (1) with a compound of a formula (2) in a solvent under the action of an amine catalyst, and carrying out post-treatment after the reaction is finished to obtain the compound of the formula (4). According to the invention, an amine catalyst is added into a reaction system to activate a halogen bond and reduce the reaction temperature, and then a compound of formula (1) for forming perfluoropropyl free radicals is used to intercept hydrogen atoms on para-carbon on a phenyl group of a compound of formula (2) to generate carbon free radicals, so that C-C bonding reaction is finally realized, the yield of the prepared compound of formula (4) is more than or equal to 70%, and the GC purity is more than or equal to 99%, and the purposes of improving the yield and purity of 2-trifluoromethyl-4-heptafluoroisopropylaniline are achieved, so that the method is suitable for industrial production and 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 insecticide.
Background
The bisamide insecticide is a hotspot in the field of insecticide research in recent years, the ryanodine of insects with the action domain has the characteristics of novel and efficient action mechanism, no cross resistance with traditional pesticides, safety to non-target organisms and good environmental compatibility, attracts people's attention, and some large pesticide companies abroad enter the field of bisamide insecticide research one after another and participate in the synthesis research of the compounds, so that the bisamide insecticide becomes a hotspot in the research and development of insecticides. From the advent of flubendiamide to date, 8 products have been commercialized or are about to be commercialized, becoming the most market-potential pesticide varieties at present.
At present, the novel insecticides of flubendiamide and 2-bromofenoxanil are both pesticides with important market values. Wherein, the 2-methyl-4-heptafluoro-isopropyl aniline is a key intermediate of flubendiamide, and the 2-trifluoromethyl-4-heptafluoro-isopropyl aniline is a key intermediate of 2-bromofenoxanil. 2-trifluoromethyl-4-heptafluoroisopropylaniline has low activity due to the introduction of ortho-trifluoromethyl, and the yield of 2-trifluoromethyl-4-heptafluoroisopropylaniline directly synthesized from 2-trifluoromethylaniline is low.
The existing synthesis 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 heptafluoroiodopropane as a raw material in the method has high cost, low yield and unmatched yield and economic benefit, so that the process lacks market competitiveness; 2) the method adopts heptafluoro bromopropane as a raw material, so that the production cost can be reduced, but the reaction activity of the heptafluoro bromopropane is lower, the reaction needs to be carried out at a higher temperature for improving the reaction yield, the boiling point of the heptafluoro bromopropane is only 14 ℃, so the reaction needs to be carried out in closed equipment, the highest reaction conversion rate is only 70 percent, the actual yield is far lower than 70 percent, and the reduction of the production cost is not facilitated.
Therefore, there is a need to develop a method for synthesizing an intermediate (2-trifluoromethyl-4-heptafluoroisopropylaniline) of bisamide insecticides, so that the yield and purity of the 2-trifluoromethyl-4-heptafluoroisopropylaniline can be improved on the basis of using perfluorohalides, 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 method for synthesizing an intermediate of a bisamide insecticide, which solves the problems of high cost and low yield of the conventional synthesis method and achieves the purpose of improving the yield and purity of 2-trifluoromethyl-4-heptafluoroisopropyl aniline.
The above object of the present invention is achieved by the following technical solutions:
a synthetic method of an intermediate of a bisamide insecticide comprises the following steps,
the synthesis method comprises the following steps of reacting a compound of the formula (1) with a compound of the formula (2) in a solvent under the action of an amine catalyst, and carrying out post-treatment after the reaction is finished to obtain a compound of the formula (4);
wherein X is selected from halogen.
By adopting the technical scheme, the amine catalyst is added into the reaction system, the compound of the formula (1) and the amine catalyst form an N … X halogen bond compound, 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 a perfluoropropyl radical, the radical intercepts the hydrogen atom on the para-carbon of the phenyl of the compound of the formula (2) to generate a carbon radical, and finally the C-C bonding reaction is realized, and 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 shown in the formula (1) is controlled, the yield is effectively improved compared with the existing synthesis method, the impurities are controlled, the yield of the prepared compound shown in the formula (4) is more than or equal to 70 percent, the GC purity is more than or equal to 99 percent, the purpose of improving the yield and the purity of the 2-trifluoromethyl-4-heptafluoroisopropyl aniline is achieved, and the method is suitable for industrial production and has higher implementation value and social and economic benefits.
Specifically, in the above formula compound of the present invention, the meaning of the "halogen" refers to a halogen element, which may be, for example, F, Cl, Br or I without limitation.
Further, the amine catalyst is one or a combination of a plurality of compounds shown in 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): (0.01-0.80). 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 for improving the yield of the compound of the above formula (4).
Further, the synthesis method also comprises the step of adding one or a combination of more of an initiator, a basic compound and a surfactant into the mixed solvent. Specifically, the initiator, the basic compound and the surfactant are added to the solvent before the start of the reaction, and a part of the basic compound is added to the solvent after the end of the reaction, to accelerate the reaction and neutralize the acid formed by the reaction.
Preferably, the initiator is sodium hydrosulfite, potassium hydrosulfite, zinc hydrosulfite or zinc sulfite, the alkaline compound is an inorganic base or an organic base, and the surfactant is a quaternary ammonium salt surfactant, a phosphate salt surfactant or a crown ether 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 the above formula (1), the basic compound, the surfactant and the 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 the above formula (1), the basic compound, the surfactant and the initiator is 1.00: 1.20: 0.01: 1.20, is favorable for improving the yield of the compound of the formula (4).
Furthermore, the reaction temperature is-20 to 100 ℃, and the reaction time is 10 to 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 ℃ in advance, and the compound of the formula (1) is stored in an environment of-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 the water is 1.00: (0.75 to 1.00). Wherein, the organic solvent is firstly used as the solvent of the compound of the formula (1) to obtain the compound/organic solvent of the formula (1), and after the compound of the formula (2) and the amine catalyst are added, the rest water is added for mixing and stirring; or after the reaction is finished, the organic solvent is distilled off and diluted by adding water.
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 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 the above formula (2) to the organic solvent is 1: (2-20). By adopting the above ratio, the compound of the above formula (2) can be sufficiently dissolved.
Further, the synthesis method comprises the following steps of firstly adding the compound/organic solvent of the formula (1), the compound of the formula (2) and water into a reaction vessel in sequence, uniformly stirring, then sequentially adding an alkaline compound, a surfactant and an amine catalyst, uniformly stirring, then adding an initiator for reaction, and after the reaction is finished, carrying out extraction, liquid separation, washing, drying, filtering and reduced pressure distillation on a reaction product to obtain the compound of the formula (4).
Further, the synthesis method comprises the following steps of firstly adding the compound/organic solvent of the formula (1), the compound of the formula (2) and an amine catalyst into a reaction vessel in sequence, uniformly stirring, then adding the first part of alkaline compound and a surfactant in sequence, uniformly stirring, then adding an initiator for reaction, distilling a reaction product and recovering the organic solvent after the reaction is finished, adding water for diluting a distillation residue, adding the second part of alkaline compound, and then carrying out extraction, liquid separation, washing, drying, filtering and reduced pressure distillation on the reaction product to obtain the compound of the formula (4); the molar ratio of the first part of basic compound to the second part of basic compound is 0.20: (0.80-1.30).
Preferably, the extractant for extracting and separating liquid is selected from ethyl acetate or dichloroethane, the washing detergent is selected from water and/or sodium carbonate, and the drying desiccant is selected from anhydrous sodium sulfate.
In conclusion, the beneficial technical effects of the invention are as follows: the method comprises the steps of adding an amine catalyst into a reaction system to activate a halogen bond and reduce the reaction temperature, and then adding a compound of formula (1) for forming a perfluoropropyl radical to intercept a hydrogen atom on a para-carbon on a phenyl group of a compound of formula (2) to generate a carbon radical, so as to finally realize C-C bonding reaction, wherein the yield of the prepared compound of formula (4) is more than or equal to 70%, and the GC purity is more than or equal to 99%, so that the aim of improving the yield and purity of 2-trifluoromethyl-4-heptafluoroisopropylaniline is fulfilled, and the method is suitable for industrial production and has high implementation value and social and economic benefits.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a reaction product of example 2 of the present invention;
FIG. 2 is a nuclear magnetic resonance spectrum of a reaction product of example 3 of the present invention;
FIG. 3 is a nuclear magnetic resonance spectrum of a reaction product of example 4 of the present invention;
FIG. 4 is a nuclear magnetic resonance spectrum of a reaction product of example 5 of the present invention;
FIG. 5 is a nuclear magnetic resonance spectrum of a reaction product of example 6 of the present invention;
FIG. 6 is a nuclear magnetic resonance spectrum of a 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 a reaction product of example 9 of the present invention.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the functions of the invention clearer and easier to understand, the invention is further explained in the following with the accompanying drawings and the detailed description.
Examples
Example 1: the invention discloses a synthetic method of an intermediate of a bisamide insecticide, which comprises the following steps,
the synthesis method comprises the following steps of reacting a compound of the formula (1) with a compound of the formula (2) in a solvent under the action of an amine catalyst, an initiator, an alkaline compound and a surfactant, and performing post-treatment after the reaction to obtain a compound of the formula (4);
wherein X is selected from halogen.
The reaction system is added with an amine catalyst, the compound of the formula (1) and the amine catalyst form an N … X halogen bond compound, 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 a perfluoropropyl radical, the radical intercepts the hydrogen atom on the para-carbon of the phenyl of the compound of the formula (2) to generate a carbon radical, and finally the C-C bonding reaction is realized, and 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 shown in the formula (1) is controlled, the yield is effectively improved compared with the existing synthesis method, impurities are controlled, the yield of the prepared compound shown 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 the purity of the 2-trifluoromethyl-4-heptafluoro-isopropyl aniline is achieved, the method is suitable for industrial production, and has high implementation value and social and economic benefits.
Preferably, the reaction temperature is-20 to 100 ℃, and the reaction time is 10 to 12 hours.
The amine catalyst is any one of compounds shown in the following formulas (31) to (35),
the alkaline compound is an inorganic base or an organic base, and the inorganic base is preferably sodium carbonate, sodium hydrogen carbonate, 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 surfactant, phosphate surfactant or crown ether surfactant, preferably tetrabutylammonium hydrogen sulfate, benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride or tetradecyltrimethylammonium chloride.
The initiator is sodium hydrosulfite, potassium hydrosulfite, zinc hydrosulfite or zinc sulfite.
The molar ratio of the compound of the formula (1) to the compound of the formula (2) to the amine catalyst to the basic compound to the surfactant to the 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 comprises one or a mixture of two of organic solvent and water; in the solvent mixture, the volume ratio of the organic solvent to the water is 1.00: (0.75 to 1.00). The mass ratio of the compound of the above formula (2) to the organic solvent is 1: (2-20). The organic solvent is halogenated alkane 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 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.
Example 2: the invention discloses a method for synthesizing an intermediate of a bisamide insecticide, which is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling the reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment at 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, uniformly stirring, sequentially adding sodium bisulfate (a first part of alkaline compound) and tetrabutylammonium bisulfate (a surfactant), uniformly stirring, adding sodium hydrosulfite (an initiator) for reaction, controlling the reaction temperature to be 10 ℃ and the reaction time to be 12 hours, and obtaining a reaction product;
after the reaction of S3 is finished, distilling the reaction product and recovering the organic solvent, diluting the distillation residue with 150mL of water, adding sodium bicarbonate (the second alkaline compound), extracting with 100mL of dichloroethane for 3 times, combining the organic phases, washing the organic phases with water and 5% of sodium carbonate in sequence, drying with anhydrous sodium sulfate, filtering, evaporating the organic solvent, and distilling under reduced pressure to obtain the compound of the formula (4);
wherein the molar ratio of the compound of the formula (1) to the compound of the formula (2) to the amine catalyst to the basic compound to the surfactant to 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 reaction product was produced as the compound of formula (4) above, and the yield of 2-trifluoromethyl-4-heptafluoroisopropylaniline was 76%, and the GC purity was 99% or more.
Example 3: the invention discloses a method for synthesizing an intermediate of a bisamide insecticide, which is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling the reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment at 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, uniformly stirring, sequentially adding potassium carbonate (a first alkaline compound) and benzyltriethylammonium chloride (a surfactant), uniformly stirring, adding sodium hydrosulfite (an initiator) for reaction, controlling the reaction temperature to be-20 ℃ and the reaction time to be 10 hours, and obtaining a reaction product;
after the reaction of S3 is finished, distilling the reaction product and recovering the organic solvent, diluting the distillation residue with 150mL of water, adding sodium bicarbonate (the second alkaline compound), extracting with 100mL of dichloroethane for 3 times, combining the organic phases, washing the organic phases with water and 5% of sodium carbonate in sequence, drying with anhydrous sodium sulfate, filtering, evaporating the organic solvent, and distilling under reduced pressure to obtain the compound of the formula (4);
wherein the molar ratio of the compound of the formula (1) to the compound of the formula (2) to the amine catalyst to the basic compound to the surfactant to the initiator is 1.00: 1.00: 0.01: 1.50: 0.80: 1.00, the molar ratio of the first portion of basic compound to the second portion of basic compound is 0.20: 1.30.
Referring to FIG. 2, the reaction product was produced as the compound of formula (4) above, and the yield of 2-trifluoromethyl-4-heptafluoroisopropylaniline was 80% and the GC purity was 99% or more.
Example 4: the invention discloses a method for synthesizing an intermediate of a bisamide insecticide, which is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling the reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment at 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, uniformly stirring, sequentially adding lithium carbonate (a first alkaline compound) and tetrabutylammonium bromide (a surfactant), uniformly stirring, adding potassium dithionite (an initiator) for reaction, controlling the reaction temperature to be-10 ℃ and the reaction time to be 11 hours, and obtaining a reaction product;
after the reaction of S3 is finished, distilling the reaction product and recovering the organic solvent, diluting the distillation residue with 150mL of water, adding sodium bicarbonate (the second alkaline compound), extracting with 100mL of dichloroethane for 3 times, combining the organic phases, washing the organic phases with water and 5% of sodium carbonate in sequence, drying with anhydrous sodium sulfate, filtering, evaporating the organic solvent, and distilling under reduced pressure to obtain the compound of the formula (4);
wherein the molar ratio of the compound of the formula (1) to the compound of the formula (2) to the amine catalyst to the basic compound to the surfactant to the initiator is 1.00: 1.50: 0.50: 1.20: 1.00: 1.50, the molar ratio of the first portion of basic compound to the second portion of basic compound is 0.20: 1.00.
Referring to FIG. 3, the reaction product was obtained in the form of the compound of the above formula (4) in a yield of 77% and a GC purity of 99% or more, based on 2-trifluoromethyl-4-heptafluoroisopropylaniline.
Example 5: the invention discloses a method for synthesizing an intermediate of a bisamide insecticide, which is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling the reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment at 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, uniformly stirring, sequentially adding sodium hydroxide (a first part of alkaline compound) and tetrabutylammonium chloride (a surfactant), uniformly stirring, adding sodium hydrosulfite (an initiator) for reaction, controlling the reaction temperature to be 0 ℃ and the reaction time to be 12 hours, and obtaining a reaction product;
after the reaction of S3 is finished, distilling the reaction product and recovering the organic solvent, diluting the distillation residue with 150mL of water, adding sodium bicarbonate (the second alkaline compound), extracting with 100mL of dichloroethane for 3 times, combining the organic phases, washing the organic phases with water and 5% of sodium carbonate in sequence, drying with anhydrous sodium sulfate, filtering, evaporating the organic solvent, and distilling under reduced pressure to obtain the compound of the formula (4);
wherein the molar ratio of the compound of the formula (1) to the compound of the formula (2) to the amine catalyst to the basic compound to the surfactant to the initiator is 1.00: 1.40: 0.80: 1.30: 0.90: 1.40, the molar ratio of the first portion of basic compound to the second portion of basic compound is 0.20: 1.10.
Referring to FIG. 4, the compound of formula (4) is produced in the reaction product, and the yield of 2-trifluoromethyl-4-heptafluoroisopropyl aniline is 73%, and the GC purity is 99% or more.
Example 6: the invention discloses a method for synthesizing an intermediate of a bisamide insecticide, which is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling the reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment at 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, uniformly stirring, sequentially adding sodium dihydrogen phosphate (a first alkaline compound) and trioctylmethylammonium chloride (a surfactant), uniformly stirring, adding zinc hydrosulfite (an initiator) for reaction, controlling the reaction temperature to be 60 ℃ and the reaction time to be 10 hours, and obtaining a reaction product;
after the reaction of S3 is finished, distilling the reaction product and recovering the organic solvent, diluting the distillation residue with 150mL of water, adding sodium bicarbonate (the second alkaline compound), extracting with 100mL of dichloroethane for 3 times, combining the organic phases, washing the organic phases with water and 5% of sodium carbonate in sequence, drying with anhydrous sodium sulfate, filtering, evaporating the organic solvent, and distilling under reduced pressure to obtain the compound of the formula (4);
wherein the molar ratio of the compound of the formula (1) to the compound of the formula (2) to the amine catalyst to the basic compound to the surfactant to the initiator is 1.00: 1.10: 0.05: 1.40: 0.50: 1.30, the molar ratio of the first portion of basic compound to the second portion of basic compound is 0.20: 1.20.
Referring to FIG. 5, the reaction product was obtained in the form of the compound of the above formula (4) in a 75% yield and a GC purity of 99% or more.
Example 7: the invention discloses a method for synthesizing an intermediate of a bisamide insecticide, which is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling the reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment at 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, uniformly stirring, sequentially adding lithium hydroxide (a first alkaline compound) and dodecyl trimethyl ammonium chloride (a surfactant), uniformly stirring, adding sodium hydrosulfite (an initiator) for reaction, controlling the reaction temperature to be 100 ℃ and the reaction time to be 11 hours, and obtaining a reaction product;
after the reaction of S3 is finished, distilling the reaction product and recovering the organic solvent, diluting the distillation residue with 150mL of water, adding sodium bicarbonate (the second alkaline compound), extracting with 100mL of dichloroethane for 3 times, combining the organic phases, washing the organic phases with water and 5% of sodium carbonate in sequence, drying with anhydrous sodium sulfate, filtering, evaporating the organic solvent, and distilling under reduced pressure to obtain the compound of the formula (4);
wherein the molar ratio of the compound of the formula (1) to the compound of the formula (2) to the amine catalyst to the basic compound to the surfactant to 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 reaction product was obtained in the form of the compound of the above formula (4) in a yield of 78% and a GC purity of 99% or more, based on 2-trifluoromethyl-4-heptafluoroisopropylaniline.
Example 8: the invention discloses a method for synthesizing an intermediate of a bisamide insecticide, which is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling the reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment at 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, uniformly stirring, sequentially adding dipotassium hydrogen phosphate (a first part of alkaline compound) and tetradecyl trimethyl ammonium chloride (surfactant), uniformly stirring, 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;
after the reaction of S3 is finished, distilling the reaction product and recovering the organic solvent, diluting the distillation residue with 150mL of water, adding sodium bicarbonate (the second alkaline compound), extracting with 100mL of dichloroethane for 3 times, combining the organic phases, washing the organic phases with water and 5% of sodium carbonate in sequence, drying with anhydrous sodium sulfate, filtering, evaporating the organic solvent, and distilling under reduced pressure to obtain the compound of the formula (4);
wherein the molar ratio of the compound of the formula (1) to the compound of the formula (2) to the amine catalyst to the basic compound to the surfactant to the initiator is 1.00: 1.20: 0.10: 1.20: 0.60: 1.10, the molar ratio of the first portion of basic compound to the second portion of basic compound is 0.20: 1.00.
Referring to FIG. 7, the reaction product was obtained in the form of the compound of the above formula (4), and the yield of 2-trifluoromethyl-4-heptafluoroisopropylaniline was 70% and the GC purity was 99% or more.
Example 9: the invention discloses a method for synthesizing an intermediate of a bisamide insecticide, which is different from the embodiment 1 in that the method comprises the following steps,
s1, cooling the reaction container to 0 ℃, and preserving the compound of the formula (1) in an environment at 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 vessel, uniformly stirring, sequentially adding sodium carbonate, tetrabutylammonium hydrogen sulfate and an amine catalyst, uniformly stirring, adding sodium hydrosulfite for reaction, controlling the reaction temperature to be 10 ℃ and the reaction time to be 12 hours, and obtaining a reaction product;
after the reaction of S3 is finished, separating the water phase and the organic phase of the reaction product, extracting the water phase with 20mL ethyl acetate, separating liquid, combining the organic phases, washing the organic phases with water and 5% sodium carbonate in sequence, drying with anhydrous sodium sulfate, filtering, evaporating the organic solvent, and distilling under reduced pressure to obtain the compound of the formula (4);
wherein the molar ratio of the compound of the formula (1) to the compound of the formula (2) to the amine catalyst to the basic compound to the surfactant to the initiator is 1.00: 1.20: 0.10: 1.20: 0.01: 1.20.
Referring to FIG. 8, the reaction product was obtained in the form of the compound of the above formula (4) in a yield of 78% and a GC purity of 99% or more, based on 2-trifluoromethyl-4-heptafluoroisopropylaniline.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, 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 or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. A synthetic method of an intermediate of a bisamide insecticide is characterized by comprising the following steps: the route of the synthetic method is as follows,
the synthesis method comprises the following steps of reacting a compound of the formula (1) with a compound of the formula (2) in a solvent under the action of an amine catalyst, and carrying out post-treatment after the reaction is finished to obtain a compound of the formula (4);
wherein X is selected from halogen.
2. The method for synthesizing the intermediate of the bisamide insecticide according to claim 1, wherein the intermediate comprises the following steps: the amine catalyst is one or a combination of a plurality of compounds shown in the following formulas (31) - (35),
3. the synthesis method of the intermediate of the bisamide insecticide according to claim 2, wherein the intermediate comprises the following steps: 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).
4. The method for synthesizing the intermediate of the bisamide insecticide according to claim 1, wherein the intermediate comprises the following steps: the synthesis method also comprises the step of adding one or a combination of more of an initiator, an alkaline compound and a surfactant into the mixed solvent.
5. The method for synthesizing the intermediate of the bisamide insecticide according to claim 4, wherein the intermediate comprises the following steps: the initiator is sodium hydrosulfite, potassium hydrosulfite, zinc hydrosulfite or zinc sulfite, the alkaline compound is inorganic base or organic base, and the surfactant is quaternary ammonium salt surfactant, phosphate salt surfactant or crown ether surfactant.
6. The method for synthesizing the intermediate of the bisamide insecticide according to claim 4, wherein the intermediate comprises the following steps: the molar ratio of the compound of the above formula (1), the basic compound, the surfactant and the initiator is 1.00: (1.00-1.50): (0.01-0.10): (1.00-1.50).
7. The method for synthesizing the intermediate of the bisamide insecticide according to any one of claims 1 to 6, wherein the intermediate comprises the following steps: the reaction temperature is-20-100 ℃, and the reaction time is 10-12 h.
8. The method for synthesizing the intermediate of the bisamide insecticide according to any one of claims 1 to 6, wherein the intermediate comprises the following steps: the solvent comprises one or a mixture of two of organic solvent and water; in the solvent mixture, the volume ratio of the organic solvent to the water is 1.00: (0.75 to 1.00).
9. The method for synthesizing the intermediate of the bisamide insecticide according to claim 8, wherein the intermediate comprises the following steps: the organic solvent is halogenated alkane solvent, ether solvent, alcohol solvent, ketone solvent, amide solvent, ester solvent or nitrile solvent.
10. The method for synthesizing the intermediate of the bisamide insecticide according to claim 8, wherein the intermediate comprises the following steps: the mass ratio of the compound of the above formula (2) to the organic solvent is 1: (2-20).
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102112437A (en) * | 2008-08-01 | 2011-06-29 | 三井化学Agro株式会社 | Amide derivative, pest control agent containing amide derivative and pest controlling method |
| JP2011157294A (en) * | 2010-01-29 | 2011-08-18 | Mitsui Chemicals Agro Inc | Pest-controlling composition |
| CN102740695A (en) * | 2010-01-29 | 2012-10-17 | 三井化学Agro株式会社 | Composition for control of animal parasites, and method for control of animal parasites |
| CN102731321A (en) * | 2012-07-10 | 2012-10-17 | 中化蓝天集团有限公司 | Method for preparing 2-methyl-4-(1,1,1,2,3,3,3-heptafluoro-2-propyl) aniline |
| CN106103414A (en) * | 2013-11-05 | 2016-11-09 | 拜耳作物科学股份公司 | The substituted benzamides processed for arthropod |
| JP2017071604A (en) * | 2016-10-07 | 2017-04-13 | 住友化学株式会社 | Pest control composition and application thereof |
| CN106748807A (en) * | 2017-01-16 | 2017-05-31 | 衢州学院 | A kind of sevoflurane isopropyl amine preparation method of 2 methyl of high-purity 4 |
| CN113828355A (en) * | 2021-11-24 | 2021-12-24 | 南京科力硕生物科技有限公司 | Preparation method of nano-phase transfer catalyst hydrogel for synthesizing 2-methyl-4-heptafluoroisopropyl aniline |
-
2022
- 2022-03-23 CN CN202210291283.4A patent/CN114478264B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102112437A (en) * | 2008-08-01 | 2011-06-29 | 三井化学Agro株式会社 | Amide derivative, pest control agent containing amide derivative and pest controlling method |
| JP2011157294A (en) * | 2010-01-29 | 2011-08-18 | Mitsui Chemicals Agro Inc | Pest-controlling composition |
| CN102740695A (en) * | 2010-01-29 | 2012-10-17 | 三井化学Agro株式会社 | Composition for control of animal parasites, and method for control of animal parasites |
| CN102731321A (en) * | 2012-07-10 | 2012-10-17 | 中化蓝天集团有限公司 | Method for preparing 2-methyl-4-(1,1,1,2,3,3,3-heptafluoro-2-propyl) aniline |
| CN106103414A (en) * | 2013-11-05 | 2016-11-09 | 拜耳作物科学股份公司 | The substituted benzamides processed for arthropod |
| JP2017071604A (en) * | 2016-10-07 | 2017-04-13 | 住友化学株式会社 | Pest control composition and application thereof |
| CN106748807A (en) * | 2017-01-16 | 2017-05-31 | 衢州学院 | A kind of sevoflurane isopropyl amine preparation method of 2 methyl of high-purity 4 |
| CN113828355A (en) * | 2021-11-24 | 2021-12-24 | 南京科力硕生物科技有限公司 | Preparation method of nano-phase transfer catalyst hydrogel for synthesizing 2-methyl-4-heptafluoroisopropyl aniline |
Non-Patent Citations (3)
| Title |
|---|
| CHUNYAN LUO等: "Development of an Efficient Synthetic Process for Broflanilide", 《ORGANIC PROCESS RESEARCH & DEVELOPMENT》, vol. 24, no. 06, pages 1024 - 1031, XP055730033, DOI: 10.1021/acs.oprd.0c00028 * |
| HUANYUAN LONG等: "Design, synthesis, and insecticidal activities of novel meta-diamide compounds containing sulfide, sulfoxide and sulfone", 《TETRAHEDRON LETTERS》, pages 154388 * |
| 沈佳萍等: "2-乙基-4-七氟异丙基苯胺的合成", 《广州化工》, vol. 39, no. 17, pages 65 - 66 * |
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