An amide compound, a preparation method and application thereof

Abstract

The application provides an amide compound, a preparation method and application thereof, and the amide compound has a structure shown in formula I. The amide compound has high insecticidal activity and good quick-acting property at a low dose; and due to the good effect at the low dose, the drug use amount is reduced, the amide compound is more beneficial to environmental protection, and has a wide application prospect.

Description

Technical Field

[0001] This invention belongs to the field of insecticides, and relates to an amide compound, its preparation method, and its application. Background Technology

[0002] In agricultural and horticultural crop production, damage caused by pests remains significant. Due to pest resistance to existing pesticides and the environmental unfriendliness of current pesticides, there is a continuous need to develop new pesticides with better activity, lower dosage, and greater environmental friendliness.

[0003] The insecticidal activity of amide compounds has been reported. For example, CN1926094A discloses compounds KC1 (i.e., compound 2001 in CN1926094A), KC2 (i.e., compound 2004 in CN1926094A), KC3 (i.e., compound 2034 in CN1926094A), and KC4 (i.e., compound 2037 in CN1926094A) and their insecticidal activities. These disclosed compounds have insecticidal activity; however, their insecticidal effect is poor or their action is not rapid at low doses.

[0004]

[0005] There is still a need to actively develop new insecticides that can have rapid and high insecticidal activity at low doses to meet the needs of agriculture and forestry. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the purpose of this invention is to provide an amide compound, its preparation method and application, wherein the amide compound has a good insecticidal effect at low doses, and has good rapid effect, low dosage, and is more environmentally friendly.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] On one hand, the present invention provides an amide compound having the structure shown in Formula I:

[0009]

[0010] In formula I,

[0011] Q is selected from one of the following: Q1, Q2, Q3, or Q4:

[0012]

[0013] Z1, Z2, Z3, Z4, and Z5 are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, C1-C6 alkyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C3-C8 halocycloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, or C1-C6 haloalkylsulfonyl.

[0014] R1 is selected from halogens;

[0015] R2 is selected from difluoromethoxy;

[0016] W1 and W2 are either oxygen atoms or sulfur atoms.

[0017] Amide compounds having the structure shown in Formula I of this invention can achieve good insecticidal activity at low doses and have a rapid onset of action. They can exert insecticidal activity one day after application and achieve high insecticidal activity within three days, exhibiting good rapid-acting properties. Furthermore, due to their good efficacy at low doses, they reduce the harm to plants and humans caused by excessive drug concentrations and result in less drug residues during application, making them more environmentally friendly.

[0018] In this invention, as a preferred technical solution, in Formula I, Z1, Z2, Z3, Z4, and Z5 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, trifluoromethyl, pentafluoroethyl, heptafluoron-propyl, heptafluoroisopropyl, difluoromethoxy, trifluoromethoxy, pentafluoroethoxy, methylsulfinyl, trifluoromethylsulfinyl, methanesulfonyl, or trifluoromethanesulfonyl; R1 is selected from chlorine, bromine, or iodine; and R2 is selected from difluoromethoxy.

[0019] As a further preferred technical solution of the present invention, the amide compound is any one of the compounds shown in Table 1 below that have general formula I.

[0020] Table 1

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029] It should be noted that "H" represents a hydrogen atom, "O" represents an oxygen atom, "S" represents a sulfur atom, "F" represents a fluorine atom, "Cl" represents a chlorine atom, "Br" represents a bromine atom, "I" represents an iodine atom, and "OCF2H" represents a difluoromethoxy group.

[0030] In this invention, as a more preferred technical solution, in Formula I, Z1, Z2, Z3, Z4, and Z5 are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methanesulfonyl, or trifluoromethanesulfonyl; R1 is selected from chlorine, bromine, or iodine; R2 is selected from difluoromethoxy; and W1 and W2 are selected from oxygen.

[0031] In this invention, as a particularly preferred technical solution, the amide compound is selected from any one of the following compounds:

[0032]

[0033]

[0034] The compound numbers correspond to the compound numbers in Table 1.

[0035] The alkyl group referred to in this invention refers to a straight-chain or branched alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc. A haloalkyl group is a group in which the hydrogen atom on the alkyl group is replaced by one or more halogen atoms. An alkoxy group is a group with an oxygen atom attached to the alkyl terminus, such as methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, etc. A haloalkoxy group is a group in which the hydrogen atom on the alkoxy group is replaced by one or more halogen atoms. The halogen is F, Cl, Br, or I.

[0036] As used in this invention, the term "C1-C6 alkyl" refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and includes, without limitation, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, etc. The term "C1-C6 alkoxy" refers to a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, and includes, without limitation, methoxy, ethoxy, n-propoxy, isopropoxy, and tert-butoxy, etc. "C1-C6 haloalkyl" refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms substituted with halogen atoms, and includes, without limitation, trifluoromethyl, difluoromethyl, 1,1,1-trifluoroethyl, pentafluoroethyl, heptafluoroisopropyl, etc. "C1-C6 haloalkoxy" refers to a straight-chain or branched alkoxy group having 1 to 6 carbon atoms substituted with halogen atoms, and includes, without limitation, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, etc. As used in this invention, the term "C3-C8 cycloalkyl" refers to a cyclic alkyl group having 3 to 8 carbon atoms, and includes, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. The term "C3-C8 halocycloalkyl" as used in this invention refers to a cyclic alkyl group having 3 to 8 carbon atoms with halogen substitution on the ring, and includes, without limitation, 1-chlorocyclopropyl, 1-fluorocyclopropyl, perfluorocyclopropyl, etc.

[0037] In this invention, C1-C6, C3-C8, etc., preceding the specific group indicate the number of carbon atoms contained in the group. For example, C1-C6 indicates a group with 1, 2, 3, 4, 5 or 6 carbon atoms, C3-C8 indicates a group with 3, 4, 5, 6, 7 or 8 carbon atoms, and so on.

[0038] Additionally, it should be noted that in this invention, “OCF2H” represents difluoromethoxy, “H” represents hydrogen atom, “F” represents fluorine atom, “Cl” represents chlorine atom, “Br” represents bromine atom, “I” represents iodine atom, “O” represents oxygen atom, “S” represents sulfur atom, “OMe” represents methoxy, “-CN” represents cyano, and “-NO2” represents nitro.

[0039] The compound of general formula I of the present invention can be prepared by the following method, unless otherwise specified, the definitions of each group in the reaction formula are the same as above.

[0040] Preparation method 1:

[0041] The structure of the compound of general formula I of the present invention is as follows, and it can be prepared by the following method:

[0042]

[0043] Among them, LG is selected from fluorine, chlorine, bromine, and C1-C. 12 Alkoxy, C1-C 12 Alkyloxyacyloxy or C1-C12 Alkyl acyloxy group; Hal is selected from fluorine, chlorine, bromine or iodine; the limitations of R1, R2, Q, W1 and W2 are the same as above, and will not be repeated here.

[0044] 1-(i): Compound II of general formula reacts with compound III of general formula to give compound IV of general formula.

[0045] Preferably, the molar ratio of the compound of general formula II to the compound of general formula III is 0.5-2:1.

[0046] In this invention, the reaction in step 1-(i) is carried out in the presence of an alkaline substance, which is an organic base and / or an inorganic base.

[0047] Preferably, the organic base is any one or a combination of at least two of triethylamine, N,N-diisopropylethylamine, pyridine, sodium methoxide, or sodium ethoxide.

[0048] Preferably, the inorganic base is any one or a combination of at least two of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, or sodium hydride.

[0049] Preferably, the solvent for the reaction in step 1-(i) is selected from any one or a combination of at least two of dichloromethane, chloroform, toluene, ethyl acetate, tetrahydrofuran, N,N-dimethylformamide or dimethyl sulfoxide.

[0050] Preferably, the reaction temperature in step 1-(i) is greater than or equal to -10°C and less than or equal to the boiling point of the reaction solvent, such as -10°C, 0°C, 10°C, 30°C, 50°C, 75°C, 90°C, etc., or the reaction is carried out at the boiling point of the solvent, i.e., under reflux.

[0051] Preferably, the reaction time in step 1-(i) is 0.5-48 hours.

[0052] 1-(ii): Hydrolysis of general formula compound IV yields general formula compound V.

[0053] The hydrolysis described in step 1-(ii) is carried out in any one or a mixture of at least two of the following solvents: water, methanol, ethanol, tetrahydrofuran, or dioxane.

[0054] Preferably, the hydrolysis in step 1-(ii) is carried out in the presence of an alkaline substance, which is preferably lithium hydroxide, sodium hydroxide or potassium hydroxide.

[0055] Preferably, the amount of the alkaline substance is 1-5 times the molar amount of the compound of general formula IV.

[0056] 1-(iii): Compound V of general formula undergoes a substitution reaction to give compound VI of general formula.

[0057] In this step, a known method is used to react compound V of general formula with a compound containing an LG group, such as thionyl chloride, oxalyl chloride, or triphosgene, to prepare a compound represented by general formula VI.

[0058] 1-(iv): Compound VI reacts with compound VII to give compound I.

[0059] Preferably, the molar ratio of general formula compound VI to general formula compound VII is 0.5-2:1.

[0060] In this invention, the reaction described in step 1-(iv) is carried out in the presence of an alkaline substance, which is an organic base and / or an inorganic base.

[0061] Preferably, the organic base is any one or a combination of at least two of the following: triethylamine, diisopropylethylamine, pyridine, piperidine, 4-N,N-dimethylaminopyridine, alkali metal alkoxides, and lithium amine.

[0062] Preferably, the alkali metal alkoxide is sodium methoxide and / or sodium ethoxide. Preferably, the lithium amino group is lithium diisopropylamino.

[0063] Preferably, the inorganic base is any one or a combination of at least two of alkali metal hydroxides, carbonates, or phosphates.

[0064] Preferably, the alkali metal hydroxide is any one or a combination of at least two of lithium hydroxide, sodium hydroxide, or potassium hydroxide. Preferably, the carbonate is any one or a combination of at least two of sodium bicarbonate, sodium carbonate, or potassium carbonate. Preferably, the phosphate is dipotassium hydrogen phosphate and / or trisodium hydrogen phosphate.

[0065] Preferably, the solvent for the reaction in step 1-(iv) is any one or a combination of at least two of the following: haloalkanes, aromatic hydrocarbons, chain or cyclic ethers, esters, ketones, nitriles or aprotic polar inert solvents.

[0066] Preferably, the halogenated hydrocarbon is any one or a combination of at least two of dichloromethane or chloroform. Preferably, the aromatic hydrocarbon is any one or a combination of at least two of toluene, xylene, or chlorobenzene. Preferably, the chain or cyclic ether is any one or a combination of at least two of diethyl ether, tetrahydrofuran, dioxane, or 1,2-dimethoxyethane. Preferably, the ester is ethyl acetate. Preferably, the ketone is acetone. Preferably, the nitrile is acetonitrile. Preferably, the aprotic polar inert solvent is any one or a combination of at least two of 1,3-dimethyl-2-imidazolinone, sulfolane, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, or N,N-dimethylacetamide.

[0067] Preferably, the temperature of the reaction in step 1-(iv) is greater than or equal to -70°C and less than or equal to the boiling point of the reaction solvent, such as -70°C, -50°C, -10°C, 0°C, 45°C, 90°C, etc., or the reaction is carried out at the boiling point of the solvent, i.e., under reflux.

[0068] Preferably, the reaction time in step 1-(iv) is 0.5-48 hours.

[0069] Preparation method 2:

[0070] The compound of general formula I of the present invention can be prepared by another method as follows:

[0071]

[0072] The limitations of Q, W1, W2, R1, R2, LG, and Hal are the same as those mentioned above, and will not be repeated here.

[0073] 2-(i): Compound VIII of general formula undergoes a substitution reaction to give compound IX of general formula.

[0074] In this step, a known method is used to react general formula compound VIII with thionyl chloride, oxalyl chloride, triphosgene, etc., to prepare a compound represented by general formula IX containing an LG group.

[0075] 2-(ii): Compound IX of general formula reacts with compound VII of general formula to give compound X of general formula.

[0076] The compound represented by general formula IX is reacted with the compound represented by general formula VII under the same conditions as described in 1-(iv) to prepare the compound represented by general formula X.

[0077] 2-(iii): Compound X of general formula undergoes a reduction reaction to give compound XI of general formula.

[0078] Aromatic carboxylic acid amide derivatives with nitro groups, represented by general formula X, can be converted into aromatic carboxylic acid amide derivatives with amine groups, represented by general formula XI, through reduction reactions.

[0079] As a reduction reaction, examples include methods using hydrogenation reactions and methods using metal compounds (such as stannous chloride) or metals (zinc powder, iron powder, etc.).

[0080] Hydrogenation can be carried out in a suitable solvent, in the presence of a catalyst, under normal or pressurized pressure, and in a hydrogen atmosphere. Catalysts in hydrogenation reactions can include palladium-carbon catalysts, cobalt catalysts, ruthenium catalysts, platinum catalysts, etc. Solvents can include alcohols such as methanol and ethanol; aromatic hydrocarbons such as benzene and toluene; chain or cyclic ethers such as diethyl ether and tetrahydrofuran; and esters such as ethyl acetate.

[0081] Preferably, the pressure of the hydrogenation reaction is 0.1-10 MPa.

[0082] Preferably, the hydrogenation reaction is carried out at a temperature greater than or equal to -20°C and less than or equal to the boiling point of the reaction solvent, such as -20°C, 0°C, 15°C, 45°C, 75°C, etc., or at the boiling point of the solvent, i.e., under reflux conditions.

[0083] Preferably, the hydrogenation reaction takes 0.5-48 hours.

[0084] Preferably, the method using a metal compound or metal is carried out in any one or a mixture of at least two of methanol, ethanol, or ethyl acetate.

[0085] Preferably, the metal compound is stannous chloride, and the metal is any one or a combination of at least two of zinc powder or iron powder.

[0086] Preferably, the reaction temperature using the metal compound or metal method is greater than or equal to -10°C and less than or equal to the boiling point of the reaction solvent, such as -10°C, 20°C, 45°C, 80°C, etc., or the reaction is carried out at the boiling point of the solvent, i.e., under reflux.

[0087] Preferably, the reaction time of the method using metal compounds or metals is 0.5-48 hours.

[0088] 2-(iv): The reaction of a compound of general formula XI with a compound of general formula III yields a compound of general formula I.

[0089] The compound represented by general formula XI is reacted with the compound represented by general formula III under the same conditions as described in step 1-(i) to prepare the compound represented by general formula XII.

[0090] On the other hand, the present invention also provides an intermediate for preparing the amide compounds as described above, having the structure shown in Formula XI:

[0091]

[0092] W2, R1, and R2 have the same limiting range as those in compounds of general formula I, and will not be repeated here.

[0093] The preparation method of the intermediate compound described in Formula XI in this invention has been mentioned in the description of the preparation method of Formula I above, and will not be repeated here.

[0094] In this invention, representative compounds of the intermediate compounds of formula XI of the present invention are shown in Table 2, but the intermediate compounds of the present invention are not limited to the compounds shown in Table 2.

[0095] Table 2

[0096]

[0097] On the other hand, the present invention provides tautomers, enantiomers, diastereomers or salts thereof of the amide compounds as described above.

[0098] In this invention, the tautomers, enantiomers, diastereomers or salts of the amide compounds can also exert the same effects as the amide compounds, and have good insecticidal effect and fast action at low doses.

[0099] On the other hand, the present invention provides the application of the amide compounds described above in the control of pests and nematodes in the fields of agriculture, forestry and horticulture.

[0100] The amide compounds of this invention are suitable for controlling various agricultural, forestry, and horticultural pests, sanitary pests, and nematodes that harm rice, corn, wheat, potatoes, fruit trees, vegetables, other crops, and flowers.

[0101] In this invention, the pests include Lepidoptera, Coleoptera, Hemiptera, Thysanoptera, Diptera, Orthoptera, Homoptera, Isoptera, Hymenoptera, spider mites, nematodes, mosquitoes, flies, ants, etc.

[0102] Preferably, the pests include, but are not limited to: cotton bollworm, diamondback moth, beet armyworm, cotton bollworm, cabbage caterpillar, rice stem borer, rice leaf roller, rice thrips, western flower thrips, melon thrips, onion thrips, ginger thrips, mango thrips, peach aphid, cotton aphid, alfalfa aphid, apple aphid, wheat aphid, flea beetle, stink bug, gray planthopper, brown planthopper, white-backed planthopper, termite, mosquito fly, carmine spider mite, and citrus red spider mite.

[0103] The compounds of this invention have a wide range of applications, and the plants or ranges to which they are applied mainly include the following categories: fruits and vegetables, such as cucumber, loofah, watermelon, cantaloupe, pumpkin, gourd, spinach, celery, cabbage, Chinese cabbage, gourd, chili pepper, eggplant, tomato, onion, ginger, garlic, leek, lettuce, green beans, cowpeas, broad beans, radish, carrot, potato, and yam; cereals, such as wheat, barley, corn, rice, and sorghum; fruit trees, such as apple, pear, banana, citrus, grape, lychee, and mango; flowers, such as peony, rose, and flamingo; oil crops, such as peanut, soybean, rapeseed, sunflower, and sesame; sugar crops, such as sugar beet and sugarcane; other crops, such as strawberry, potato, sweet potato, tobacco, and tea; horticulture, forestry, household hygiene, and public health areas, etc. The above-listed plants or ranges do not limit the scope of use of the amide compounds of this invention.

[0104] On the other hand, the present invention provides an insecticide composition comprising an active ingredient and a pesticide-acceptable carrier, wherein the active ingredient is an amide compound as described above.

[0105] The compositions of the present invention can be applied in the form of a formulation, wherein the compound of general formula I is dissolved or dispersed in a carrier as an active component or formulated to facilitate dispersion when used as an insecticide.

[0106] In this invention, the insecticide composition can be formulated into wettable powder, suspension, water-in-oil emulsion or emulsifiable concentrate, etc.

[0107] The insecticide composition described in this invention can be used in agriculture, forestry, sanitation and other fields.

[0108] Preferably, the active ingredient in the insecticide composition has a weight percentage of 1-99%, for example, 1%, 10%, 20%, 35%, 55%, 75%, 95%, or 99%.

[0109] Preferably, the pesticide-acceptable carrier includes a surfactant.

[0110] In this invention, the surfactant is an ionic surfactant or a nonionic surfactant.

[0111] The surfactants include emulsifiers, dispersants, or wetting agents. Emulsifiers can be polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty amines, and commercially available emulsifiers (such as Agricultural Emulsion 2201B, Agricultural Emulsion 0203B, Agricultural Emulsion 100#, Agricultural Emulsion 500#, Agricultural Emulsion 600#, Agricultural Emulsion 600-2#, Agricultural Emulsion 1601, Agricultural Emulsion 2201, Agricultural Emulsion NP-10, Agricultural Emulsion NP-15, Agricultural Emulsion 507#, Agricultural Emulsion OX-635, Agricultural Emulsion OX-622, Agricultural Emulsion OX-653, Agricultural Emulsion OX-667, Ningru 36#, etc.). Dispersants include sodium lignosulfonate, dispersing agents, calcium lignosulfonate, and methylnaphthalenesulfonic acid formaldehyde condensate. Wetting agents include sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and sodium alkylnaphthalenesulfonate.

[0112] Preferably, the pesticide-acceptable carrier includes a solid carrier and / or a liquid carrier.

[0113] Preferably, the solid carrier comprises natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicates, such as talc; magnesium aluminum silicates, such as kaolinite, montmorillonite, and mica; white carbon black, calcium carbonate, and light calcium carbonate; calcium sulfate; limestone; sodium sulfate; and amine salts such as ammonium sulfate and hexamethylethylenediamine. The liquid carrier comprises water and organic solvents, which can also be used as auxiliaries or antifreeze additives when water is used as a solvent or diluent. Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, and toluene; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, chloroform, and dichloromethane; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, and light mineral oils; alcohols such as isopropanol, butanol, ethylene glycol, glycerol, and cyclohexanol; their ethers and esters; and ketones such as acetone, cyclohexanone, dimethylformamide, and N-methylpyrrolidone.

[0114] In the formulation of insecticide compositions, the active ingredients can be mixed with liquid and / or solid carriers, and surfactants (such as emulsifiers, dispersants, stabilizers, and wetting agents) can be added. Other adjuvants (such as binders, defoamers, and oxidants) can also be added.

[0115] On the other hand, the present invention provides a method for controlling pests, the method being: applying an effective dose of the amide compound or insecticide composition as described above to the pest that needs to be controlled or its growth medium.

[0116] Preferably, the effective dose is 7.5-1000g per hectare, such as 7.5g, 50g, 100g, 180g, 250g, 350g, 450g, 600g, 800g or 1000g, and more preferably 15-600g per hectare.

[0117] The compositions of the present invention can be applied to pests or their growth media in the form of formulations. Compound I of general formula is dissolved or dispersed in a carrier or formulated as an active ingredient for easier dispersion when used as an insecticide. For example, these chemical formulations can be formulated into various liquids, emulsifiable concentrates, suspensions, aqueous suspensions, microemulsions, emulsions, water-in-oil emulsions, powders, wettable powders, soluble powders, granules, water-dispersible granules, or capsules.

[0118] For certain applications, such as in agriculture, one or more other insecticides, fungicides, herbicides, plant growth regulators, or fertilizers may be added to the insecticidal composition of the present invention, thereby producing additional advantages and effects.

[0119] Compared with the prior art, the present invention has the following beneficial effects:

[0120] The amide compounds of this invention have significant effects on the control of pests and diseases in agriculture and forestry, nematodes, and pests in the field of public health. They can achieve good insecticidal effects at low doses, have a rapid onset of action, and can exert insecticidal activity within one day of application and achieve high insecticidal activity within three days. They have good rapid-acting properties, can be applied at low doses, reduce the harm to plants and humans caused by excessive drug concentrations, and produce less drug residues, which is more environmentally friendly. Furthermore, their preparation method is simple, efficient, and easy to scale up for production, and has broad application prospects. Detailed Implementation

[0121] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be considered as specific limitations thereof. Unless otherwise specified in the embodiments and the present invention: when characterizing the compounds by 1H NMR spectroscopy, the corresponding samples are dissolved in deuterated dimethyl sulfoxide (DMSO-d6), and 1H NMR data are obtained using a 400MHz NMR spectrometer, with chemical shift units in ppm (i.e., δ:ppm); the eluent used for column chromatography purification is prepared according to the indicated volume ratio of petroleum ether (PE): ethyl acetate (EA).

[0122] Synthesis Examples

[0123] Synthesis Example 1

[0124] Preparation of 6-benzoamide-N-[2-chloro-6-(difluoromethoxy)-4-(perfluoroprop-2-yl)phenyl]pyridinecarboxamide (compound number 1):

[0125] (1) Synthesis of N-[2-chloro-6-(difluoromethoxy)-4-(perfluoroprop-2-yl)phenyl]-6-nitropyridinecarboxamide

[0126]

[0127] 6-Nitropyridine-2-carboxylic acid (1.86 g, 9.96 mmol), toluene (20 mL), and thionyl chloride (5.92 g, 49.8 mmol) were added sequentially to a reaction flask. The mixture was stirred at 120 °C for 2 hours and then concentrated under reduced pressure to obtain 6-nitro-2-pyridinecarboxyl chloride.

[0128] 2-Chloro-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-difluoromethoxyaniline (3.00 g, 8.3 mmol) and potassium iodide (0.66 g, 4.00 mmol) were added to a solution of 6-nitro-2-pyridinecarboxyl chloride in acetonitrile (35 mL). The mixture was heated to 99 °C and reacted for 2 hours. The reaction progress was monitored by TLC. The reaction solution was cooled to room temperature and extracted with ethyl acetate (70 mL) and water (70 mL). The organic layer was concentrated under reduced pressure, and the residue was purified by column chromatography (PE:EA = 9:1) to give a reddish-brown solid (2.94 g, yield 69.34%).

[0129] 1 H NMR: 10.65(s,1H),8.62–8.57(m,1H),8.56–8.53(m,1H),8.51(d,J=7.60Hz,1H),7.82(s,1H),7.52(s,1H),7.39(t,J=72.0Hz,1H).

[0130] (2) Synthesis of 6-amino-N-[2-chloro-6-(difluoromethoxy)-4-(perfluoroprop-2-yl)phenyl]pyridinecarboxamide

[0131]

[0132] N-[2-chloro-6-(difluoromethoxy)-4-(perfluoroprop-2-yl)phenyl]-6-nitropyridinecarboxamide (2.86 g, 5.59 mmol) was dissolved in a mixture of ethanol (30 mL) and water (30 mL). Iron powder (3.12 g, 55.89 mmol) and ammonium chloride (2.99 g, 55.89 mmol) were added with stirring. The mixture was heated to 99 °C and reacted for 2 hours. The reaction progress was monitored by TLC. The reaction solution was cooled to room temperature, filtered, and the mother liquor was evaporated to dryness. Ethyl acetate (70 mL) and water (70 mL) were added for extraction. The organic layer was concentrated under reduced pressure, and the residue was purified by column chromatography (PE:EA = 6:1) to give a yellow solid (2.53 g, yield 93.70%).

[0133] 1H NMR: 10.05(s,1H),7.79(d,J=1.6Hz,1H),7.60(dd,J=8.4,7.2Hz,1H),7.49(s, 1H),7.34(t,J=72.0Hz,1H),7.28–7.23(m,1H),6.81–6.67(m,1H),6.23(s,2H).

[0134] (3) Synthesis of 6-benzoylamino-N-[2-chloro-6-(difluoromethoxy)-4-(perfluoroprop-2-yl)phenyl]pyridinecarboxamide

[0135]

[0136] Benzoic acid (0.06 g, 0.50 mmol), toluene (8 mL), and thionyl chloride (0.30 g, 2.5 mmol) were added sequentially to the reaction flask. The mixture was stirred at 120 °C for 2 hours and then concentrated under reduced pressure to obtain benzoyl chloride.

[0137] 6-Amino-N-[2-chloro-6-(difluoromethoxy)-4-(perfluoroprop-2-yl)phenyl]pyridinecarboxamide (0.2 g, 0.42 mmol) and potassium iodide (0.03 g, 0.20 mmol) were added to a benzoyl chloride solution in acetonitrile (4 mL). The mixture was heated to 99 °C and reacted for 2 hours. The reaction progress was monitored by TLC. The reaction solution was cooled to room temperature, and ethyl acetate (20 mL) and water (20 mL) were added. The mixture was extracted and separated. The organic layer was concentrated under reduced pressure, and the residue was purified by column chromatography (PE:EA = 4:1) to give a white solid (0.29 g, yield 95.69%).

[0138] 1 H NMR: 10.63(s,1H),10.30(s,1H),8.40(d,J=8.0Hz,1H),8.05(d,J=7.2Hz,2H),7.96–7.95(m,1H),7.94–7.9 3(m,1H),7.88(d,J=7.2Hz,1H),7.84(s,1H),7.57(s,1H),7.54(s,1H),7.50(s,1H),7.40(t,J=72.0Hz,1H).

[0139] Some of the compounds in Table 3 were prepared using a method similar to that in Synthesis Example 1. The NMR data of some of the compounds synthesized in Synthesis Example 1 are given in Table 3 below.

[0140] Table 3

[0141]

[0142] Synthesis Example 2

[0143] Preparation of N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-(difluoromethoxy)phenyl]-6-(4-cyano-2-methylbenzamido)pyridine amide (compound number 123):

[0144] (1) Synthesis of N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-difluoromethoxyphenyl]-6-nitropyridine amide

[0145]

[0146] 6-Nitropyridinecarboxylic acid (3.36 g, 20.00 mmol), toluene (15 mL), and thionyl chloride (8.57 g, 72.0 mmol) were added sequentially to the reaction flask. The mixture was stirred under reflux for 2 h and then concentrated under reduced pressure to obtain 6-nitrobenzoyl chloride. 2-Bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-difluoromethoxyaniline (6.77 g, 16.67 mmol), potassium iodide (1.38 g, 8.34 mmol), and 30 mL of acetonitrile were added to 6-nitrobenzoyl chloride. The mixture was heated to 84 °C and reacted for 4 hours. The reaction solution was then cooled to room temperature, and 80 mL of ethyl acetate and 40 mL of water were added. The mixture was extracted and separated. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 6:1) to obtain the target product (8.20 g, yield 88.5%).

[0147] 1 H NMR: 10.66 (s, 1H), 8.62 ~ 8.57 (m, 1H), 8.56 ~ 8.47 (m, 2H), 7.92 (s, 1H), 7.55 (s, 1H), 7.38 (t, J = 72.8Hz, 1H).

[0148] (2) Synthesis of 6-amino-N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-difluoromethoxyphenyl]pyridine amide

[0149]

[0150] N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-difluoromethoxyphenyl]-6-nitropyridine amide (11.2 g, 20 mmol) was dissolved in ethanol (40 mL) and water (40 mL), followed by the addition of ammonium chloride (10.70 g, 200 mmol) and iron powder (11.17 g, 200 mmol). The mixture was heated under reflux for 5 h. The reaction was monitored by TLC until completion. The ethanol was removed from the reaction solution under reduced pressure, followed by filtration. 80 mL of ethyl acetate and 40 mL of water were added, and the mixture was extracted and separated. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 4:1) to obtain the target product (9.10 g, yield 86.5%).

[0151] 1 H NMR: 10.20(s,1H),7.89(s,1H),7.53(s,1H),7.32(t,J=72.0Hz,1H),7.03–6.89(m,2H),6.80(t,J=6.8Hz,1H),5.39(s,2H).

[0152] (3) Synthesis of N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-(difluoromethoxy)phenyl]-6-(4-cyano-2-methylbenzamido)pyridine amide

[0153]

[0154] In a solution of 6-amino-N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-difluoromethoxyphenyl]pyridine amide (0.17 g, 0.32 mmol) in acetonitrile (5 mL), potassium iodide (27 mg, 0.16 mmol) and 2-methyl-4-cyanobenzoyl chloride (70 mg, 0.39 mmol) were added sequentially, and the reaction was carried out at 80 °C for 4 hours. The reaction solution was cooled to room temperature, diluted with 40 mL of ethyl acetate, washed successively with 2 M hydrochloric acid (5 mL), saturated sodium bicarbonate aqueous solution (30 mL), and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE:EA = 3:1) to obtain the target product (0.15 g, yield 69.4%).

[0155] Compound 123 1H NMR: 11.11(s,1H),10.04(s,1H),8.40(s,1H),8.15(t,J=8.0Hz,1H),7.92(s,1H),7.90(d,J=7.2Hz ,1H),7.85(s,1H),7.81(d,J=8.0Hz,1H),7.73(d,J=8.0Hz,1H),7.56(s,1H),7.38(t,J=72.8Hz,1H)

[0156] Some of the compounds in Table 4 were prepared using a method similar to that in Synthesis Example 2. The NMR data of some of the compounds synthesized in Synthesis Example 2 are given in Table 4 below.

[0157] Table 4

[0158]

[0159]

[0160] Synthesis Example 3

[0161] Preparation of N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-(difluoromethoxy)phenyl]-6-[5-fluoro-pyridinecarboxamido]-pyridineamide (compound number 167):

[0162]

[0163] In a solution of 6-amino-N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-difluoromethoxyphenyl]pyridinecarboxamide (0.17 g, 0.32 mmol) in acetonitrile (5 mL), 5-fluoropyridinecarboxyl chloride (62 mg, 0.39 mmol) and potassium iodide (27 mg, 0.16 mmol) were added sequentially, and the mixture was reacted at 85 °C for 2 hours. The reaction solution was cooled to room temperature, concentrated under reduced pressure, diluted with 20 mL of ethyl acetate, washed successively with 30 mL of saturated sodium bicarbonate aqueous solution and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE:EA = 4:1) to give the target product (0.19 g, yield 90.10%).

[0164] Compound 167 1 H NMR: 10.80(s,1H),10.31(s,1H),8.60–8.53(m,1H),8.36–8.30(m,1H),8.23 –8.15(m,2H),7.94–7.91(m,2H),7.61–7.56(m,2H),7.37(t,J=72.8Hz,1H).

[0165] Some of the compounds in Table 5 were prepared using a method similar to that in Synthesis Example 3. The NMR data of some of the compounds synthesized in Synthesis Example 3 are given in Table 5 below.

[0166] Table 5

[0167]

[0168] Synthesis Example 4

[0169] Preparation of N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-difluoromethoxyphenyl]-6-nicotinamide pyridine amide (compound number 142):

[0170]

[0171] In a solution of 6-amino-N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-difluoromethoxyphenyl]pyridine amide (0.18 g, 0.34 mmol) in acetonitrile (5 mL), potassium iodide (28.4 mg, 0.17 mmol) and nicotinyl chloride (58.1 mg, 0.41 mmol) were added sequentially, and the reaction was carried out at 80 °C for 4 hours. The reaction solution was cooled to room temperature, diluted with 40 mL of ethyl acetate, washed successively with 2 M hydrochloric acid (5 mL), saturated sodium bicarbonate aqueous solution (30 mL), and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE:EA = 2:1) to give the target product (0.21 g, yield 96.73%). Compound 142... 1 H NMR: 10.99(s,1H),10.20(s,1H),9.19(d,J=1.6Hz,1H),8.81(dd,J=4.8,1.6Hz,1H),8.41~8.36(m,2H),8.16(t,J=8. 0Hz,1H),7.94(d,J=1.6Hz,1H),7.91(dd,J=7.6,0.8Hz,1H),7.63~7.59(m,1H),7.57(s,1H),7.39(t,J=72.8Hz,1H).

[0172] Some of the compounds in Table 6 were prepared using a similar method to that in Synthesis Example 4. The NMR data of some of the compounds synthesized in Table 6 below are given.

[0173] Table 6

[0174]

[0175]

[0176] Synthesis Example 5

[0177] Preparation of N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-difluoromethoxyphenyl]-6-isonicotinamide pyridine amide (compound number 146):

[0178]

[0179] In a solution of 6-amino-N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)-6-difluoromethoxyphenyl]pyridine amide (0.18 g, 0.34 mmol) in acetonitrile (5 mL), potassium iodide (28.4 mg, 0.17 mmol) and isonicotinamide chloride (58.1 mg, 0.41 mmol) were added sequentially, and the reaction was carried out at 80 °C for 4 hours. The reaction solution was cooled to room temperature, diluted with 40 mL of ethyl acetate, washed successively with 2 M hydrochloric acid (5 mL), saturated sodium bicarbonate aqueous solution (30 mL), and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE:EA = 2:1) to give the target product (0.16 g, yield 74.09%). Compound 146... 1 H NMR: 11.03(s,1H),10.20(s,1H),8.83(dd,J=4.4,1.6Hz,2H),8.38(dd,J=8.4,0.8 Hz,1H),8.26~8.11(m,1H),7.96~7.90(m,4H),7.57(s,1H),7.39(t,J=72.8Hz,1H).

[0180] Some of the compounds in Table 7 were prepared using a method similar to that in Synthesis Example 5. The NMR data of some of the compounds synthesized in Synthesis Example 5 are given in Table 7 below.

[0181] Table 7

[0182]

[0183] Synthesis Example 6

[0184] Preparation of N-[2-(difluoromethoxy)-6-iodo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-6-[4-(methanesulfonyl)-benzamide]pyridineamide (compound number 193):

[0185] (1) Synthesis of N-[2-(difluoromethoxy)-6-iodo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-6-nitropyridine amide

[0186]

[0187] 6-nitro-2-pyridinecarboxylic acid (3.60 g, 21.41 mmol), toluene (30 mL), and thionyl chloride (10.19 g, 85.66 mmol) were added sequentially to the reaction flask. The mixture was stirred under reflux for 2 h and then concentrated under reduced pressure to obtain 6-nitropyridine chloride. Acetonitrile (80 mL), potassium iodide (1.17 g, 7.06 mmol), and 2-(difluoromethoxy)-6-iodo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)aniline (8.00 g, 17.76 mmol) were added to 6-nitropyridine chloride. The mixture was heated to 90 °C and reacted for 2 hours. The reaction solution was then cooled to room temperature, and 100 mL of ethyl acetate and 50 mL of water were added. The mixture was extracted and separated. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 5:1) to obtain the target product (10.0 g, yield 93.90%).

[0188] 1 H NMR: 10.61(s,1H),8.60(dd,J=7.6,1.2Hz,1H),8.57-8.47(m,2H),8.03(s,1H),7.53(s,1H),7.33(t,J=72.6Hz,1H).

[0189] (2) Synthesis of 6-amino-N-[2-(difluoromethoxy)-6-iodo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-6-nitropyridine amide

[0190]

[0191] N-[2-(difluoromethoxy)-6-iodo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-6-nitropyridine amide (10.0 g, 16.58 mmol) was dissolved in ethanol (100 mL), and concentrated hydrochloric acid (10 mL) and stannous chloride dihydrate (16.83 g, 74.61 mmol) were added sequentially. The mixture was heated to reflux for 3 h. The reaction was monitored by TLC until the reaction was complete. The reaction solution was evaporated to near dryness under reduced pressure. The pH of the residue was adjusted to 12 with 10% sodium hydroxide aqueous solution. The residue was extracted with ethyl acetate (200 mL). The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 5:1) to give 8.42 g of yellow oil, with a yield of 84.21%.

[0192] 1H NMR: 9.98(s,1H),7.98(d,J=4.0Hz,1H),7.66-7.56(m,1H),7.50(s,1H),7.27(t J=72.6Hz,1H),7.26(dd,J=7.2,0.8Hz,1H),6.81-6.66(m,1H),6.23(s,2H).

[0193] (3) Synthesis of N-[2-(difluoromethoxy)-6-iodo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-6-[4-(methanesulfonyl)-benzamide]pyridine amide

[0194]

[0195] In a solution of 6-amino-N-[2-(difluoromethoxy)-6-iodo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-6-nitropyridine amide (0.2 g, 0.35 mmol) in acetonitrile (5 mL), potassium iodide (23.17 mg, 0.14 mmol) and 4-(methanesulfonyl)benzoyl chloride (91.56 mg, 0.42 mmol) were added sequentially, and the reaction was carried out at 90 °C for 2 hours. The reaction was monitored by TLC until completion. The reaction solution was evaporated to near dryness under reduced pressure, cooled to room temperature, diluted with 20 mL of ethyl acetate, washed successively with 20 mL of saturated sodium bicarbonate aqueous solution and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE:EA = 4:1) to obtain the target product (0.16 g, yield 60.70%).

[0196] Compound 193 1 H NMR: 11.01(s,1H),10.15(s,1H),8.41(d,J=8.4Hz,1H),8.26(d,J=1.6Hz,1H),8.25(d,J=1.6Hz,1H),8.19-8.14(m,1H),8.1 3(d,J=1.6Hz,1H),8.11(s,1H),8.05(s,1H),7.92(dd,J=7.6,0.8Hz,1H),7.55(s,1H),7.35(t,J=72.6Hz,1H),3.31(s,3H).

[0197] Some of the compounds in Table 8 were prepared using a method similar to that in Synthesis Example 6. The NMR data of some of the compounds synthesized in Synthesis Example 6 are given in Table 8 below.

[0198] Table 8

[0199]

[0200]

[0201] Synthesis Example 7

[0202] Preparation of N-[2-(difluoromethoxy)-6-iodo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-6-(nicotinamide)pyridineamide (compound number 230):

[0203]

[0204] In a solution of 6-amino-N-[2-(difluoromethoxy)-6-iodo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-6-nitropyridine amide (0.2 g, 0.35 mmol) in acetonitrile (5 mL), potassium iodide (23.17 mg, 0.14 mmol) and nicotinyl chloride (59.27 mg, 0.42 mmol) were added sequentially, and the reaction was carried out at 90 °C for 2 hours. The reaction was monitored by TLC until completion. The reaction solution was evaporated to near dryness under reduced pressure, cooled to room temperature, diluted with 20 mL of ethyl acetate, washed successively with 20 mL of saturated sodium bicarbonate aqueous solution and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE:EA = 4:1) to obtain the target product (0.21 g, yield 88.31%).

[0205] Compound 230 1 H NMR: 10.99(s,1H),10.14(s,1H),9.19(d,J=1.6Hz,1H),8.80(dd,J=4.8,1.6Hz,1H),8.41-8.36(m,2H),8.16(t,J=8. 0Hz, 1H), 8.05 (d, J = 1.2Hz, 1H), 7.92 (dd, J = 7.6, 0.8Hz, 1H), 7.62-7.59 (m, 1H), 7.55 (s, 1H), 7.32 (t, J = 72.6Hz, 1H).

[0206] Some of the compounds in Table 9 were prepared using a method similar to that in Synthesis Example 7. The NMR data of some of the compounds synthesized in Synthesis Example 7 are given in Table 9 below.

[0207] Table 9

[0208]

[0209] Synthesis Example 8

[0210] Preparation of N-[2-(difluoromethoxy)-6-iodo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-6-(isonicotinamide)pyridineamide (compound number 233):

[0211]

[0212] In a solution of 6-amino-N-[2-(difluoromethoxy)-6-iodo-4-(1,1,1,2,3,3,3-heptafluoroprop-2-yl)phenyl]-6-nitropyridine amide (0.2 g, 0.35 mmol) in acetonitrile (5 mL), potassium iodide (23.17 mg, 0.14 mmol) and isonicotinyl chloride (59.27 mg, 0.42 mmol) were added sequentially, and the reaction was carried out at 90 °C for 2 hours. The reaction was monitored by TLC until completion. The reaction solution was evaporated to near dryness under reduced pressure, cooled to room temperature, diluted with 20 mL of ethyl acetate, washed successively with 20 mL of saturated sodium bicarbonate aqueous solution and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE:EA = 4:1) to obtain the target product (0.14 g, yield 59.15%).

[0213] Compound 233 1 H NMR: 11.03(s,1H),10.14(s,1H),8.83(d,J=6.0Hz,2H),8.39(dd,J=8.4,0.8Hz,1H),8.17(t, J=8.0Hz,1H),8.04(d,J=1.2Hz,1H),7.94-7.92(m,3H),7.55(s,1H),7.34(t,J=72.6Hz,1H).

[0214] Some of the compounds in Table 10 were prepared using a method similar to that in Synthesis Example 8. The NMR data of some of the compounds synthesized in Synthesis Example 8 are given in Table 10 below.

[0215] Table 10

[0216]

[0217] Other compounds of general formula I of the present invention can be synthesized by referring to the above method.

[0218] Formulation Example 1

[0219] In this embodiment, a formulation was prepared using compound 1 of the present invention as a representative compound, as detailed below:

[0220] 30 parts by weight of Compound 1 of the present invention, 15 parts by weight of polyoxyethylene styrene phenyl ether, 10 parts by weight of phosphorous acid, and 45 parts by weight of xylene were uniformly mixed to obtain an emulsifiable concentrate of Compound 1 of the present invention with a concentration of 30%.

[0221] Formulation Example 2

[0222] In this embodiment, a formulation was prepared using compound 86 of the present invention as a representative compound, as detailed below:

[0223] 20 parts by weight of compound 86 of the present invention, 2 parts by weight of sodium dodecyl sulfate, 2 parts by weight of dialkyl sulfosuccinate, 1 part by weight of sodium salt of β-naphthalenesulfonic acid formaldehyde condensate, and 75 parts by weight of diatomaceous earth were uniformly stirred and mixed to obtain a 20% wettable powder of compound 86 of the present invention.

[0224] Formulation Example 3

[0225] In this embodiment, a formulation was prepared using compound 156 of the present invention as a representative compound, as detailed below:

[0226] A 30% suspension of compound 156 of the present invention is obtained by mixing 30 parts by weight of compound 156 of the present invention, 10 parts by weight of ethylene glycol, 6 parts by weight of nonylphenol polyethylene glycol ether, 10 parts by weight of sodium lignosulfonate, 10 parts by weight of carboxymethyl cellulose, 1 part by weight of silicone oil aqueous solution, and water to make up to 100 parts by weight.

[0227] Bioactivity testing examples

[0228] The compounds of the present invention obtained above were tested against various pests. Unless otherwise specified in the embodiments and the present invention: the sample preparation method is as follows: weigh 10 mg of the original sample to be tested, dissolve it in 1 mL of DMF to prepare a 10000 ppm stock solution, and dilute the stock solution with 0.05% Tween-80 water to the required concentration for activity testing. The mortality rate is the mortality rate caused by the compound at the test concentration, and the calculation formula is: mortality rate (%) = number of dead insects / total number of insects * 100.

[0229] Test of the insecticidal activity of the compound in Example 1 against armyworms

[0230] The activity test was conducted using a corn seedling immersion feeding method. Fresh corn seedlings grown indoors were cut into sections approximately 10cm long from the above-ground portion and prepared for use. The seedlings were immersed in the pesticide solution for 10 seconds, then air-dried in a cool place. The sections were then cut into 3-5cm leaf segments and placed in petri dishes, with 3 leaf segments per dish. Ten third-instar armyworm larvae were added to each dish, and the process was repeated three times. The dishes were placed in a light incubator at 25℃ with a light intensity of 14 hL:10 hD. The number of dead insects was assessed 1, 2, and 3 days after treatment, and the mortality rate was calculated.

[0231] The compounds 1, 6, 39, 61, 63, 69, 85, 86, 90, 91, 101, 107, 110, 123, 129, 142, 146, 152, 153, 182, and 239 of this invention, at a concentration of 1 ppm, exhibit a mortality rate of ≥90% against armyworms 3 days after application.

[0232] Following the above method, compounds 61, 69, 85, 86, 90, 123, 129, 153, and 182, along with KC1 and KC2, were selected for parallel determination of their insecticidal activity against armyworms to compare their insecticidal activity and rapid insecticidal effect. The experimental results are shown in Table 11.

[0233] Table 11: Comparison of the insecticidal activity and rapid action of compound 61 of the present invention with KC1 and KC2 against armyworms.

[0234]

[0235] As can be seen from Table 11, the compounds of the present invention have better rapid effects and high insecticidal activity at lower doses compared with existing compounds.

[0236] Measurement Example 2 The compound's indoor bioactivity against Tetranychus carmine

[0237] Cut single leaves with stems from broad beans and insert them into a penicillin bottle filled with 20 mL of water. Inoculate each leaf with approximately 20 adult spider mites. After 24 hours, check the adult mite population and select single leaves with more than 15 mites for the experiment. Immerse the leaves with adult mites in the solution for 10 seconds, remove and air dry, then place them in an observation room for cultivation at a temperature of 20–26℃, a light intensity of 14 hL:10 hD, and a humidity of 40–60%. Observe the number of live and dead mites 3 days after treatment and calculate the mortality rate.

[0238] The test results are as follows:

[0239] Compounds 6, 39, 60, 61, 69, 85, 86, 91, 101, 106, 110, 123, 129, 133, 135, 136, 142, 146, 152, 155, 156, 160, 161, 162, 182, 193, 215, 218, 221, 223, 224, 230, 233, 239, 242, 243, 247, 248, and 249 of this invention, at a concentration of 100 ppm, caused a mortality rate of ≥90% against Tetranychus carmineus 3 days after application.

[0240] The compounds 39, 86, 101, 123, 129, 133, 136, 146, 156, 162, 193, 215, 218, 221, 224, 233, and 243 of this invention, at a concentration of 10 ppm, caused a mortality rate of ≥90% in Tetranychus cinnabarinus 3 days after application.

[0241] Following the above method, compounds 39, 86, 123, 129, 136, 146, 218, 224, and 243, along with KC1 and KC2, were selected for parallel determination of the activity of Tetranychus cinnabarinus. The experimental results are shown in Table 12.

[0242] Table 12 Comparison of the activity of compound 39 of the present invention with KC1 and KC2 against Tetranychus cinnabarinus.

[0243]

[0244] As can be seen from Table 12, the compounds of the present invention have the advantage of achieving better insecticidal effects at lower doses compared with existing compounds.

[0245] Measurement Example 3 Insecticidal activity of the compound against diamondback moth

[0246] The activity test was conducted using the leaf-dip feeding method. Leaf discs were immersed in the drug solution for 10 seconds, dried, and then placed in petri dishes (4 dishes per dish). Filter paper was placed inside each petri dish to maintain humidity. Ten diamondback moths were inoculated into each dish, with three replicates. The dishes were placed in a light incubator at 25℃ with a light intensity of 14 hL:10 hD. The number of dead diamondback moths was assessed 1, 2, and 3 days after application, and the mortality rate was calculated.

[0247] The test results are as follows:

[0248] Compounds 6, 61, 63, 68, 69, 85, 86, 90, 101, 110, 129, 152, 153, 155, 156, 160, 161, 162, 182, 193, 202, 218, 224, 239, 242, 243, 247, 248, and 249, at a concentration of 1 ppm, showed a mortality rate of ≥90% against diamondback moth 3 days after application.

[0249] Following the above method, compounds 86, 90, 153, 202, 218, 243, and 248 were selected and their insecticidal activity against diamondback moth (Prunella vulgaris) was compared with KC1 and KC2 in parallel. The experimental results are shown in Table 13.

[0250] Table 13 Comparison of the insecticidal activity and fast-acting effect of compound 86 of the present invention with KC1 and KC2 against diamondback moth.

[0251]

[0252] As can be seen from Table 13, the compounds of the present invention have better rapid effects and high insecticidal activity at lower doses compared with existing compounds.

[0253] Test Example 4 Insecticidal activity of the compound against alfalfa aphids

[0254] Preparation of 3-day-old nymphs: Cut single leaves with stems from broad beans and insert them into a 20mL bottle filled with penicillin water. Inoculate each single leaf with 5 adult aphids, and cover with a perforated plastic cup. Remove the adult aphids after 24 hours. Conduct a baseline survey before the experiment, and select single leaves with more than 15 nymphs for the experiment.

[0255] Immersion method: Immerse single leaves of broad beans infested with aphids in the pesticide solution for 10 seconds, remove and air dry, repeat 3 times. Place on a culture rack in an observation room, cover with a perforated plastic cup, and incubate at 20-25℃ with a light intensity of 14 hL:10 hD. After 3 days, investigate the number of dead and live insects and calculate the mortality rate.

[0256] Compounds 85, 142, 146, 152, 153, 182, 230, and 239, at a concentration of 100 ppm, resulted in a mortality rate of ≥80% against alfalfa aphids 3 days after application.

[0257] Compound 142, at a concentration of 10 ppm, caused a mortality rate of ≥90% against alfalfa aphids 3 days after application.

[0258] Following the above method, compounds 142, 230, and 239, along with KC1 and KC2, were selected for parallel determination of their alfalfa aphid-killing activity. The experimental results are shown in Table 14.

[0259] Table 14 Comparison of the insecticidal activity of compound 142 of the present invention with KC1 and KC2 against alfalfa aphids.

[0260] medicine concentration Mortality rate (%, 3 days after medication) 142 100ppm 100.00 230 100ppm 100.00 239 100ppm 100.00 KC1 100ppm 0.00 KC2 100ppm 0.00

[0261] As can be seen from Table 14, the compounds of the present invention have the advantage of achieving better insecticidal effects at lower doses compared with existing compounds.

[0262] This invention illustrates the amide compounds, their preparation methods, and applications through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection and disclosure scope of this invention.

Claims

1. An amide compound, characterized in that, The amide compound is any one selected from the group consisting of the following compounds:

2. An intermediate compound for the preparation of the amide compound of any one of claim 1, characterized by which has the following structure XI: In formula XI, R1 is selected from Cl or I; R2 is selected from difluoromethoxy; and W2 is selected from oxygen.

3. Use of the amide compound according to any one of claim 1 in the control of plant pests, characterized in that, The plant pest is armyworm, diamondback moth, alfalfa aphid, or Tetranychus cinnabarinus.

4. The amide compound according to claim 3, for use in the control of plant pests, characterized in that, The plant pest is Tetranychus cinnabarinus.

5. An insecticide composition, characterized by, The insecticide composition comprises an active ingredient which is the amide compound as claimed in any one of claims 1 and a pesticidally acceptable carrier.

6. The insecticide composition according to claim 5, wherein The weight percentage of the active ingredient in the insecticide composition is 1-99%.

7. A method for controlling pests, characterized by, The method is to apply an effective dose of the amide compound as claimed in any one of claims 1 or the insecticide composition as claimed in claim 5 or 6 to a harmful organism in need of control or a medium in which the harmful organism grows.

8. A method for controlling pests according to claim 7, characterized in that, The effective dose is 7.5-1000 g per hectare.

9. A method for controlling pests according to claim 7, wherein, The effective dose is 15-600 g per hectare.

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