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, specifically relating 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, CN102112437A discloses compounds KC1 and KC2 (i.e., compounds 6-22 and 6-25 in CN102112437A) and their insecticidal activity. 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 be fast-acting and highly active 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 hydrogen, halogen atom, C1-C6 alkyl, and C1-C6 haloalkyl;

[0015] R2 is selected from OH, NH2, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, N-C1-C4 alkylamino, and N,N-di(C1-C4 alkyl)amino.

[0016] R3 is selected from difluoromethoxy or trifluoromethyl;

[0017] W1 and W2 are either oxygen atoms or sulfur atoms.

[0018] 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.

[0019] In this invention, as a preferred technical solution, Z1, Z2, Z3, Z4, and Z5 are each 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, and trifluoromethyl. R1 is selected from hydrogen, halogen atom, C1-C6 alkyl; R2 is selected from NH2, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, N-C1-C4 alkylamino; R3 is selected from difluoromethoxy or trifluoromethyl; W1 and W2 are selected from oxygen.

[0020] 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.

[0021]

[0022] Table I

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035] It should be noted that "H" represents hydrogen atom, "O" represents oxygen atom, "S" represents sulfur atom, "F" represents fluorine atom, "Cl" represents chlorine atom, "Br" represents bromine atom, "I" represents iodine atom, "Me" represents methyl, "MeO" represents methoxy, "EtO" represents ethoxy, "n-PrO" represents n-propoxy, "i-PrO" represents isopropoxy, "CF3" represents trifluoromethyl, and "OCF2H" represents difluoromethoxy.

[0036] In this invention, as a more preferred technical solution, in Formula I, Z1, Z2, Z3, Z4, and Z5 are independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methanesulfonyl, or trifluoromethanesulfonyl; R1 is selected from hydrogen or methyl; R2 is selected from methyl, ethyl, n-propyl, isopropyl, N-methylamino, N-ethylamino, N-propylamino, or N-isopropylamino; R3 is selected from difluoromethoxy or trifluoromethyl; and W1 and W2 are selected from oxygen.

[0037] In this invention, as a particularly preferred technical solution, the amide compound is selected from any one of the following compounds:

[0038]

[0039]

[0040] The compound numbers correspond to the compound numbers in Table 1.

[0041] 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.

[0042] 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 non-limitingly includes 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 non-limitingly includes 1-chlorocyclopropyl, 1-fluorocyclopropyl, perfluorocyclopropyl, etc.

[0043] 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.

[0044] 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.

[0045] Preparation method 1:

[0046] 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:

[0047]

[0048] Among them, LG is selected from fluorine, chlorine, bromine, and C1-C. 12 Alkoxy, C1-C 12 Alkyloxy acyloxy or C1-C 12 Alkyl acyloxy group; Hal is selected from fluorine, chlorine, bromine or iodine; L is selected from chlorine, bromine, iodine or C1-C6 alkyl sulfonate group.

[0049] 1-(i): Compound of general formula III reacts with compound of general formula IV to give compound of general formula V.

[0050] In this invention, in step 1-(i), the molar ratio of compound III to compound IV is 0.5-2:1, and the reaction is carried out in the presence of an alkaline substance such as an organic base and / or an inorganic base. 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. 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. The reaction temperature is greater than or equal to room temperature and less than or equal to the boiling point of the reaction solvent. The reaction time is 0.5-48 hours.

[0051] 1-(ii): The reaction of compound V with compound VI yields compound VII.

[0052] In this invention, the molar ratio of compound V to compound VI in step 1-(ii) is 0.5-2:1, and the reaction is carried out in the presence of an alkaline substance such as an organic base and / or an inorganic base. 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. 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. The reaction temperature is greater than or equal to -10°C and less than or equal to the boiling point of the reaction solvent. The reaction time is 0.5-48 hours.

[0053] 1-(iii): Hydrolysis of compound of general formula VII yields compound of general formula VIII.

[0054] Step 1-(iii) involves the hydrolysis of the compound of general formula VII in the presence of an alkaline substance to prepare the compound of general formula VIII. Preferably, the alkaline substance is lithium hydroxide, sodium hydroxide, or potassium hydroxide. Preferably, the amount of the alkaline substance is 1-5 times the molar amount of the compound of general formula VII.

[0055] 1-(iv): Compound of general formula VIII undergoes a substitution reaction to give compound of general formula II.

[0056] In this step, a known method is used to react a compound of general formula VIII with a compound containing an LG group, such as thionyl chloride, oxalyl chloride, or triphosgene, to prepare a compound represented by general formula II.

[0057] 1-(v): The reaction of compound II with compound IX yields compound I.

[0058] In this invention, the molar ratio of compound II to compound IX is 0.5-2:1, and the reaction is carried out in the presence of an alkaline substance, which is an organic base and / or an inorganic base. Preferably, the organic base is any one or a combination of at least two of triethylamine, N,N-diisopropylethylamine, pyridine, piperidine, 4-N,N-dimethylaminopyridine, alkali metal alkoxides, and lithium amide. Preferably, the alkali metal alkoxide is sodium methoxide and / or sodium ethoxide. Preferably, the lithium amide is diisopropylaminolithium. Preferably, the inorganic base is any one or a combination of at least two of alkali metal hydroxides, carbonates, or phosphates. 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 phosphate.

[0059] The solvent for the reaction in step 1-(v) 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. The reaction temperature is greater than or equal to -70°C and less than or equal to the boiling point of the reaction solvent. The reaction time is 0.5–48 hours.

[0060] Preparation method 2:

[0061] The compound of general formula I of the present invention can be prepared by another method as follows:

[0062]

[0063] 2-(i): Compound of general formula X undergoes a substitution reaction to give compound of general formula XI.

[0064] In this step, a known method is used to react a compound of general formula X with thionyl chloride, oxalyl chloride, triphosgene, etc., to prepare a compound of general formula XI containing an LG group.

[0065] 2-(ii): The reaction of compound of general formula XI with compound of general formula IX yields compound of general formula XII.

[0066] The compound represented by general formula XI is reacted with the compound represented by general formula IX under the same conditions as described in 1-(v) to prepare the compound represented by general formula XII.

[0067] 2-(iii): The reduction of compound XII yields compound XIII.

[0068] Aromatic carboxylic acid amide derivatives with nitro groups, represented by general formula XII, can be reduced to aromatic carboxylic acid amide derivatives with amine groups, represented by general formula XIII. Examples of reduction reactions include methods using hydrogenation and methods using metal compounds (such as stannous chloride) or metals (zinc powder, iron powder, etc.).

[0069] 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. The catalyst in the hydrogenation reaction can be palladium-carbon catalysts, cobalt catalysts, ruthenium catalysts, platinum catalysts, etc. The solvent can be alcohols such as methanol and ethanol; aromatic hydrocarbons such as benzene and toluene; chain or cyclic ethers such as diethyl ether and tetrahydrofuran; esters such as ethyl acetate. Preferably, the hydrogenation reaction is carried out at a pressure of 0.1-10 MPa, a temperature greater than or equal to -20°C and less than or equal to the boiling point of the reaction solvent, and a reaction time of 0.5-48 hours.

[0070] The reaction is carried out using a metal compound or a metal method in a solvent containing any one or a mixture of at least two of methanol, ethanol, or ethyl acetate. 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. 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. Preferably, the reaction time using the metal compound or metal method is 0.5-48 hours.

[0071] 2-(iv): Compound of general formula XIII reacts with compound of general formula IV to give compound of general formula XIV.

[0072] The compound represented by general formula XIII is reacted with the compound represented by general formula IV under the same conditions as described in step 1-(i) to prepare the compound represented by general formula XII.

[0073] 2-(v): Compound of general formula XIV reacts with compound of general formula VI to give compound of general formula I.

[0074] The compound represented by general formula XIV is reacted with the compound represented by general formula VI under the same conditions as described in step 1-(ii) to prepare the compound represented by general formula XII.

[0075] Preparation method 3:

[0076] The compound of general formula I of the present invention can be prepared by the following method:

[0077]

[0078] 3-(i): Compound of general formula X undergoes a substitution reaction to give compound of general formula XI.

[0079] The compound represented by general formula X is reacted with the compound represented by general formula XI under the same conditions as described in 2-(i) to prepare the compound represented by general formula XI.

[0080] 3-(ii): The reaction of compound of general formula XI with compound of general formula IX yields compound of general formula XII.

[0081] The compound represented by general formula XI is reacted with the compound represented by general formula IX under the same conditions as described in 1-(v) to prepare the compound represented by general formula XII.

[0082] 3-(iii): The reduction of compound XII yields compound XIII.

[0083] The compound represented by general formula XII was reacted under the same conditions as described in 2-(iii) to prepare the compound represented by general formula XIII.

[0084] 3-(iv): Compound of general formula XIII reacts with compound of general formula XV to give compound of general formula XIV.

[0085] In this invention, the molar ratio of compound XIII to compound XV is 0.5-2:1. Step 3-(iv) is carried out in the presence of an acidic substance and a reducing agent. The acidic substance is an organic acid and / or an inorganic acid, and the reducing agent is a borohydride. Preferably, the organic acid is any one or a combination of at least two of formic acid, acetic acid, trifluoroacetic acid, or methanesulfonic acid. Preferably, the inorganic acid is any one or a combination of at least two of hydrochloric acid, phosphoric acid, or sulfuric acid. The reducing agent is sodium borohydride, sodium cyanoborohydride, or sodium triacetoxyborohydride. The solvent for the reaction is selected from any one or a combination of at least two of dichloromethane, toluene, ethyl acetate, acetone, tetrahydrofuran, dioxane, and N,N-dimethylformamide. The reaction temperature is greater than or equal to room temperature and less than or equal to the boiling point of the reaction solvent. The reaction time is 0.5-48 hours.

[0086] 3-(v): Compound of general formula XIV reacts with compound of general formula VI to give compound of general formula I.

[0087] The compound represented by general formula XIV is reacted with the compound represented by general formula VI under the same conditions as described in step 1-(ii) to prepare the compound represented by general formula I.

[0088] 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 XIV:

[0089]

[0090] W2, R1, R2, and R3 have the same limiting range as those in compounds of general formula I, and will not be repeated here.

[0091] The preparation method of the intermediate compound described in Formula XIV in this invention has been mentioned in the description of the preparation method of Formula I above, and will not be repeated here.

[0092] In this invention, representative compounds of the intermediate compounds of formula XIV of the present invention are shown in Table 2, but the intermediate compounds of the present invention are not limited to those shown in Table 2.

[0093] Table 2

[0094]

[0095]

[0096] On the other hand, the present invention provides tautomers, enantiomers, diastereomers or salts thereof of the amide compounds as described above.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] In this invention, the pests include Lepidoptera, Coleoptera, Hemiptera, Thysanoptera, Diptera, Orthoptera, Homoptera, Isoptera, Hymenoptera, spider mites, nematodes, mosquitoes, flies, ants, etc.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] In this invention, the insecticide composition can be formulated into wettable powder, suspension, water-in-oil emulsion or emulsifiable concentrate, etc.

[0106] The insecticide composition described in this invention can be used in agriculture, forestry, sanitation and other fields.

[0107] 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%.

[0108] Preferably, the pesticide-acceptable carrier includes a surfactant.

[0109] In this invention, the surfactant is an ionic surfactant or a nonionic surfactant.

[0110] 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.

[0111] Preferably, the pesticide-acceptable carrier includes a solid carrier and / or a liquid carrier.

[0112] 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 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.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] The compositions of the present invention can be applied to pests or their growth media in formulation form. 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.

[0117] 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.

[0118] Compared with the prior art, the present invention has the following beneficial effects:

[0119] 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 take effect more quickly at low concentrations of 0.1-1 ppm: they can exert good insecticidal activity one day after application and reach >90% insecticidal activity within 3 days. This reduces the harm to plants, the environment, and humans caused by excessive drug concentrations, and also results in less drug residue after application, which is more conducive to environmental protection and ecological civilization. Detailed Implementation

[0120] 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, the corresponding samples for characterization of the compounds by 1H NMR spectroscopy were dissolved in deuterated dimethyl sulfoxide (DMSO-d6), and 1H NMR data were obtained using a 400MHz NMR spectrometer. The chemical shift unit is ppm (i.e., δ:ppm). The eluent for column chromatography purification was prepared according to the indicated volume ratio of petroleum ether (PE): ethyl acetate (EA).

[0121] Synthesis Examples

[0122] Synthesis Example 1

[0123] Preparation of N-benzoyl-N-(3-((2-bromo-4-(perfluoroisopropyl)-6-(trifluoromethyl)phenyl)carbamoyl)-2-fluorophenyl)glycine ethyl ester (compound 2):

[0124] (1)(3-((2-bromo-4-(perfluoroisopropyl)-6-(trifluoromethyl)phenyl)carbamoyl)-2-fluorophenyl)glycine ethyl ester

[0125]

[0126] 3-Amino-N-[2-bromo-4-(perfluoroisopropyl)-6-trifluoromethylphenyl]-2-fluorobenzamide (5.0 g, 9.20 mmol) was dissolved in 1,2-dichloroethane (100 mL), followed by the addition of ethyl glyoxylate (0.93 g, 9.20 mmol) and acetic acid (3.31 g, 55.20 mmol). The mixture was stirred at room temperature for 1 h, and then sodium triacetoxyborohydride (5.90 g, 27.60 mmol) was added. The reaction was monitored by TLC until completion. The reaction solution was adjusted to pH 8 with saturated sodium bicarbonate solution and extracted with dichloromethane (100 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 = 20:1) to give a yellow oil (2.0 g, yield 34%).

[0127] 1 H NMR: 10.59(s,1H),8.42(s,1H),7.96(s,1H),7.09(s,1H),6.88(s,1H),6 .79(s,1H),6.17(s,1H),4.13(d,J=7.2Hz,2H),4.01(s,2H),1.21(s,3H).

[0128] (2) Synthesis of N-benzoyl-N-(3-((2-bromo-4-(perfluoroisopropyl)-6-(trifluoromethyl)phenyl)carbamoyl)-2-fluorophenyl)glycine ethyl ester

[0129]

[0130] In a solution of ethyl glycine (0.20 g, 0.32 mmol) in tetrahydrofuran (5 mL), DMAP (29 mg, 0.24 mmol) and benzoyl chloride (133 mg, 0.95 mmol) were added sequentially, and the mixture was reacted at 50 °C for 8 hours. The reaction solution was cooled to room temperature, diluted with 40 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 = 5:1) to give the target product (0.19 g, yield 93.20%).

[0131] Compound 2 1HNMR: 10.61(s,1H),8.42(s,1H),7.96(s,1H),7.58-7.46(m,2H),7.42-7 .19(m,6H),4.72-4.44(m,2H),4.16(q,J=7.2Hz,2H),1.24-1.20(m,3H).

[0132] Synthesis Example 2

[0133] Preparation of N-(4-(methanesulfonyl)benzoyl)-N-(3-((2-bromo-4-(perfluoroisopropyl)-6-(trifluoromethyl)phenyl)carbamoyl)-2-fluorophenyl)glycine ethyl ester (compound 46):

[0134]

[0135] In a solution of ethyl glycine (0.20 g, 0.32 mmol) in acetonitrile (5 mL), potassium iodide (25 mg, 0.15 mmol) and 4-methanesulfonylbenzoyl chloride (83 mg, 0.38 mmol) were added sequentially, and the mixture was reacted at 80 °C for 4 hours. The reaction solution was cooled to room temperature, and 40 mL of ethyl acetate was added. The mixture was washed successively with 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 = 4:1) to obtain the target product (0.17 g, yield 65.38%).

[0136] Compound 46 1 HNMR: 10.61(s,1H),8.42(s,1H),7.95(s,1H),7.85(d,J=8.0Hz,2H),7.57(s,4H),7.32( t,J=7.6Hz,1H),4.75(s,1H),4.54(s,1H),4.17(s,2H),3.17(s,3H),1.26–1.23(m,3H).

[0137] Synthesis Example 3

[0138] Preparation of N-(nicotinyl)-N-(3-((2-bromo-4-(perfluoroisopropyl)-6-(trifluoromethyl)phenyl)carbamoyl)-2-fluorophenyl)glycine ethyl ester (compound 75):

[0139]

[0140] In a solution of ethyl glycine (0.20 g, 0.32 mmol) in acetonitrile (6 mL), potassium iodide (25 mg, 0.15 mmol) and nicotinyl chloride (54 mg, 0.38 mmol) were added sequentially, and the mixture was reacted at 80 °C for 6 hours. The reaction solution was cooled to room temperature, and 40 mL of ethyl acetate was added. The mixture was washed successively with 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 = 5:1) to obtain the target product (0.07 g, yield 30.43%).

[0141] Compound 75 1 HNMR: 10.66(s,1H),8.54(d,J=2.8Hz,1H),8.46(s,1H),8.42(s,1H),7.96(s,1H),7.74(d,J=6.4Hz,1H),7.66–7.51(m ,2H),7.38–7.28(m,2H),4.75(d,J=13.2Hz,1H),4.50(d,J=16.4Hz,1H),4.17(q,J=7.2Hz,2H),1.23(d,J=4.8Hz,3H).

[0142] Synthesis Example 4

[0143] Preparation of N-(isonicotinyl)-N-(3-((2-bromo-4-(perfluoroisopropyl)-6-(trifluoromethyl)phenyl)carbamoyl)-2-fluorophenyl)glycine ethyl ester (compound 76):

[0144]

[0145] In a solution of ethyl glycine (0.20 g, 0.32 mmol) in acetonitrile (6 mL), potassium iodide (25 mg, 0.15 mmol) and isonicotinyl chloride (54 mg, 0.38 mmol) were added sequentially, and the mixture was reacted at 80 °C for 6 hours. The reaction solution was cooled to room temperature, and 40 mL of ethyl acetate was added. The mixture was washed successively with 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 = 5:1) to obtain the target product (0.10 g, yield 43.47%).

[0146] Compound 76 1HNMR: 10.62(s,1H),8.53(d,J=4.4Hz,2H),8.42(s,1H),7.96(s,1H),7.65–7.53(m,2H),7.31(t,J=7.6 Hz,1H),7.25(d,J=4.8Hz,2H),4.76(s,1H),4.52(s,1H),4.18(d,J=7.2Hz,2H),1.23(t,J=7.2Hz,3H).

[0147] Synthesis Example 5

[0148] Preparation of N-(4-fluorobenzoyl)-N-(3-((2-bromo-4-(perfluoroisopropyl)-6-(difluoromethoxy)phenyl)carbamoyl)-2-fluorophenyl)glycine ethyl ester (compound 123):

[0149] (1)(3-((2-bromo-4-(perfluoroisopropyl)-6-(difluoromethoxy)phenyl)carbamoyl)-2-fluorophenyl)glycine ethyl ester)

[0150]

[0151] 3-Amino-N-[2-bromo-4-(perfluoroisopropyl)-6-difluoromethoxyphenyl]-2-fluorobenzamide (1.5 g, 2.70 mmol) was dissolved in dichloromethane (150 mL), and titanium tetrachloride (1.0 g, 5.40 mmol), ethyl glyoxylate (0.51 g, 5.40 mmol), and sodium triacetoxyborohydride (1.10 g, 5.40 mmol) were added sequentially. The mixture was stirred at room temperature. The reaction was monitored by TLC until completion. The reaction solution was adjusted to pH 8 with saturated sodium bicarbonate aqueous solution and extracted with dichloromethane (100 mL). The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (PE:EA = 20:1) to give a yellow oil (0.70 g, yield 41.42%).

[0152] (2) Synthesis of N-(4-fluorobenzoyl)-N-(3-((2-bromo-4-(perfluoroisopropyl)-6-(difluoromethoxy)phenyl)carbamoyl)-2-fluorophenyl)glycine ethyl ester

[0153]

[0154] In a 5 mL solution of toluene containing ethyl glycine (0.20 g, 0.31 mmol) of 3-((2-bromo-4-(perfluoroisopropyl)-6-(difluoromethoxy)phenyl)carbamoyl)-2-fluorophenyl)glycine, pyridine (50 mg, 0.62 mmol) and p-fluorobenzoyl chloride (60 mg, 0.37 mmol) were added sequentially, and the mixture was reacted under reflux for 8 hours. The reaction solution was cooled to room temperature, diluted with 40 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 = 5:1) to give the target product (0.13 g, yield 56.03%).

[0155] Compound 123 1 H NMR: 10.35(s,1H),7.91(s,1H),7.58–7.24(m,7H),7.19–7.08(m,2H),4.58(d,J=102.8Hz,2H),4.16(q,J=7.2Hz,2H),1.24–1.20(m,3H).

[0156] Synthesis Example 6

[0157] Preparation of N-(nicotinyl)-N-(3-((2-bromo-4-(perfluoroisopropyl)-6-(difluoromethoxy)phenyl)carbamoyl)-2-fluorophenyl)glycine ethyl ester (compound 178):

[0158]

[0159] In a 6 mL solution of toluene containing ethyl glycine (0.16 g, 0.25 mmol) of 3-((2-bromo-4-(perfluoroisopropyl)-6-(difluoromethoxy)phenyl)carbamoyl)-2-fluorophenyl)glycine, pyridine (40 mg, 0.50 mmol) and nicotinyl chloride (53 mg, 0.30 mmol) were added sequentially, and the mixture was reacted under reflux for 6 hours. The reaction solution was cooled to room temperature, and 40 mL of ethyl acetate was added. The mixture was washed successively with 30 mL of 2N HCl 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 (67 mg, yield 36.61%).

[0160] Compound 178 1H NMR: 10.39(s,1H),8.66–8.26(m,2H),7.91(d,J=2.0Hz,1H),7.74(d,J=7.6Hz,1H),7.65–7.4 5(m,3H),7.44–6.95(m,3H),4.63(d,J=98.6Hz,2H),4.17(q,J=7.2Hz,2H),1.31–1.21(m,3H).

[0161] Synthesis Example 7

[0162] Preparation of N-(isonicotinyl)-N-(3-((2-bromo-4-(perfluoroisopropyl)-6-(difluoromethoxy)phenyl)carbamoyl)-2-fluorophenyl)glycine ethyl ester (compound 179):

[0163]

[0164] In a toluene (6 mL) solution of ethyl glycine (0.16 g, 0.25 mmol) of 3-((2-bromo-4-(perfluoroisopropyl)-6-(difluoromethoxy)phenyl)carbamoyl)-2-fluorophenyl)glycine, pyridine (40 mg, 0.50 mmol) and isonicotinyl chloride (55 mg, 0.30 mmol) were added sequentially, and the mixture was reacted under reflux for 8 hours. The reaction solution was cooled to room temperature, and 40 mL of ethyl acetate was added. The mixture was washed successively with 2N HCl (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 give the target product (0.15 g, yield 81.97%).

[0165] Compound 179 1 H NMR: 10.37(s,1H),8.53(d,J=5.2Hz,2H),7.91(d,J=2.0Hz,1H),7.61–7.51(m,3H), 7.41–7.10(m,4H),4.83–4.42(m,2H),4.18(q,J=7.2Hz,2H),1.23(t,J=7.2Hz,3H).

[0166] Some of the compounds in Table 1 were prepared using similar methods to those described in Synthesis Examples 1-7. Table 3 below describes the NMR data obtained from testing them.

[0167] Table 3

[0168]

[0169]

[0170] Other compounds of general formula I of the present invention can be synthesized by referring to the above method.

[0171] Formulation Example 1

[0172] In this embodiment, a formulation was prepared using compound 2 of the present invention as a representative compound, as detailed below:

[0173] 30 parts by weight of compound 2 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 2 of the present invention with a concentration of 30%.

[0174] Formulation Example 2

[0175] In this embodiment, a formulation was prepared using compound 15 of the present invention as a representative compound, as detailed below:

[0176] 20 parts by weight of compound 15 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 15 of the present invention.

[0177] Formulation Example 3

[0178] In this embodiment, a formulation was prepared using compound 183 of the present invention as a representative compound, as detailed below:

[0179] A 30% suspension of compound 183 of the present invention is obtained by mixing 30 parts by weight of compound 183 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.

[0180] Bioactivity testing examples

[0181] 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.

[0182] Example 1 of bioassay Insecticidal activity of the compound against fall armyworm

[0183] The activity test was conducted using a corn seedling immersion feeding method. Approximately 10cm of the above-ground portion of freshly grown indoor corn seedlings was cut and prepared. The seedlings were immersed in the pesticide solution for 10 seconds, then air-dried in a cool place. The seedlings were then cut into 3-5cm leaf segments and placed in petri dishes, with 3 leaf segments per dish. Ten third-instar larvae of the fall armyworm were added to each dish, 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 fall armyworms was assessed 1, 2, and 3 days after the pesticide application, and the mortality rate was recorded.

[0184] Compounds 2, 12, 15, 16, 20, 26, 34, 46, 51, 57, 58, 75, 76, 80, 84, 88, 94, 98, 100, 105, 129, 183, and 193, at a concentration of 1 ppm, caused a mortality rate of ≥90% in fall armyworm 3 days after application.

[0185] Compounds 12, 15, 16, 20, 26, 34, 58, 80, 84, 94, 129, and 183, at a concentration of 0.1 ppm, caused a mortality rate of ≥90% in fall armyworm 3 days after application.

[0186] Following the above method, a number of compounds from this invention were selected and their insecticidal activity against fall armyworm was determined in parallel with that of KC1 and KC2. The experimental results are shown in Table 4.

[0187] Table 4 Comparison of the insecticidal activity of the compounds of this invention with KC1 and KC2 against fall armyworm.

[0188]

[0189] As can be seen from Table 4, compared with existing compounds, the compounds of the present invention not only have better rapid effect but also more efficient insecticidal activity at a low dose of 0.1 ppm.

[0190] Example 2 of biological testing Insecticidal activity of the compound against diamondback moth

[0191] 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.

[0192] The test results are as follows:

[0193] Compounds 2, 20, 26, 46, 51, 57, 58, 80, 84, 88, 94, 98, 100, 123, and 169, at a concentration of 1 ppm, showed a mortality rate of ≥90% against diamondback moth 3 days after application.

[0194] Compounds 26 and 84, at a concentration of 0.1 ppm, caused a mortality rate of ≥90% in diamondback moths 3 days after application.

[0195] Following the above method, a number of compounds from this invention were selected for parallel determination of their insecticidal activity against diamondback moth and comparison of their rapid-acting properties with KC1 and KC2. The experimental results are shown in Table 5.

[0196] Table 5. Comparison of the insecticidal activity and rapid action of the compounds of this invention with KC1 and KC2 against diamondback moth.

[0197]

[0198] As can be seen from Table 5, the compounds of the present invention, compared with existing compounds, not only have better rapid effect at a low dose of 1 ppm, but also have higher insecticidal activity.

[0199] 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 selected from any one of the following compounds: 、 、 、 、 、 。 2. The application of any of the amide compounds described in claim 1 in the control of plant pests.

3. An insecticide composition, characterized in that, The insecticide composition comprises an active ingredient and a pesticide-acceptable carrier, wherein the active ingredient is any of the amide compounds as described in claim 1.

4. The insecticide composition according to claim 3, characterized in that, The insecticide composition contains 1-99% by weight of the active ingredient.

5. A method for controlling pests, characterized in that, The method is to apply an effective dose of any amide compound as described in claim 1 or an insecticide composition as described in claim 3 or 4 to the pest that needs to be controlled or its growth medium.

6. The method for controlling pests according to claim 5, characterized in that, The effective dosage is 7.5-1000g per hectare.

7. The method for controlling pests according to claim 5, characterized in that, The effective dosage is 15-600g per hectare.

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