Azole-containing bisamide compound as well as preparation method and application thereof

Abstract

The invention provides an azole-containing bisamide compound as well as a preparation method and application thereof. The azole-containing bisamide compound has a structure as shown in a formula I in the specification. The azole-containing bisamide compound disclosed by the invention can have high insecticidal activity and good quick-acting property at a low dosage; and due to good effect under low dosage, the medicine dosage is reduced, environmental protection is facilitated, and the application prospect is wide.

Description

Technical Field

[0001] The present invention belongs to the field of insecticides, and particularly relates to a compound containing a triazole dicarboxamide, a preparation method thereof, and an application thereof. Background Art

[0002] In crop production such as agriculture and horticulture, damage caused by pests and the like is still very significant. Due to reasons such as pests developing resistance to existing insecticides and the environmental unfriendliness of existing pesticides, there has always been a need to develop new insecticides that are more efficient, less toxic, and more environmentally friendly.

[0003] The insecticidal activity of compounds containing triazole dicarboxamide has been reported. For example, patents CN102574777A and CN102414181A respectively disclose the compounds KC1 (i.e., compound I-43 in CN102574777A) and KC2 (i.e., compound D2 in CN102414181A) and their insecticidal activities. Although these disclosed compounds have insecticidal activities, their insecticidal effects at low doses are not good or their quick-acting properties are not good.

[0004]

[0005] In this field, there is still an active need to develop new insecticides that have quick-acting properties and high activities at low doses to meet the needs of agriculture and forestry. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a compound containing a triazole dicarboxamide, a preparation method thereof, and an application thereof. The amide compound has good insecticidal effects at low doses, has good quick-acting properties, low dosage, and is more conducive to environmental protection.

[0007] To achieve this purpose, the present invention adopts the following technical solutions:

[0008] On the one hand, the present invention provides a compound containing a triazole dicarboxamide, and the compound containing a triazole dicarboxamide has a structure shown in the following 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] or Z2 and Z3 are linked to form a substituted saturated five-membered heterocycle;

[0015] R is selected from hydrogen or trifluoromethyl;

[0016] A is selected from CH or N;

[0017] X1 is selected from fluorine, chlorine, bromine, or iodine;

[0018] X2 is selected from fluorine, chlorine, bromine, iodine, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, or C1-C6 haloalkylsulfonyl;

[0019] W is selected from an oxygen atom or a sulfur atom.

[0020] In the present invention, as a 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, 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, heptafluoropropyl, heptafluoroisopropyl, difluoromethoxy, trifluoromethoxy, pentafluoroethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl, or trifluoromethylsulfonyl; or Z2 and Z3 are linked to form a substituted saturated five-membered heterocycle; R is selected from hydrogen or trifluoromethyl; A is selected from CH or N; X1 is selected from chlorine, bromine, or iodine; X2 is selected from chlorine, bromine, iodine, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, or C1-C6 haloalkylsulfonyl; W is selected from an oxygen atom or a sulfur atom.

[0021] In the present 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, methylthio, ethylthio, n-propylthio, isopropylthio, mesyl or triflyl; R is selected from hydrogen or trifluoromethyl; A is selected from CH or N; X1 is selected from chlorine, bromine or iodine; X2 is selected from chlorine, bromine, iodine, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 haloalkylthio, C1-C4 alkanesulfinyl, C1-C4 haloalkanesulfinyl, C1-C4 alkylsulfonyl or C1-C4 haloalkylsulfonyl; or Z2 and Z3 are linked to form a substituted saturated five-membered heterocycle; W is selected from an oxygen atom or a sulfur atom.

[0022] As a further preferred technical solution of the present invention, the oxazole bisamide compound is any one of the compounds shown in Table 1 below having the general formula I.

[0023]

[0024] Table 1

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084] It should be noted that "H" represents a hydrogen atom, "N" represents a nitrogen atom, "O" represents an oxygen atom, "S" represents a sulfur atom, "F" represents a fluorine atom, "Br" represents a bromine atom, "CF3" represents a trifluoromethyl group, "OCF2H" represents a difluoromethoxy group, "Me" represents a methyl group, "Et" represents an ethyl group, "nPr" represents a n-propyl group, "iPr" represents an isopropyl group, "nBu" represents a n-butyl group, "tBu" represents a tert-butyl group, "SMe" represents a methylthio group, "SOMe" represents a methylsulfinyl group, "SO2Me" represents a methylsulfonyl group, "SEt" represents an ethylthio group, "SOEt" represents an ethylsulfinyl group, "SO2Et" represents an ethylsulfonyl group, "SnPr" represents a n-propylthio group, "SOnPr" represents a n-propylsulfinyl group, "SO2nPr" represents a n-propylsulfonyl group, "SiPr" represents an isopropylthio group, "SOiPr" represents an isopropylsulfinyl group, "SO2iPr" represents an isopropylsulfonyl group, "SnBu" represents a n-butylthio group, "SOnBu" represents a n-butylsulfinyl group, "SO2nBu" represents a n-butylsulfonyl group, "StBu" represents a tert-butylthio group, "SOtBu" represents a tert-butylsulfinyl group, "SO2tBu" represents a tert-butylsulfonyl group.

[0085] In the present invention, as a particularly preferred technical solution, the oxazole amide compound is any one selected from the following compounds, where the compound numbers correspond to the compound numbers in Table 1:

[0086]

[0087]

[0088] The alkyl group in the present invention refers to an alkyl group in a straight-chain or branched-chain form, such as groups like methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc. The haloalkyl group refers to a group in which one or more hydrogen atoms on the alkyl group are replaced by halogen atoms. The alkoxy group refers to a group in which an oxygen atom is connected to the end of the alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, etc. The haloalkoxy group refers to a group in which one or more hydrogen atoms on the alkoxy group are replaced by halogen atoms. The halogen is F, Cl, Br or I.

[0089] As used herein, the term "C1-C6 alkyl" refers to a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, including, 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-chain alkoxy group having 1 to 6 carbon atoms, including, without limitation, methoxy, ethoxy, n-propoxy, isopropoxy, and tert-butoxy, etc. "C1-C6 haloalkyl" refers to a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms substituted with halogen atoms, including, without limitation, trifluoromethyl, difluoromethyl, 1,1,1-trifluoroethyl, pentafluoroethyl, heptafluoroisopropyl, etc. "C1-C6 haloalkoxy" refers to a straight-chain or branched-chain alkoxy group having 1 to 6 carbon atoms substituted with halogen atoms, including, without limitation, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, etc.

[0090] In the present invention, C1-C6, C3-C8, etc. before the specific group indicate the number of carbon atoms contained in the group. For example, C1-C6 indicates a group in which the number of carbon atoms can be 1, 2, 3, 4, 5, or 6, and C3-C8 indicates a group in which the number of carbon atoms can be 3, 4, 5, 6, 7, or 8, and so on.

[0091] 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:

[0092]

[0093] (i): Reacting a compound of general formula II with a compound of general formula III to obtain a compound of general formula I.

[0094] In the present invention, the molar ratio of the compound of general formula II to the compound of general formula III is 0.5-2:1, and the reaction is carried out in the presence of a basic substance such as an organic base and / or an inorganic base. The temperature of the reaction 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 2-48 hours.

[0095] (ii): Reacting a compound of general formula IV with cyclopropanecarbaldehyde to obtain a compound of general formula II.

[0096] In the present invention, the molar ratio of the compound of general formula IV to cyclopropanecarbaldehyde is 0.98-1.0:1, and the reaction is carried out in the presence of a reducing agent. The temperature of the reaction 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.

[0097] (iii): Obtaining a compound of general formula IV by reducing a compound of general formula V.

[0098] As the reduction reaction, methods using hydrogenation reaction and methods using metal compounds (such as stannous chloride) or metals (zinc powder, iron powder, etc.) can be cited. The method using hydrogenation reaction can be carried out in a suitable solvent, in the presence of a catalyst, under normal pressure or under pressure, in a hydrogen atmosphere. As the catalyst in the hydrogenation reaction, palladium catalysts such as palladium-carbon, cobalt catalysts, ruthenium catalysts, platinum catalysts, etc. can be used. As the solvent, alcohols such as methanol and ethanol; aromatic hydrocarbons such as benzene and toluene; chain or cyclic ethers such as ether and tetrahydrofuran; esters such as ethyl acetate can be used. The method using metal compounds or metals is carried out in a mixed solvent of any one or at least two of methanol, ethanol or ethyl acetate.

[0099] (iv): The compound of general formula VI reacts with the compound of general formula VII to obtain the compound of general formula V.

[0100] In the present invention, the molar ratio of the compound of general formula VI to the compound of general formula VII is 0.3 - 1.0:1, and the reaction is carried out in the presence of a basic substance, and the basic substance is an organic base and / or an inorganic base.

[0101] (v): The compound of general formula VIII reacts with the compound of general formula IX to obtain the compound of general formula VI.

[0102] In the present invention, the molar ratio of the compound of general formula VIII to the compound of general formula IX is 1.0 - 2.0:1, and the reaction is carried out in the presence of a basic substance or a catalyst, and the basic substance is an organic base and / or an inorganic base. The catalyst is an alkali metal iodide.

[0103] (vi): The compound of general formula X undergoes a substitution reaction to obtain the compound of general formula VIII.

[0104] In this step, by using a known method, the compound of general formula X is reacted with a chlorinating reagent such as thionyl chloride, oxalyl chloride or triphosgene, etc., and then the compound represented by general formula VIII is prepared.

[0105] On the other hand, the present invention provides tautomers, enantiomers, diastereomers or salts of the azole bisamide compounds as described above.

[0106] In the present invention, the tautomers, enantiomers, diastereomers or salts of the azole bisamide compounds can also exert the same effect as the azole bisamide compounds, and have good insecticidal effect and quick effect at low doses.

[0107] On the other hand, the present invention provides the application of the azole bisamide compounds as described above in the prevention and control of pests and nematodes in the fields of agriculture, forestry and horticulture.

[0108] The azole bisamide compounds of the present invention are suitable for controlling various agricultural and forestry, horticultural pests, sanitary pests and nematodes that harm rice, corn, wheat, potatoes, fruit trees, vegetables, other crops and flowers, etc.

[0109] In the present invention, the pests include Lepidoptera, Coleoptera, Hemiptera, Thysanoptera, Diptera, Orthoptera, Homoptera, Isoptera, Hymenoptera, spider mite pests and nematodes, mosquitoes, flies, ants, etc.

[0110] Preferably, the pests include but are not limited to: Helicoverpa armigera, Plutella xylostella, Spodoptera exigua, Spodoptera litura, Pieris rapae, Chilo suppressalis, Tryporyza incertulas, Sesamia inferens, Spodoptera frugiperda, Cnaphalocrocis medinalis, Thrips oryzae, Frankliniella occidentalis, Thrips palmi, Thrips tabaci, Thrips zingiberis, Thrips mangiferae, Myzus persicae, Aphis gossypii, Aphis medicaginis, Aphis citricola, Sitobion avenae, flea beetles, stink bugs, Laodelphax striatellus, Nilaparvata lugens, Sogatella furcifera, termites, mosquitoes and flies, Tetranychus cinnabarinus, Panonychus citri.

[0111] The compounds of the present invention have a wide range of applications. The plants or ranges to which they are applied mainly include the following categories: fruits and vegetables, such as cucumber, towel gourd, watermelon, muskmelon, pumpkin, hanging melon, spinach, celery, cabbage, calabash, pepper, eggplant, tomato, onion, ginger, garlic, leek, asparagus lettuce, kidney bean, cowpea, broad bean, radish, carrot, potato, yam; cereals, such as wheat, barley, corn, rice, sorghum; fruit trees, such as apple, pear, banana, citrus, grape, litchi, mango; flowers, such as peony, rose, anthurium; oil crops, such as peanut, soybean, rapeseed, sunflower, sesame; sugar crops, such as beet, sugarcane; other crops, such as strawberry, potato, sweet potato, tobacco and tea; horticulture, forestry, household hygiene, public health areas, etc.; the above-listed plants or ranges do not limit the scope of use of the azole bisamide compounds of the present invention.

[0112] On the other hand, the present invention provides an insecticide composition, which includes an active ingredient and a pharmaceutically acceptable carrier, and the active ingredient is the azole bisamide compound as described above.

[0113] The composition of the present invention can be applied in the form of a preparation. When the compound of general formula I is used as an active ingredient and is dissolved or dispersed in a carrier or formulated into a preparation, it is more easily dispersed when used as an insecticide.

[0114] In the present invention, the insecticide composition can be made into dosage forms such as wettable powder, suspension concentrate, emulsion in water or emulsifiable concentrate.

[0115] The insecticide composition of the present invention can be used in the fields of agriculture, forestry, hygiene, etc.

[0116] Preferably, in the pesticide composition, the weight percentage of the active ingredient is 1-99%, such as 1%, 10%, 20%, 35%, 55%, 75%, 95% or 99%.

[0117] Preferably, the agrochemically acceptable carrier includes a surfactant.

[0118] In the present invention, the surfactant is an ionic surfactant or a non-ionic surfactant.

[0119] The surfactant includes an emulsifier, a dispersant or a wetting agent. The emulsifier can be polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene fatty amine, and commercially available emulsifiers (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, ning emulsion 36#, etc.). The dispersant includes sodium lignosulfonate, Nekal, calcium lignosulfonate, methylnaphthalenesulfonic acid formaldehyde condensate, etc. The wetting agent includes sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkylnaphthalenesulfonate, etc.

[0120] Preferably, the agrochemically acceptable carrier includes a solid carrier and / or a liquid carrier.

[0121] Preferably, the solid carrier includes natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicate such as talc; magnesium aluminum silicate such as kaolinite, kaolin, montmorillonite and mica; silica white, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylenediamine. The liquid carrier includes water and organic solvents. When water is used as a solvent or diluent, the organic solvent can also be used as an adjuvant or an antifreeze additive. Suitable organic solvents include aromatic hydrocarbons such as xylene, toluene, etc.; chlorinated hydrocarbons, such as chlorobenzene, vinyl chloride, chloroform, dichloromethane, etc.; aliphatic hydrocarbons, such as petroleum fractions, cyclohexane, light mineral oil; alcohols, such as isopropyl alcohol, butanol, ethylene glycol, glycerol and cyclohexanol, etc.; and their ethers and esters; and ketones, such as acetone, cyclohexanone, and dimethylformamide and N-methylpyrrolidone.

[0122] In the preparation process of the pesticide composition, the active component can be mixed with the liquid carrier and / or the solid carrier, and at the same time, a surfactant (such as an emulsifier, a dispersant, a stabilizer, a wetting agent) can be added, and other auxiliaries (such as a binder, an antifoaming agent, an oxidant, etc.) can also be added.

[0123] On the other hand, the present invention provides a method for controlling pests, which method comprises applying an effective dose of the above-mentioned oxazole diamide compound or insecticide composition to the pests to be controlled or the medium on which they grow.

[0124] Preferably, the effective dose is 7.5 - 1000 g per hectare, such as 7.5 g, 50 g, 100 g, 180 g, 250 g, 350 g, 450 g, 600 g, 800 g or 1000 g; more preferably, the effective dose is 15 - 600 g per hectare.

[0125] The composition of the present invention can be applied to pests or their growth medium in the form of a preparation. When the general formula compound I is used as an active ingredient and dissolved or dispersed in a carrier or formulated into a preparation for easier dispersion as an insecticide. For example: these chemical preparations can be formulated into various liquid agents, emulsifiable concentrates, suspension concentrates, aqueous suspension concentrates, microemulsions, emulsions, aqueous emulsions, powders, wettable powders, soluble powders, granules, water-dispersible granules or capsules.

[0126] For certain applications, such as in agriculture, one or more other insecticides, fungicides, herbicides, plant growth regulators or fertilizers, etc. can be added to the insecticidal composition of the present invention, whereby additional advantages and effects can be produced.

[0127] Compared with the prior art, the present invention has the following beneficial effects:

[0128] The oxazole diamide compound of the present invention has a significant effect on controlling pests, nematodes in the fields of agriculture and forestry, and pests in the sanitary field. It can take effect faster at a low concentration of 2 ppm: it can exhibit good insecticidal activity one day after application and reach >90% insecticidal activity within 3 days, thereby reducing the harm caused by excessive drug concentration to plants, the environment and humans, and also resulting in less drug residue during application, which is more conducive to environmental protection and ecological civilization. Detailed Embodiments

[0129] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations of the present invention. Unless otherwise specified, when the nuclear magnetic resonance hydrogen spectrum test and characterization of the compound are carried out in the embodiments and the present invention, the corresponding samples are all dissolved in deuterated dimethyl sulfoxide (DMSO-d6), and the hydrogen spectrum data are obtained by using a 400 MHz nuclear magnetic resonance spectrometer. The chemical shift unit is ppm (i.e., δ: ppm); the eluent for column chromatography purification is configured according to the volume ratio of the indicated petroleum ether (abbreviation: PE): ethyl acetate (abbreviation: EA).

[0130] Synthesis Examples

[0131] Synthesis Example 1

[0132] Preparation of 6-(N-(cyclopropylmethyl)benzamide)-N-(2,6-dibromo-4-(2,2,2-trifluoropropan-2-yl)phenyl)-5-(1H-1,2,4-triazol-1-yl)benzamide (Compound 1):

[0133] (1) Synthesis of N-(2,6-dibromo-4-(2,2,2-trifluoropropan-2-yl)phenyl)-4-fluoro-3-nitrobenzamide

[0134]

[0135] 4-Fluoro-3-nitrobenzoic acid (10.00 g, 54.00 mmol), toluene (50 mL), and thionyl chloride (12.85 g, 108.01 mmol) were successively added to a reaction flask, and the mixture was stirred under reflux for 2 h and then concentrated under reduced pressure to obtain 4-fluoro-3-nitrobenzoyl chloride. The above acyl chloride was added to 2,6-dibromo-4-(2,2,2-trifluoropropan-2-yl)aniline (9.59 g, 22.89 mmol), potassium iodide (1.53 g, 9.20 mmol), and acetonitrile (50 mL). After heating to 80 °C and reacting for 3 h, the reaction solution was cooled to room temperature, 200 mL of ethyl acetate and 100 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, filtered, and then concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 3:1) to obtain the target product (8.40 g, yield 63%).

[0136] (2) Synthesis of N-(2,6-dibromo-4-(2,2,2-trifluoropropan-2-yl)phenyl)-3-nitro-4-(1H-1,2,4-triazol-1-yl)benzamide

[0137]

[0138] N-(2,6-dibromo-4-(2,2,2-trifluoropropan-2-yl)phenyl)-4-fluoro-3-nitrobenzamide (8.40 g, 14.38 mmol) and N,N-dimethylformamide (60 mL) were successively added to a reaction flask. Sodium hydride (1.32 g, 33.07 mmol) and 1,2,4-triazole (1.19 g, 17.26 mmol) were successively added under an ice bath, and the mixture was then reacted at room temperature for 3 h. 100 mL of water and 200 mL of ethyl acetate were added to the reaction solution, and the mixture was extracted and separated. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and then concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 1:1) to obtain the target product (8.40 g, yield 93%).

[0139] (3) Synthesis of N-(2,6-dibromo-4-(2,2,2-trifluoropropyl)phenyl)-3-amino-4-(1H-1,2,4-triazol-1-yl)benzamide

[0140]

[0141] To the reaction flask, add N-(2,6-dibromo-4-(2,2,2-trifluoropropyl)phenyl)-3-nitro-4-(1H-1,2,4-triazol-1-yl)benzamide (8.40 g, 13.27 mmol), tetrahydrofuran (100 mL), water (10 mL), acetic acid (4.30 g, 71.67 mmol), and reduced iron powder (2.97 g, 53.09 mmol) in sequence. Stir and react under reflux conditions for 2 h. Cool the reaction solution to room temperature, filter it through diatomaceous earth, and then rotary evaporate the filtrate. Add 200 mL of ethyl acetate and 100 mL of water, extract and separate the layers. Wash the organic layer with saturated brine, dry it over anhydrous sodium sulfate, filter it, and then concentrate it under reduced pressure. The residue is purified by column chromatography (PE:EA = 1:1) to obtain the target product (3.00 g, yield 38%).

[0142] (4) Synthesis of N-(cyclopropylmethyl)amino-N-(2,6-dibromo-4-(2,2,2-trifluoropropyl)phenyl)-4-(1H-1,2,4-triazol-1-yl)benzamide

[0143]

[0144] To the reaction flask, add N-(2,6-dibromo-4-(2,2,2-trifluoropropyl)phenyl)-3-amino-4-(1H-1,2,4-triazol-1-yl)benzamide (3.00 g, 4.51 mmol), chloroform (40 mL), cyclopropanecarbaldehyde (0.50 g, 7.50 mmol), and acetic acid (5.00 g, 0.30 mmol) in sequence. After reacting at 80 °C for 1 h, add sodium triacetoxyborohydride (2.10 g, 9.91 mmol) and continue to react for 3 h. Cool the reaction solution to room temperature, adjust the reaction solution to pH 8 with saturated sodium bicarbonate aqueous solution, add 200 mL of dichloromethane and 100 mL of water, extract and separate the layers. Wash the organic layer with saturated brine, dry it over anhydrous sodium sulfate, filter it, and then concentrate it under reduced pressure. The residue is purified by column chromatography (PE:EA = 1:1) to obtain the target product (2.20 g, yield 67%).

[0145] (5) Synthesis of 6-(N-(cyclopropylmethyl)benzamido)-N-(2,6-dibromo-4-(2,2,2-trifluoropropyl)phenyl)-5-(1H-1,2,4-triazol-1-yl)benzamide (Compound 1)

[0146]

[0147] In a solution of 6-(cyclopropylmethyl)amino-N-(2,6-dibromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl)-5-(1H-1,2,4-triazol-1-yl)benzamide (180.00 mg, 0.27 mmol) in tetrahydrofuran (5 mL), triethylamine (55.0 mg, 0.54 mmol) and benzoyl chloride (46.00 mg, 0.32 mmol) were successively added. After reacting at room temperature for 3 hours, 10 mL of water and 50 mL of ethyl acetate were added respectively. After extraction and liquid separation, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and then concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 1:1) to obtain the target product (138.00 mg, yield 66%).

[0148] of Compound 1 1 H NMR: δ 9.32 (s, 1H), 8.43 (s, 1H), 8.14 (s, 2H), 7.96 - 7.93 (m, 2H), 7.82 (s, 1H), 7.63 (t, J = 7.2 Hz, 1H), 7.52 - 7.48 (m, 3H), 7.45 - 7.42 (m, 1H), 3.09 - 3.00 (m, 2H), 1.09 - 1.03 (m, 1H), 0.54 - 0.48 (m, 2H), 0.29 - 0.24 (m, 2H).

[0149] Synthesis Example 2

[0150] Synthesis of N-(cyclopropylmethyl)-N-(5-(2,6-dibromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl)carbamoyl)-2-(1H-1,2,4-triazol-1-yl)phenyl)-6-trifluoromethylnicotinamide (Compound 169)

[0151]

[0152] In a solution of 3-(cyclopropylmethyl)amino-N-(2,6-dibromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl)-4-(1H-1,2,4-triazol-1-yl) (200.00 mg, 0.30 mmol) in tetrahydrofuran (5 mL), N,N-diisopropylethylamine (77.55 mg, 0.60 mmol) and 4-trifluoromethylnicotinoyl chloride (69.15 mg, 0.33 mmol) were successively added. After reacting at room temperature for 3 hours, 10 mL of water and 50 mL of ethyl acetate were added respectively. After extraction and liquid separation, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and then concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 2:1) to obtain the target product (40.00 mg, yield 16%).

[0153] Of Compound 169 1 H NMR: δ 10.78 (s, 1H), 8.97 (s, 1H), 8.62 (s, 1H), 8.40 (s, 1H), 8.22 (s, 1H), 8.08 (s, 3H), 7.91 (d, J = 8.0 Hz, 1H), 7.82 (t, J = 9.2 Hz, 2H), 4.05 (dd, J = 14.0, 6.8 Hz, 1H), 2.89 (dd, J = 14.0, 7.6 Hz, 1H), 1.05 - 0.98 (m, 1H), 0.42 - 0.38 (m, 2H), 0.20 - 0.05 (m, 2H).

[0154] Synthesis Example 3

[0155] N-(Cyclopropylmethyl)-N-(5-(2,6-dibromo-4-(2,2,2-trifluoro-1-(trifluoromethyl)ethyl)phenyl)carbamoyl)-2-(1H-1,2,4-triazol-1-yl)phenyl)-2-fluoro-4-cyanobenzamide (Compound 85)

[0156]

[0157] To a solution of 3-(cyclopropylmethyl)amino-N-(2,6-dibromo-4-(2,2,2-trifluoro-1-(trifluoromethyl)ethyl)phenyl)-4-(1H-1,2,4-triazol-1-yl)benzamide (202.00 mg, 0.31 mmol) in tetrahydrofuran (5 mL) were successively added N,N-diisopropylethylamine (77.55 mg, 0.60 mmol) and 2-fluoro-4-cyanobenzoyl chloride (60.39 mg, 0.33 mmol). The reaction was carried out at room temperature for 4 hours. 10 mL of water and 50 mL of ethyl acetate were added respectively, and the mixture was extracted and separated. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 2:1) to obtain the target product (90.00 mg, yield 37%).

[0158] Of Compound 85 1 H NMR: δ 10.79 (s, 1H), 8.98 (s, 1H), 8.42 (s, 1H), 8.11 (s, 1H), 8.09 (s, 3H), 7.81 (d, J = 8.4 Hz, 2H), 7.55 (dd, J = 8.0, 1.2 Hz, 1H), 7.32 - 7.27 (m, 1H), 4.08 (dd, J = 14.0, 7.2 Hz, 1H), 2.91 - 2.85 (m, 1H), 1.07 - 1.01 (m, 1H), 0.46 - 0.42 (m, 2H), 0.23 - 0.18 (m, 1H), 0.11 - 0.07 (m, 1H).

[0159] Synthesis Example 4

[0160] Preparation of 3-(N-(cyclopropylmethyl)benzamide)-N-(2,6-dibromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl)-4-(3-(trifluoromethyl)-1H-pyrazol-1-yl)benzamide (Compound 3):

[0161]

[0162] To a toluene (5 mL) solution of 3-(cyclopropylmethyl)amino-N-(2,6-dibromo-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl)-4-(3-(trifluoromethyl)-1H-pyrazol-1-yl)benzamide (201.00 mg, 0.27 mmol), N,N-diisopropylethylamine (41.75 mg, 0.30 mmol) and benzoyl chloride (69.80 mg, 0.54 mmol) were added successively. After reacting at 130 °C for 5 h, the reaction solution was cooled to room temperature. 10 mL of water and 50 mL of ethyl acetate were added respectively, and after extraction and liquid separation, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and then concentrated under reduced pressure. The residue was purified by column chromatography (PE:EA = 3:1) to obtain the target product (180.00 mg, yield 81%).

[0163] For Compound 3 1 1H NMR: δ 10.79 (s, 1H), 8.25 - 7.92 (m, 5H), 7.52 - 7.00 (m, 6H), 4.14 - 3.97 (m, 1H), 3.08 - 2.97 (m, 1H), 0.94 - 0.92 (m, 1H), 0.45 - 0.28 (m, 2H), 0.28 - 0.10 (m, 2H).

[0164] Other compounds in Table 1 were prepared by referring to the similar methods in Synthesis Examples 1 - 4. The following Table 2 describes the NMR data obtained from testing them.

[0165] Table 2

[0166]

[0167]

[0168] Other general formula I compounds of the present invention can be synthesized by referring to the above method.

[0169] Formulation Example 1

[0170] In this example, the preparation of a preparation using Compound 169 of the present invention as a representative compound is as follows:

[0171] Mix 30 parts by weight of Compound 169 of the present invention, 15 parts by weight of polyoxyethylene styrenyl phenyl ether, 10 parts by weight of phosphorous acid, and 45 parts by weight of xylene uniformly to obtain an emulsifiable concentrate with a concentration of 30% of Compound 169 of the present invention.

[0172] Formulation Example 2

[0173] In this example, preparations were prepared using Compound 169 of the present invention as a representative compound, as follows:

[0174] Stir and mix 20 parts by weight of Compound 169 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-naphthalene sulfonic acid formaldehyde condensate, and 75 parts by weight of diatomaceous earth uniformly to obtain a wettable powder of 20% of Compound 169 of the present invention.

[0175] Formulation Example 3

[0176] In this example, preparations were prepared using Compound 169 of the present invention as a representative compound, as follows:

[0177] Mix 30 parts by weight of Compound 169 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 make up the water to 100 parts by weight to obtain a 30% suspension concentrate of Compound 169 of the present invention.

[0178] Biological Activity Test Example

[0179] The obtained Compound of the present invention was used to test various pests. Unless otherwise specified in the biological activity test examples and the present invention: The sample preparation method was to weigh 10 mg of the technical sample to be tested, dissolve it with 1 mL of DMF, prepare a 10000 ppm stock solution, and dilute the stock solution to the required concentration with 0.05% Tween-80 water for activity testing. The mortality rate was the mortality rate that caused pests to die at the test concentration of the compound, and the calculation formula was mortality rate (%) = number of dead insects / total number of insects * 100.

[0180] Biological Activity Test Example 1 Insecticidal activity of the compound against Plutella xylostella

[0181] The activity test was carried out by the leaf disc feeding method. Immerse the cabbage leaf discs in the liquid medicine for 10 s, air dry and place them in a petri dish, 4 discs per dish, and place filter paper in the petri dish to keep moist. Release 10 test insects of Plutella xylostella per dish, with 3 replicates. Place them in a light incubator at a temperature of 25 °C, with a light cycle of 14 hL:10 hD for cultivation. Investigate the number of dead insects of Plutella xylostella 1, 2, and 3 days after treatment, and calculate the mortality rate.

[0182] The test results are as follows:

[0183] Compounds such as 757, 85, 169, 800, 967, 719, 803, 761, 177, 257, and 1225 had a mortality rate of ≥90% against Plutella xylostella 5 days after treatment at a concentration of 200 ppm.

[0184] Compounds 761 and 169 had a mortality rate of ≥90% against Plutella xylostella 3 days after treatment at a concentration of 20 ppm.

[0185] Compound 169 had a mortality rate of ≥90% against Plutella xylostella 3 days after treatment at a concentration of 1 ppm.

[0186] According to the above method, some compounds of the present invention were selected for parallel determination of the insecticidal activity against Plutella xylostella and comparison of the quick-acting property with KC1 and KC2. The test results are shown in Table 3.

[0187] Table 3 Comparison of the insecticidal activity and quick-acting property of the compounds of the present invention with KC1 and KC2 against Plutella xylostella

[0188]

[0189] As can be seen from Table 3, compared with the existing compounds, the compounds of the present invention not only had better quick-acting property but also higher insecticidal activity at a low dose of 2 ppm.

[0190] Biological Activity Test Example 2 Insecticidal activity of the compounds against Mythimna separata

[0191] The activity test was carried out by the method of immersing corn seedlings for feeding. Cut the above-ground part of the fresh corn seedlings grown indoors, about 10 cm long, for standby. Immerse the corn seedlings in the liquid medicine for 10 s, dry them in the shade, then cut them into leaf segments of 3 - 5 cm and place them in a petri dish, with 3 leaf segments in each dish. Put 10 third-instar larvae of Mythimna separata in each dish, and repeat 3 times. Place them in a light incubator at a temperature of 25°C, with a light cycle of 14 hL:10 hD for cultivation. Investigate the number of dead insects 1, 2, and 3 days after treatment and calculate the mortality rate.

[0192] Compounds 803, 761, 169, etc. of the present invention had a mortality rate of ≥80% against Mythimna separata 3 days after treatment at a concentration of 20 ppm.

[0193] According to the above method, some compounds of the present invention were selected for parallel determination of the insecticidal activity against Mythimna separata with KC1 and KC2. The test results are shown in Table 4.

[0194] Table 4 Comparison of the insecticidal activity of the compounds of the present invention with KC1 and KC2 against Mythimna separata

[0195]

[0196]

[0197] As can be seen from Table 4, compared with the existing compounds, the compounds of the present invention not only have better quick-acting properties but also more efficient insecticidal activities at a low dose of 2 ppm.

[0198] The present invention illustrates the azole bisamide compounds of the present invention and their preparation methods and applications through the above embodiments. However, the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent substitution of each raw material of the products of the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A compound containing oxazolidinedione amide, characterized in that, The azole-containing bisamide compound has the structure shown in Formula I below: In Formula I, Q is selected from one of the following Q1, Q2, Q3 or Q4: 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; or Z2 and Z3 are linked to form a substituted five-membered heterocycle; R is selected from hydrogen or trifluoromethyl; A is selected from CH or N; X1 is selected from fluorine, chlorine, bromine or iodine; X2 is selected from fluorine, chlorine, bromine, iodine, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl; W is selected from an oxygen atom or a sulfur atom.

2. The bisoxazoline carboxamide compound according to claim 1, wherein In Formula I, 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, trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, heptafluoro-isopropyl, difluoromethoxy, trifluoromethoxy, pentafluoroethoxy, methylthio, ethylthio, n-propylthio, isopropylthio, methylsulfinyl, trifluoromethylsulfinyl, methylsulfonyl or trifluoromethylsulfonyl; or Z2 and Z3 are linked to form a substituted five-membered heterocycle; R is selected from hydrogen or trifluoromethyl; A is selected from CH or N; X1 is selected from chlorine, bromine or iodine; X2 is selected from chlorine, bromine, iodine, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C 1- C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl; W is selected from an oxygen atom or a sulfur atom.

3. The bisoxazoline amide compound according to claim 1-2, characterized in that, 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, methylthio, ethylthio, n-propylthio, isopropylthio, methylsulfonyl or trifluoromethylsulfonyl; or Z2 and Z3 are linked to form a substituted five-membered heterocycle; R is selected from hydrogen or trifluoromethyl; A is selected from CH or N; X1 is selected from chlorine, bromine or iodine; X2 is selected from chlorine, bromine, iodine, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 haloalkylthio, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C1-C4 alkylsulfonyl or C1-C4 haloalkylsulfonyl; W is selected from an oxygen atom or a sulfur atom.

4. The benzoxaborole compound according to any one of claims 1-3, wherein The azole-containing bisamide compound is any one selected from the following compounds:

5. The tautomer, enantiomer, diastereomer or salt thereof of the oxazole dicarboxamide compound according to any one of claims 1-4.

6. The use of the oxazole dicarboxamide compound according to any one of claims 1-4 or the tautomer, enantiomer, diastereomer or salt thereof of the oxazole dicarboxamide compound according to claim 5 in controlling plant pests.

7. An insecticide composition, characterized in that, The pesticide composition comprises an active ingredient and a pesticidally acceptable carrier, and the active ingredient is the oxazole dicarboxamide compound according to any one of claims 1-4 or the tautomer, enantiomer, diastereomer or salt thereof of the oxazole dicarboxamide compound according to claim 5.

8. The pesticidal composition according to claim 7, wherein The weight percentage content of the active ingredient in the pesticide composition is 1-99%.

9. A method for controlling pests, characterized in that, The method is: applying an effective dose of the oxazole dicarboxamide compound according to any one of claims 1-4 or the tautomer, enantiomer, diastereomer or salt thereof of the oxazole dicarboxamide compound according to claim 5 or the pesticide composition according to claim 7 or 8 to the pest to be controlled or the medium on which it grows; Preferably, the effective dose is 7.5-1000 g per hectare; more preferably, the effective dose is 15-600 g per hectare.

Images