Pyrazole compounds or salts thereof, pesticide compositions and herbicides

Abstract

The present invention provides a pyrazole compound that has herbicidal activity capable of controlling various important weeds that occur in fields, orchards, paddy fields, non-agricultural land, etc., even under conditions of water fluctuations, and that has high safety for agricultural crops such as rice, as well as an agricultural chemical composition and herbicide containing the same. Formulas [A-1], [A-2] and [A-3] A pyrazole compound represented by any of TIFF0007905560000028.tif44166 or a salt thereof, a pesticide composition containing the same as an active ingredient, and a herbicide.

Description

[Technical Field]

[0001] The present invention relates to a novel pyrazole compound or a salt thereof, a pesticide composition containing said compound or salt thereof as an active ingredient, and a herbicide. [Background technology]

[0002] Conventionally, pyrazole compounds having herbicidal activity, such as those described in Patent Document 1 or 2, are known. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 1994 / 08999 [Patent Document 2] International Publication No. 1998 / 03506 [Overview of the project] [Problems that the invention aims to solve]

[0004] Numerous herbicides have been developed for crop cultivation, playing a crucial role in improving crop productivity. For example, 1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)-5-[methyl(propa-2-inyl)amino]pyrazole-4-carbonitrile (generic name: pyraclonil), a pyrazole compound described in Example 4.73 of Patent Document 1, is effective in controlling a wide range of weeds. However, in environments with fluctuating water levels, the control effect of conventional herbicides against important weeds is not always sufficient.

[0005] In recent years, climate change caused by global warming has had a significant impact on crop cultivation. For example, extreme weather events have led to large fluctuations in rainfall, resulting in heavy rains and floods, which frequently cause water fluctuations in crop cultivation. When water fluctuations occur in crop cultivation, sprayed pesticides are washed away, reducing their concentration and weakening their effectiveness, leading to a decrease in crop yield and quality. Therefore, there is a need for pesticides that can maintain sufficient effectiveness even in environments with fluctuating water levels.

[0006] Furthermore, the long-lasting effect of the pesticide (residual effect) is important from the perspective of reducing labor in agricultural work, decreasing the number of times pesticides are sprayed, and lowering costs.

[0007] Furthermore, a low impact of the pesticide on crop growth and yield (crop safety) is considered an essential performance characteristic. In addition, crop safety at higher doses than those intended is also required. For example, during pesticide application, strong winds may prevent uniform application, resulting in localized high concentrations, or errors in dilution ratios may lead to high pesticide concentrations, potentially causing phytotoxicity. This phytotoxicity can suppress crop growth and reduce yield. Therefore, pesticides that offer high crop safety even at doses higher than those intended are required.

[0008] Furthermore, the above-mentioned Patent Documents 1 and 2 do not disclose any pyrazole compounds represented by any of the formulas [A-1], [A-2], and [A-3] described later, nor any salts thereof.

[0009] The present invention has been made in view of the above circumstances, and its objective is to provide a pyrazole compound that has herbicidal activity capable of controlling various important weeds that occur in fields, orchards, paddy fields, non-agricultural land, etc., even under conditions of water fluctuations, and that has high safety for agricultural crops such as rice, as well as an agricultural chemical composition and herbicide containing the same. [Means for solving the problem]

[0010] To achieve the above objectives, the inventors synthesized pyrazole compounds and diligently investigated their herbicidal activity and usefulness. As a result, they found that a pyrazole compound represented by any of the following formulas [A-1], [A-2], and [A-3] (hereinafter referred to as "the compound of the present invention," "the pyrazole compound of the present invention," or "the compound of the present invention [A-1]," etc.) has remarkable herbicidal activity that controls various weeds over a long period of time even under water fluctuation conditions, and also has high crop safety for agricultural crops such as rice. Further research led to the completion of the present invention.

[0011] In other words, the present invention has the following characteristics: (1) A pyrazole compound represented by any one of formulas [A-1], [A-2], and [A-3], or a salt thereof. TIFF0007905560000001.tif44166(2) A pesticide composition containing the pyrazole compound or a salt thereof described in (1) above as an active ingredient. (3) The pesticide composition according to (2) further containing a surfactant. (4) A herbicide containing the pyrazole compound described in (1) above or a salt thereof as an active ingredient. (5) The herbicide described in (4) further containing a surfactant. (6) The herbicide described in (4) or (5) above, which has herbicidal activity against weeds that occur in fields, paddy fields, orchards, lawns, non-agricultural land, greenhouses, seedling facilities, or plant factories where useful plants for agricultural, horticultural, or industrial purposes are cultivated. (7) The herbicide according to (6) above, wherein the useful plant is a plant that has been transformed in cultivation by breeding methods or genetic modification technology. (8) A method for controlling weeds using the amount of the active ingredient of the pyrazole compound or salt thereof described in (1) above. (9) A method for controlling weeds, comprising applying the pesticide composition described in (2) or (3) above to useful plants having agricultural, horticultural, or industrial uses, or to the place where such useful plants are intended to grow or are growing, simultaneously or in stages. (10) A method for controlling weeds, comprising applying the herbicide described in any of (4) to (7) above to useful plants having agricultural, horticultural, or industrial uses, or to the place where such useful plants are intended to grow or are growing, simultaneously or in stages. (11) The method for controlling weeds as described in (9), wherein the pesticide composition is applied in a paddy field, field, lawn, orchard, non-agricultural land, greenhouse, seedling facility, or plant factory. (12) The weed control method described in (10) above, wherein the herbicide is applied in a paddy field, field, lawn, orchard, non-agricultural land, greenhouse, seedling facility, or plant factory. (13) A method of using a herbicide, wherein the herbicide described in any of (4) to (7) above is used to control weeds on useful plants that have agricultural, horticultural, or industrial uses.

[0012] (14) A crystal of a pyrazole compound represented by formula [A-1], wherein the crystal has diffraction peaks at least 2θ = 8.8°±0.2°, 12.0°±0.2°, 19.0°±0.2°, 24.0°±0.2°, 25.0°±0.2° and 26.8°±0.2° in powder X-ray diffraction. TIFF0007905560000002.tif44145(15) A pesticide composition containing the crystal described in (14) above as an active ingredient. (16) A herbicide containing the crystal described in (14) above as an active ingredient. (17) A method for controlling weeds using a pesticide composition containing the crystals described in (14) above. (18) Use of the crystals described in (14) above as a herbicide. (19) A crystal of a pyrazole compound represented by formula [A-2], wherein the crystal has diffraction peaks at least 2θ = 8.3°±0.2°, 12.0°±0.2°, 12.9°±0.2°, 15.5°±0.2°, 21.8°±0.2°, 23.1°±0.2°, 24.4°±0.2° and 26.3°±0.2° in powder X-ray diffraction. TIFF0007905560000003.tif44148(20) A pesticide composition containing the crystal described in (19) above as an active ingredient. (21) A herbicide containing the crystal described in (19) above as an active ingredient. (22) A method for controlling weeds using a pesticide composition containing the crystals described in (19) above. (23) Use of the crystals described in (19) above as a herbicide. (24) A crystal of a pyrazole compound represented by formula [A-3], wherein the crystal has diffraction peaks at least 2θ = 7.8°±0.2°, 10.5°±0.2°, 12.7°±0.2°, 16.8°±0.2°, 17.1°±0.2°, 18.7°±0.2°, 21.9°±0.2°, 23.6°±0.2° and 28.0°±0.2° in powder X-ray diffraction. TIFF0007905560000004.tif44135(25) A pesticide composition containing the crystal described in (24) above as an active ingredient. (26) A herbicide containing the crystal described in (24) above as an active ingredient. (27) A method for controlling weeds using a pesticide composition containing the crystals described in (24) above. (28) Use of the crystals described in (24) above as a herbicide. [Effects of the Invention]

[0013] The pyrazole compounds represented by any one of formulas [A-1], [A-2], and [A-3] of the present invention, or their salts, can control various weeds that occur in fields, paddy fields, orchards, non-agricultural land, etc. They have remarkable herbicidal activity that controls various weeds over a long period of time even under conditions of water fluctuations, and have high crop safety for agricultural crops such as rice, and have excellent efficacy as pesticides.

[0014] Furthermore, the pesticide composition and herbicide of the present invention contain any of the compounds [A-1], [A-2], and [A-3] of the present invention, or a salt thereof, as an active ingredient. The pesticide composition and herbicide of the present invention have excellent herbicidal efficacy and exhibit excellent selectivity between useful plants and weeds, making them useful as pesticide compositions, especially as herbicides, in agricultural land. That is, the pyrazole compounds or salts thereof of the present invention have herbicidal efficacy against various weeds in foliar treatment, soil treatment, seed coating treatment, soil mixing treatment, pre-sowing soil treatment, simultaneous sowing treatment, post-sowing soil treatment, simultaneous sowing and covering soil mixing treatment, etc., in cultivated fields or non-agricultural land where useful plants are grown. [Brief explanation of the drawing]

[0015] [Figure 1] This is the powder X-ray diffraction pattern of compound [A-1] of the present invention. [Figure 2] This is a spectral diagram of the compound [A-1] of the present invention obtained by Fourier transform infrared spectroscopy (FT-IR, total internal reflection). [Figure 3] This is a chart of differential scanning calorimetry (DSC measurement) of compound [A-1] of the present invention. [Figure 4] This is the powder X-ray diffraction pattern of compound [A-2] of the present invention. [Figure 5] This is a spectral diagram of the compound [A-2] of the present invention obtained by Fourier transform infrared spectroscopy (FT-IR, total internal reflection measurement). [Figure 6] This is a chart of differential scanning calorimetry (DSC measurement) of compound [A-2] of the present invention. [Figure 7] This is the powder X-ray diffraction pattern of compound [A-3] of the present invention. [Figure 8] This is a spectral diagram of the compound [A-3] of the present invention obtained by Fourier transform infrared spectroscopy (FT-IR, total internal reflection measurement). [Figure 9] This is a chart of differential scanning calorimetry (DSC measurement) results for compound [A-3] of the present invention. [Modes for carrying out the invention]

[0016] This document explains the terms used in this specification. In the present invention, "the salt" refers to a salt composed of any of the compounds [A-1], [A-2], and [A-3] of the present invention with a metal or an organic base, or a salt composed of a mineral acid or an organic acid. Examples of metals include alkali metals such as sodium or potassium, or alkaline earth metals such as magnesium or calcium. Examples of organic bases include triethylamine or diisopropylamine. Examples of mineral acids include phosphoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, boric acid, or sulfuric acid. Examples of organic acids include formic acid, acetic acid, lactic acid, ascorbic acid, succinic acid, fumaric acid, maleic acid, oxalic acid, citric acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, 4-toluenesulfonic acid, or trifluoromethanesulfonic acid.

[0017] When the pyrazole compound or salt thereof of the present invention is used in solid form, it may be crystalline or amorphous. Examples of crystals of compound [A-1] of the present invention include crystals having diffraction peaks at least at 2θ = 8.8°±0.2°, 12.0°±0.2°, 19.0°±0.2°, 24.0°±0.2°, 25.0°±0.2° and 26.8°±0.2° in powder X-ray diffraction, but other crystalline polymorphs are also acceptable. Examples of crystals of compound [A-2] of the present invention include crystals having diffraction peaks at least at 2θ = 8.3°±0.2°, 12.0°±0.2°, 12.9°±0.2°, 15.5°±0.2°, 21.8°±0.2°, 23.1°±0.2°, 24.4°±0.2° and 26.3°±0.2° in powder X-ray diffraction, but other crystalline polymorphs are also acceptable. Examples of crystals of compound [A-3] of the present invention include crystals having diffraction peaks at least at 2θ = 7.8°±0.2°, 10.5°±0.2°, 12.7°±0.2°, 16.8°±0.2°, 17.1°±0.2°, 18.7°±0.2°, 21.9°±0.2°, 23.6°±0.2°, and 28.0°±0.2° in powder X-ray diffraction, but other crystalline polymorphs are also acceptable.

[0018] The above powder X-ray diffraction was measured at room temperature using Rigaku SmartLab (tube target: Cu, tube voltage: 40 kV, tube current: 45 mA, 2θ step width: 0.010°, average wavelength: 1.5418 Å). The light source used was Cu-Kα ray, and the measurement was carried out by the transmission method.

[0019] As the crystal of the compound [A-1] of the present invention, in Fourier transform infrared spectroscopy (FT-IR, total reflection measurement method), the wave numbers are 3313 cm -1 , 2208 cm -1 , 1583 cm -1 , 1559 cm -1 , 1526 cm -1 , 1451 cm -1 , 1336 cm -1 , 944 cm -1 , 880 cm -1 , 691 cm -1 , 622 cm -1 and 512 cm -1 crystals having peaks at the positions of are mentioned, but other crystal polymorphs may also be used. Also, typical specific peaks are not limited to these. As the error of the wave number indicating the peak of Fourier transform infrared spectroscopy, usually ±2, and in some cases ±1 can be taken. Therefore, the wave numbers indicating the peaks of the above crystals considering the error are 3313 ± 2 cm -1 , 2208 ± 2 cm -1 , 1583 ± 2 cm -1 , 1559 ± 2 cm -1 , 1526 ± 2 cm -1 , 1451 ± 2 cm -1 , 1336 ± 2 cm -1 , 944 ± 2 cm -1 , 880 ± 2 cm -1 , 691 ± 2 cm -1 , 622 ± 2 cm -1 and 512 ± 2 cm -1 .

[0020] As the crystal of the compound [A-2] of the present invention, in Fourier transform infrared spectroscopy (FT-IR, total reflection measurement method), the wave numbers are 3303 cm -1 , 2955 cm -1 , 2210 cm -1 , 1591 cm-1 , 1567cm -1 ,1556cm -1 , 1524cm -1 , 1342cm -1 , 966cm -1 , 946cm -1 , 692cm -1 and 475cm -1 Examples include crystals having a peak at this position, but other crystalline polymorphs are also acceptable. Furthermore, typical specific peaks are not limited to these. As mentioned above, the wavenumber error can usually be ±2, and in some cases ±1, so the wavenumber showing the peak of the above crystal, considering the error, is 3303 ± 2 cm⁻¹. -1 , 2955±2cm -1 , 2210±2cm -1 , 1591±2cm -1 , 1567±2cm -1 ,1556±2cm -1 , 1524±2cm -1 , 1342±2cm -1 , 966±2cm -1 , 946±2cm -1 , 692±2cm -1 and 475±2cm -1 That is the case.

[0021] As for the crystal of compound [A-3] of the present invention, in Fourier transform infrared spectroscopy (FT-IR, total internal reflection measurement), the wavenumber is 3280 cm⁻¹. -1 , 2951cm -1 , 2207cm -1 , 1590cm -1 , 1559cm -1 , 1521cm -1 , 1340cm -1 , 1175cm -1 , 942cm -1 , 852cm -1 , 691cm -1 and 508cm -1Examples include crystals having a peak at this position, but other crystalline polymorphs may also be present. Furthermore, these are not the only typical specific peaks. As mentioned above, the wavenumber error can usually be ±2, and in some cases ±1, so the wavenumber showing the peak of the above crystal, taking the error into account, is 3280 ± 2 cm⁻¹. -1 , 2951±2cm -1 , 2207±2cm -1 , 1590±2cm -1 , 1559±2cm -1 , 1521±2cm -1 , 1340±2cm -1 , 1175±2cm -1 , 942±2cm -1 , 852±2cm -1 , 691±2cm -1 and 508±2cm -1 That is the case.

[0022] The above Fourier transform infrared spectroscopy analysis was performed using a JASCO FT-IR-4700typeA (measurement method: Attenuated Total Reflection, number of integrations: 64, resolution: 2cm). -1 ) was used for measurement.

[0023] Examples of the crystal of compound [A-1] of the present invention include crystals with a melting point of 154.9°C as measured by differential scanning calorimetry (DSC measurement), but other crystalline polymorphs are also acceptable. Examples of the crystal of compound [A-2] of the present invention include crystals with a melting point of 126.9°C as measured by differential scanning calorimetry (DSC measurement), but other crystalline polymorphs are also acceptable. Examples of the crystal of compound [A-3] of the present invention include crystals with a melting point of 136.6°C as measured by differential scanning calorimetry (DSC measurement), but other crystalline polymorphs are also acceptable.

[0024] The differential scanning calorimetry described above was performed using a NETZSCH Japan DSC3500 Sirius (heating: 20-(10℃ / min)-250℃, atmosphere: nitrogen, control: empty container, container: aluminum, sampling: 300pts / min).

[0025] The pesticide composition and herbicide of the present invention may, if necessary, contain additive components commonly used in pesticide formulations.

[0026] [Additional ingredients] Examples of these additives include carriers such as solid or liquid carriers, surfactants, binders, tackifiers, thickeners, colorants, spreading agents, adhesives, antifreeze agents, anticaking agents, disintegrants, and decomposition inhibitors. In addition, preservatives and plant fragments may be used as additives as needed. Furthermore, one of these additives may be used, or two or more may be used in combination.

[0027] The above-mentioned additives are described in detail below.

[0028] Examples of solid carriers include mineral carriers such as pyrophyllite clay, kaolin clay, silica clay, talc, diatomaceous earth, zeolite, bentonite, acid clay, activated clay, attapargas clay, vermiculite, perlite, pumice, white carbon (synthetic silicic acid, synthetic silicates, etc.), and titanium dioxide; plant-based carriers such as wood flour, corn stalks, walnut shells, fruit kernels, rice husks, sawdust, bran, soybean flour, powdered cellulose, starch, dextrin, and sugars; inorganic salt carriers such as calcium carbonate, ammonium sulfate, sodium sulfate, and potassium chloride; and polymer carriers such as polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, and urea-aldehyde resin.

[0029] Examples of liquid carriers include monohydric alcohols such as methanol, ethanol, propanol, 2-propanol, butanol, and cyclohexanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, and glycerin; polyhydric alcohol derivatives such as propylene glycol ethers; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and isophorone; ethers such as ethyl ether, 1,4-dioxane, cellosolve, dipropyl ether, and tetrahydrofuran; aliphatic hydrocarbons such as n-paraffin, naphthene, isoparaffin, kerosene, and mineral oil; and toluene and C9-C Examples of materials include alkylnaphthalenes such as 10-alkylbenzene, xylene, solvent naphtha, and methylnaphthalene, and aromatic hydrocarbons such as high-boiling aromatic hydrocarbons; halogenated hydrocarbons such as 1,2-dichloroethane, chloroform, and carbon tetrachloride; esters such as ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, and dimethyl adipate; lactones such as γ-butyrolactone; amides such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; nitriles such as acetonitrile; sulfur compounds such as dimethyl sulfoxide; vegetable oils such as soybean oil, rapeseed oil, cottonseed oil, coconut oil, and castor oil, and lower alkyl esters of fatty acids derived from the aforementioned vegetable oils; and water.

[0030] Examples of surfactants include sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene resin acid esters, polyoxyethylene fatty acid diesters, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylaryl ethers such as polyoxyethylene alkylphenyl ethers, polyoxyethylene dialkylphenyl ethers, polyoxyethylene alkylphenyl ether formalin condensates, polyoxyethylene polyoxypropylene block polymers, alkylpolyoxyethylene polypropylene block polymer ethers, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene fatty acid bisphenyl ethers, polyalkylene benzylphenyl ethers, polyoxyalkylene styrylphenyl ethers, acetylenediol, polyoxyalkylene-added acetylenediol, polyoxyethylene ether-type silicones, ester-type silicones, and fluorine-based surfactants. Nonionic surfactants such as castor oil, polyoxyethylene hydrogenated castor oil; alkyl sulfates such as sodium salt of lauryl alcohol sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene styrylphenyl ether sulfate, polyoxyethylene styrene-phenyl ether sulfate, alkylbenzene sulfonates such as calcium alkylbenzene sulfonate, lignin sulfonates such as sodium lignin sulfonate, alkyl sulfosuccinates, naphthalene sulfonates, alkylnaphthalene sulfonates, salts of formalin condensates of naphthalene sulfonic acid such as sodium naphthalene sulfonate, salts of formalin condensates of alkylnaphthalene sulfonic acid, fatty acid salts, polycarboxylates such as sodium polycarboxylate, N-methyl fatty acid sarcosinate, resin salts, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkylphenyl ether phosphate, and other anionic surfactants;Cationic surfactants such as laurylamine hydrochloride, stearylamine hydrochloride, oleylamine hydrochloride, stearylamine acetate, stearylaminopropylamine acetate, alkyltrimethylammonium chloride, alkyldimethylbenzalkonium chloride, and other alkylamine salts; amphoteric surfactants such as betaine-type surfactants like dialkyldiaminoethylbetaine and alkyldimethylbenzylbetaine, and amino acid-type surfactants like dialkylaminoethylglycine and alkyldimethylbenzylglycine.

[0031] Examples of binders and tackifiers include carboxymethylcellulose and its salts, dextrin, water-soluble starch, xanthan gum, guar gum, sucrose, polyvinylpyrrolidone, acacia gum, polyvinyl alcohol, polyvinyl acetate, sodium polyacrylate, polyethylene glycol, polyethylene oxide, and natural phospholipids (e.g., cephalic acid, lecithin, etc.).

[0032] Examples of thickening agents include water-soluble polymers such as xanthan gum, guar gum, carboxymethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymers, acrylic polymers, starch derivatives, and polysaccharides; inorganic fine powders such as high-purity bentonite and white carbon; and organic fine powders such as organic bentonite.

[0033] Examples of colorants include inorganic pigments such as iron oxide, titanium dioxide, and Prussian blue; and organic dyes such as alizarin dyes, azo dyes, and metal phthalocyanine dyes.

[0034] Examples of expanding agents include silicone-based surfactants, cellulose powder, dextrin, modified starch, polyaminocarboxylic acid chelate compounds, cross-linked polyvinylpyrrolidone, maleic acid / styrene copolymers, methacrylic acid copolymers, half-esters of polyhydric alcohol polymers and dicarboxylic acid anhydrides, water-soluble salts of polystyrene sulfonic acid, polyoxyethylene alkanediols, polyoxyethylene alkynediols, alkynediols, and the like.

[0035] Examples of spreading agents include various surfactants such as sodium dialkyl sulfosuccinate, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene fatty acid esters; paraffin, terpenes, polyamide resins, polyacrylates, polyoxyethylene, waxes, polyvinyl alkyl ethers, alkylphenol formalin condensates, and synthetic resin emulsions.

[0036] Examples of antifreeze agents include ethylene glycol, diethylene glycol, propylene glycol, polyhydric alcohols such as glycerin, and so on.

[0037] Examples of anti-caking agents include polysaccharides such as starch, alginic acid, mannose, and galactose; polyvinylpyrrolidone, white carbon, ester gum, and petroleum resin.

[0038] Examples of disintegrants include sodium tripolyphosphate, sodium hexametaphosphate, metal stearate, cellulose powder, dextrin, copolymers of methacrylate esters, polyvinylpyrrolidone, polyaminocarboxylic acid chelate compounds, sulfonated styrene-isobutylene-maleic anhydride copolymers, and starch-polyacrylonitrile graft copolymers.

[0039] Examples of decomposition inhibitors include desiccants such as zeolite, quicklime, and magnesium oxide; antioxidants such as phenolic, amine, sulfur, and phosphoric acid-based agents; and ultraviolet absorbers such as salicylic acid-based and benzophenone-based agents.

[0040] Examples of preservatives include potassium sorbate and 1,2-benzthiazoli-3-one.

[0041] Examples of plant materials include sawdust, coconut husks, corn cobs, and tobacco stalks.

[0042] On the other hand, when the above-mentioned additive components are included in the pesticide composition and herbicide of the present invention, the content ratio is selected on a mass basis as follows: for carriers such as solid carriers or liquid carriers, it is usually 5 to 95%, preferably 20 to 90%; for surfactants, it is usually 0.1 to 30%, preferably 0.5 to 10%; and for other additive components, it is 0.1 to 30%, preferably 0.5 to 10%.

[0043] The pesticide composition and herbicide of the present invention can be formulated and used in any dosage form, such as powder, granules, granules, wettable powder, water-soluble powder, wettable granules, tablets, jumbo formulations, emulsions, oils, liquids, flowable formulations, oily suspensions, emulsions, microemulsions, sposomal emulsions, trace sprays, microcapsules, jumbo formulations, bean-sized formulations (registered trademark), fumigants, smoke agents, aerosols, baits, cyclodextrin formulations, pastes, foams, carbon dioxide formulations, seed coatings, paints, wood protective coatings, and sealants.

[0044] These formulations can be used as is or diluted to a predetermined concentration with a diluent such as water. Various formulations containing the compound of the present invention or their dilutions can be applied by commonly used application methods, namely, spraying (e.g., misting, atomizing, powdering, granulation, surface application, box application, etc.), soil application (e.g., mixing, drenching, etc.), surface application (e.g., coating, powdering, covering, etc.), seed treatment (e.g., coating, powdering, etc.), immersion, poison bait, fumigation, etc.

[0045] The pesticide composition and herbicide of the present invention can control the growth of plants undesirable to useful plants, or plants undesirable from a land management perspective, by acting simultaneously or in stages on useful plants, places where useful plants are intended to be grown or are currently growing, or non-agricultural land.

[0046] The pesticide composition and herbicide of the present invention contain any of the compounds [A-1], [A-2], and [A-3] of the present invention, or a salt thereof, as active ingredients, and therefore have herbicidal activity against weeds that occur in fields, paddy fields, orchards, turflands, non-agricultural land, greenhouses, seedling facilities, or plant factories where useful plants for agricultural, horticultural, or industrial purposes are cultivated.

[0047] The above-mentioned useful plants may also be plants that have been transformed through cultivation using breeding methods or genetic modification technology. These trait plants are plants that have been conferred through breeding methods or genetic modification technology as described later.

[0048] [How to use herbicides] In the method of using the herbicide of the present invention, the herbicide is used to control weeds on useful plants that have agricultural, horticultural, or industrial uses. In other words, the herbicide of the present invention is used to control weeds that occur in the cultivation areas of useful plants, and is applied to farmland such as fields and rice paddies by methods such as foliar spraying, soil application, or water surface application. The terms "useful plants" and "weeds" are the same as those described later.

[0049] [Pesticide composition] The pesticide composition of the present invention contains any of the compounds [A-1], [A-2], and [A-3] of the present invention, or a salt thereof, as an active ingredient. This pesticide composition can be used by foliar application, soil application, or water surface application. The pesticide composition of the present invention (especially herbicides) is used in soil, particularly in farmland (cultivated land) such as fields or paddy fields where useful plants are grown. The pesticide composition of the present invention may contain two or more compounds selected from the compounds [A-1], [A-2], and [A-3] of the present invention and their salts as active ingredients.

[0050] The proportion (mass%) of the active ingredient in the pesticide composition of the present invention can be appropriately selected as needed. For example, when using powders, granules, or fine granules, it is preferable to appropriately select from the range of 0.01 to 20%, preferably 0.05 to 10%. When using granules, it is preferable to appropriately select from the range of 0.1 to 30%, preferably 0.5 to 20%. When using wettable powders or granular wettable powders, it is preferable to appropriately select from the range of 1 to 70%, preferably 5 to 50%. When using water-soluble powders or liquids, it is preferable to appropriately select from the range of 1 to 95%, preferably 10 to 80%. When using emulsions, it is preferable to appropriately select from the range of 5 to 90%, preferably 10 to 80%. When using oils, it is preferable to appropriately select from the range of 1 to 50%, preferably 5 to 30%. When using flowable formulations, it is preferable to appropriately select from the range of 5 to 60%, preferably 10 to 50%. For emulsions, microemulsions, suspend emulsions, etc., the appropriate concentration should be selected from 5-70%, preferably 10-60%. For tablets, baits, pastes, etc., the appropriate concentration should be selected from 1-80%, preferably 5-50%. For fumigants, etc., the appropriate concentration should be selected from 0.1-50%, preferably 1-30%. For aerosols, etc., the appropriate concentration should be selected from 0.05-20%, preferably 0.1-10%.

[0051] The application rate of the pesticide composition of the present invention varies depending on the type of compound used, the target weed, its tendency to occur, environmental conditions, and the dosage form used. For example, when using the pesticide composition of the present invention as a herbicide, such as in powder or granular form, it is preferable to appropriately select the amount of active ingredient from 1 g to 50 kg per hectare, preferably from 10 g to 10 kg. When using it in liquid form, such as in emulsion, wettable powder, or flowable formulation, or when diluting it to an appropriate concentration before spraying, it is preferable to appropriately select the concentration from 0.1 to 50,000 ppm, preferably from 10 to 10,000 ppm.

[0052] Furthermore, the pesticide composition of the present invention may be formulated, mixed, or used in combination with at least one other pesticide active ingredient, depending on the purpose of use, in addition to the compound of the present invention, such as other herbicides, fungicides, disease control agents, insecticides, acaricides, nematicides, synergists, attractants, repellents, phytotoxicity reducers, biopesticides, plant growth regulators, fertilizers, soil conditioners, etc.

[0053] When mixing or using in combination with other pesticide active ingredients or fertilizers, the individual ingredient formulations can be mixed at the time of application. Furthermore, each individual ingredient formulation may be applied sequentially, or with several days in between. When applying with several days in between, the interval will vary depending on the other ingredients used, but for example, treatment may be performed at intervals of 1 to 40 days.

[0054] When applying the pesticide composition of the present invention, which is obtained by mixing at least one compound selected from the compounds [A-1], [A-2], and [A-3] and their salts with at least one other pesticide active ingredient, the mixing ratio (mass ratio) can usually be 100:1 to 1:100, preferably 20:1 to 1:20, and particularly 10:1 to 1:10.

[0055] Furthermore, while it goes without saying that the pesticide composition of the present invention is sufficiently effective even when the compound of the present invention is used alone as the active ingredient, it can be mixed or used in combination with other pesticides as needed, such as insecticides, acaricides, nematicides, synergists, fungicides, antivirals, attractants, herbicides, plant growth regulators, etc. It can also be mixed or used in combination with spreading agents, phytotoxicity reducers, other agricultural materials, fertilizers, etc., and in this case, it may show even better effects.

[0056] Next, examples of known herbicides, herbicidal active ingredients, and plant growth regulators that may be mixed or used in combination are given below, but are not limited to these examples.

[0057] Herbicide compounds or herbicidal active ingredients: Ioxynil (including salts with lithium, sodium, octanonic acid, etc.), acronifen, acrolein, azaphenidin, acifluorfen (including salts with sodium, etc.), aziprotryne (aziprotryn), azimsulfuron, asulam, acetochlor, atrazine, atraton, anilofos, amicarbazone, amidosulfuron, amitrole, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, ametrine, Araudia Mosaic Virus (Araujia Mosaic Virus), alachlor, allidochlor (CDAA), Alternaria destruens, alloxydim (including salts with sodium, etc.), ancymidol, icafolin, icafolin-methyl (including salts with sodium, etc.), isouron, isoxachlortole, isoxapyrifop, isoxafenacil, isoxaflutol tole), isoxaben, isocyl, isodecyl alcohol ethoxylate, isoproturon, isopropalin, isomethiozin, ipazine, iptriazopyrid, ipfencarbazone, imazaquin,Imazapic (including salts with amines, etc.), Imazapyr (including salts with isopropylamine, etc.), Imazametabenz, Imazametabenz-methyl, Imazamox, Imazethapyr, Imazosulfuron, Indaziflam, Indanofan, Indolauxipyr, Indolauxipyr-cyanomethyl, Eglinazine-ethyl, Esprocarb, Ethamethosulfuron-methyl thyl), ethalfluralin, ethiozin, ethidimuron, etinofen, ethoxysulfuron, ethoxyfen, ethoxyfen-ethyl, ethofumesate, etobenzanid, epiriphenacil, endothal (including salts with sodium, etc.), oxadiazon, oxadiargyl, oxaziclomefone, oxasulfuron, oxyfluorfen, Obuda Pepper virus (Obuda Pepper Virus), oryzalin, orthosulfamuron, orbencarb, oleic acid, cacodylic acid, cafenstrole, caprylic acid, capric acid, carfentrazone-ethyl, carbutilate,Carbetamide, quizalofop, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, Xanthomonas campestris, quinoclamine, quinclorac, quinmerac, citric acid acid), cumyluron, clacyfos, glyphosate (containing salts of sodium, potassium, amine, propylamine, isopropylamine, ammonium, isopropylammonium, guanidine, monoethanolamine, choline, BAPMA (N,N-bis-(3-aminopropyl)methylamine), dimethylamine or trimethium, etc.), glufosinate (containing salts of amine, sodium, ammonium, etc.), glufosinate-P, glufosinate-P-sodium, clethodim, clodinafop, clodinafop-propargyl, clopyral Clopyralid (including monoethanolamine salt), cloproxydim, clofop, clomazone, chlomethoxyfen, clomeprop, chlorazine, chloranocryl (also known as dicryl), chloransulam-methyl, chloramben, chloridazon, chlorimuron, chlorimuron-ethyl, chlorsulfuron, chlorthal-dimethyl, chlorthiamid,Chlornitrofen, chlorfenac (also known as fenac), chlorfenprop, chlorphthalim, chlorbufam, chlorflurenol-methyl, chlorprocarb, chlorpropham, chlorbromuron, chloroxuron, chlorotoluron, ketospiradox (containing salts such as sodium, calcium, or ammonia), Colletotrichum orbiculare, Colletotrichum gloeosporioides, Colletotrichum truncatum, Chondrostercum purpurea Purpureum), saflufenacil, sarmentine, cyanazine, cyanamide, diuron, diethatyl-ethyl, dioxopyritrione, dicamba (amine, diethylamine, isopropylamine, diglycolamine, dimethylammonium, diolamine, isopropylammonium, auramine, potassium, thorax) methylamine, BAPMA (containing salts of N,N-bis-(3-aminopropyl)methylamine, choline, sodium or lithium, or esters such as methyl esters), cycloate, cyclooxydim, diclosulam, cyclosulfamuron, cyclopyranil, cyclopyrimorate, diclobenil, diclofop,Diclofop-P-methyl, Diclofop-methyl, Dichlorprop, Dichlorprop-P (containing salts of dimethylammonium, potassium, sodium, choline, etc., or esters such as butotyl ester, 2-ethylhexyl ester, isoctyl ester, methyl ester, etc.), Diquat, Diquat-dibromide Dibromide, dithiopyr, siduron, dinitramine, cinidon-ethyl, cinosulfuron, dinosam, dinoseb (containing salts of acetate, ammonium, diolamine, sodium, trolamine, etc.), dinoterb, cyhalofop, cyhalofop-butyl, cypyrafluone, diphenamid, difenoxuron, difenzoquat, cyprazine (cyprazine), diflufenican, diflufenzopyr (including sodium salts), dipropetryn, cyperquat, simazine, dimesulfazet, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, simetryn, dimepiperate, dimepyrolimet, dimefuron, Pseudomonas Fluorescens (Pseudomonas fluorescens), cinflubrolin, cinmethylin, swep, Sclerotinia minor,Sulcotrione, sulfentrazone, sulfosate, sulfosulfuron, Sulfometuron-methyl, secbumeton, setoxydim, sebuthylazine, terbacil, daimuron, thaxtomin A, Tobacco Mild Green Mosaic Tobamovirus, Tobacco Rattle Virus Virus), dalapon, thiazafluron, thiazopyr, tiafenacil, thiencarbazone (including sodium salt, methyl ester, etc.), tiocarbazil, thiobencarb, thidiazimin, thidiazuron, thifensulfuron, thifensulfuron-methyl, desmedipham, desmetryne, tetflupyrolimet, thenylchlor, Tebutam, tebuthiuron, tepraloxydim, tefuryltrione, delachlor, terbuthylazine, terbutryn, terbumeton, tembotrione, toxapyzone, topramezone, tralkoxydim, triaziflam, triasulfuron, triafamone, tri-allate, trietazine, triclopyr,Triclopyr-triethylammonium, triclopyr-butotyl, tridiphane, tritosulfuron, tripyrasulfone, trifludimoxazin, triflusulfuron-methyl, triflupyroxazin, triflural (in), trifloxysulfuron (including salts with sodium, etc.), tribenuron-methyl, tolpyralate, naptalam (including salts with sodium, etc.), naproanilide, nappropamide, nappropamide-M, nicosulfuron, nitralin, nitrofen, lactic acid, neburon, norflurazon, Burkholderia rinojensis, vernolate, paraquat, paraquat dichloride dichloride), parafluron, halauxifen, halauxifen-benzyl, halauxifen-methyl, barban, haloxyfop, haloxyfop-etotyl, haloxyfop-P, haloxyfop-P-methyl, halosafen, halosulfuron-methyl, bixlozone, picloram (dichloroammonium,(Including salts with trolamine, etc.), picolinafen, bicyclopyrone, bispyribac-sodium, pinoxaden, bipyrazone, bifenox, piperophos, pyraquinate, pyraclonil, pyrasulfotole, pyrazoxyfen, pyrazosulfuron-ethyl, pyrazolynate, bilanaphos Pyraflufen, pyraflufen-ethyl, pyridafol, pyrithiobac-sodium, pyridate, pyriftalid, pyributicarb, pyriflubenzoxim, pyribenzoxim, pyrimisulfan, pyriminobac-methyl, pyroxasulfone, pyroxsulam, phytopsola Palmibora (Phytophthora palmivora), phenisopham, fenuron, fenoxasulfone, fenoxaprop (containing methyl, ethyl, and isopropyl esters), fenoxaprop-P (containing methyl, ethyl, and isopropyl esters), fenoprop, feproxydim, fenquinotrione, fendioxypyracil, fenthiaprop, fenthiaprop-ethyl, fentrazamide,Fenpyrazone, phenmedipham, Phoma chenopodicola, Phoma herbarum, Phoma macrostoma, butachlor, butafenacil, butamifos, butyrate, Puccinia canaliculata, Puccinia suraspeos thlaspeos), buturon, butenachlor, butralin, butroxydim, flazasulfuron, flamprop (containing methyl, ethyl, and isopropyl esters), flamprop-M (containing methyl, ethyl, and isopropyl esters), prynachlor, primisulfuron, primisulfuron-methyl, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl p-P-butyl), fluazolate, fluothiuron, fluometuron, fluoroglycofen-ethyl, fluorodifen, fluoronitrofen, flucarbazone-sodium, fluchloraminopyr (containing tetrahydrofurfuryl ester), fluchloralin, flusulfinam, flucetosulfuron, fluthiacet-methyl,Flupyrsulfuron-methyl (containing salts such as sodium, calcium, or ammonia), flufenauxirim, flufenacet, flufenazopyr, flufenoximacil, flufenpyr-ethyl, flupropanate (containing sodium salt), flupoxame, flumioxazin, flumimicrolac-pentyl -pentyl), flumipropyn, flumetsulam, fluridone, flurtamone, fluroxypyr (containing esters of butomethyl, meptyl, etc., or salts of sodium, calcium, ammonia, etc.), flurochloridone, pretilachlor, procarbazone (containing salts with sodium, etc.), proglinazine, proglinazine-ethyl, Broclozone, prochlorosulfone, procyazine, prodiamine, prosulfuron, prosulfocarb, propaquizafop, propachlor, propazine, propanil, propyzamide, propisochlor, propyrisulfuron, propham, profluazol, profluralin, prohexadione-calcium, propoxycarbazone, propoxycarbazone sodium Bazone-sodium), profoxydim, bromacil, brompyrazon, bromuron, prometryn, prometon, bromoxynil (including esters of butyric acid, octanoic acid or heptanoic acid, etc.), bromofenoxime, bromobutide, f Florasum, florpyrauxifen, florpyrauxifen-benzyl, hexazinone, petoxamide, benazolin (containing salts such as dimethylammonium or potassium), benazolin-ethyl, penoxsulam, Pepino Mosaic Virus, heptamaloxyloglucan, beflubutamid, beflubutamid-M, pebulate,Pelargonic acid, perfluidone, bencarbazone, benquitrione, pendimethalin, benzthiazuron, benzfendizone, bensulide, bensulfuron, bensulfuron-methyl, benzobicyclon, benzofenap (benzofenap), bentazone, pentanochlor, pentoxazone, benfluralin, benfuresate, fosamine, fomesafen, foramsulfuron, forchlorfenuron, mecoprop (sodium, potassium, isopropylamine, triethanolamine) Salts of ciamine, dimethylamine, diolamine, troamine, choline, etc., or esters such as ethadyl ester, 2-ethylhexyl ester, isoctyl ester, methyl ester, etc.), mecoprop-P-potassium salt, medinoterb, mesosulfuron (including esters such as methyl), mesotrione, metazachlor, metazosulfuron, Metabenzthiazuron, metamitron, metamifop, metam (including salts such as sodium), disodium methanearsone (DSMA), methiozolin, methyldymuron, metoxuron, metosulam, metsulfuron-methyl, metobromuron,Metoproxybicyclone, metoprotryne, metobenzuron, metolachlor, metribuzin, mepiquat Chloride, mefenacet, mefluidide, monalide, monouron, monosulfuron (including methyl, ethyl, and isopropyl esters), monolinuron, molinate, morfamquat, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, lactofen, lancotrione, linuron, rimisoxafen, rimusulfuron (r imsulfuron), lenacil, 2,2,2-trichloroacetic acid (TCA) (containing salts such as sodium, calcium or ammonia), 2,3,6-trichlorobenzoic acid (2,3,6-TBA), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 2,4-dichlorophenoxyacetic acid (2,4-D) (amines, diethylamine, triethanolamine, isopropylamine, dimethylammonium, diolamine, dodecylammonium, heptylammonium, tetradecylammonium, triethylammonium, tris(2-hydroxypropyl)ammonium, trolamine, choline, sodium or lithium salts, or butotyl esters, 2-butoxypropyl esters, 2-ethylhexyl esters, methyl esters, ethyl esters, butyl esters, isobutyl esters, octyl esters, pentyl esters, propyl esters, (including esters such as isoctyl esters, isopropyl esters, meptyl esters, tefuryl esters), 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB) (containing salts of amines, diethylamine, triethanolamine, isopropylamine, dimethylammonium, choline, sodium or lithium, or esters such as isoctyl esters), 2-amino-3-chloro-1,4-naphthoquinone (ACN), 2-methyl-4-chlorophenoxyacetic acid (MCPA) (containing salts of sodium, dimethylammonium, choline, or 2-ethylamine, methylamine, diethylamine, triethanolamine, isopropylamine, dimethylammonium, choline, or 2-ethylamine, diethylamine, diethylamine, triethanolamine, triethanolamine, isopropylamine, dimethylammonium, choline, or 2-ethylamine, diethylamine, diethylamine, triethanolamine, triethanolamine, dimethylamine, triethanolamine, dimethylammonium, choline, or 2-ethylamine, diethylamine, diethylamine, triethanolamine, diethylamine, triethanolamine, dimethyl (including esters such as dihexyl ester, isoctyl ester, and ethyl ester), 2-methyl-4-chlorophenoxybutyric acid (MCPB) (including sodium salt and ethyl ester), 4,6-dinitro-O-cresol (DNOC) (including salts such as amine or sodium), (5S)-3-(3,5-difluorophenyl)-N-[rel-(3R,5R)-5-(trifluoromethylsulfonylcarbamoyl)telolahydrofuran-3-yl]-5-vinyl-4H-isoxazole-5-carboxamide ((5S)-3-(3,5-diflu N4-(2,6-difluorophenyl)-N-[rel-(3R,5R)-5-(trifluoromethylsulfonylcarbamoyl)tetrahydrofuran-3-yl]-5-vinyl-4H-isoxazole-5-carboxamide) (Chemical name, CAS registry number: 2266183-40-6) (International Publication No. 2018 / 228986, International Publication No. 2020 / 114934), N4-(2,6-difluorophenyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine(N4 -(2,6-difluorophenyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine)(chemical name, CAS registry number: 1606999-43-2)(International Publication No. 2014 / 064094, International Publication No. 2015 / 162164), (5S)-3-(3,5-difluorophenyl)-N-[(3R)-5-(methylsulfonylcarbamoyl)-2,3-dihydrofuran-3-yl]-5-vinyl-4H-isoxazole-5-carboxamide((5S)-3-(3,(5-difluorophenyl)-N-[(3R)-5-(methylsulfonylcarbamoyl)-2,3-dihydrofuran-3-yl]-5-vinyl-4H-isoxazole-5-carboxamide) (Chemical name, CAS registry number: 2266190-06-9) (International Publication No. 2018 / 228986, International Publication No. 2020 / 114934), (5R)-3-(3,5-difluorophenyl)-5-methyl-N-[rel-(3R,5R)-5-(methylsulfonylcarbamoyl)tetrahydrof [(5R)-3-(3,5-difluorophenyl)-5-methyl-N-[rel-(3R,5R)-5-(methylsulfonylcarbamoyl)tetrahydrofuran-3-yl]-4H-isoxazole-5-carboxamide] (Chemical name, CAS registry number: 2266164-36-5) (International Publication No. 2018 / 228986, International Publication No. 2020 / 114934), (5R)-3-(3,5-difluorophenyl)- N-[(3R)-5-(methoxycarbamoyl)-2,3-dihydrofuran-3-yl]-5-methyl-4H-isoxazole-5-carboxamide ((5R)-3-(3,5-difluorophenyl)-N-[(3R)-5-(methoxycarbamoyl)-2,3-dihydrofuran-3-yl]-5-methyl-4H-isoxazole-5-carboxamide) (Chemical name, CAS Registry Number: 2266170-31-2) (International Publication No. 2018 / 228986, International Publication No. 2020 / 114934) (Report), 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one (chemical name, CAS registry number: 1708087-22-2) (International Publication No. 2015 / 059262, International Publication No. 2018 / 015476), 6-(1-fluorocyclopentyl)-N4-(2,3,5,6-tetrafluorophenyl)-1,3,5-triazine-2,4-Diamine(6-(1-fluorocyclopentyl)-N4-(2,3,5,6-tetrafluorophenyl)-1,3,5-triazine-2,4-diamine) (Chemical name, CAS registry number: 1820807-75-7) (International Publication No. 2015 / 162164), 6-(1-fluoro-1-methylethyl)-N4-(2,3,5,6-tetrafluorophenyl)-1,3,5-triazine-2,4-diamine(6-(1-fluoro- (1-methylethyl)-N4-(2,3,5,6-tetrafluorophenyl)-1,3,5-triazine-2,4-diamine) (Chemical name, CAS registry number: 1606999-21-6) (International Publication No. 2014 / 064094, International Publication No. 2015 / 162164), (5S)-3-(3-fluoro-5-methylphenyl)-N-[rel-(3R,5R)-5-(methoxycarbamoyl)tetrahydrofuran-3-yl]-5-diamine Nyl-4H-isoxazole-5-carboxamide ((5S)-3-(3-fluoro-5-methylphenyl)-N-[rel-(3R,5R)-5-(methoxycarbamoyl)tetrahydrofuran-3-yl]-5-vinyl-4H-isoxazole-5-carboxamide) (Chemical name, CAS registry number: 2266292-43-5) (International Publication No. 2018 / 228986, International Publication No. 2020 / 114934) (Report), 6-(1-methylcyclobutyl)-N4-(2,3,5,6-tetrafluorophenyl)-1,3,5-triazine-2,4-diamine (6-(1-methylcyclobutyl)-N4-(2,3,5,6-tetrafluorophenyl)-1,3,5-triazine-4,4-diamine) (Chemical name, CAS registry number: 1607001-97-7) (International Publication No. 2014 / 064094, International Publication No. 2015 / 162164), 3-(acetyloxy)-5-[2-(methoxyimino)propyl]-2-(2,4,6-trimethylphenyl)-2-cyclopenten-1-one (CAS Registry Number: 1952327-05-7), 3-acetyl-9-[2,6-dimethyl-4-(1-propyne-1-yl)phenyl]-10-hydroxy-3 -Azaspiro[5.5]undec-9-en-8-one (3-acetyl-9-[2,6-dimethyl-4-(1-propyn-1-yl)phenyl]-10-hydroxy-3-azaspiro[5.5]undec-9-en-8-one) (CAS Registry No.: 2374705-11-8), (1S,4R)-4-({3-[(3,5-dichlorophenyl)amino]-2-methoxy-1,3-dioxopropyl}amino]-2-cyclopentene-1-carboxylate methyl(methyl (1S,4R)-4-({3-[(3,5-dichlorophenyl)amino]-2-methoxy-1,3-dioxopropyl}amino)-2-cyclopentene-1-carboxylate) (CAS Registry No.: 2699953-64-3), 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidined-2-one (4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyr [idyl]imidazolidin-2-one) (CAS Registry Number: 2023785-78-4), pyridin-2-ylmethyl [(3-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidine-1(2H)-yl]phenoxy}pyridin-2-yl)oxy]acetate (pyridin-2-ylmethyl[(3-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenoxy}pyridin-2-yl)oxy]acetate) (CAS Registry No.: 2591611-15-1), 2-methoxy-1-methyl-2-oxoethyl 1-[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenoxy]cyclopropanecarboxylate) (CAS Registry No.: 1101021-03-7), methyl 2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenoxy]phenoxy]-2-methoxy-acetate (methyl 2-[2-[2-bromo-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenoxy]phenoxy]-2-methoxy-acetate) (CAS Registry No.: 2703795-90-6), ethyl 2-[[3-[2-chloro-5-[4-(1,1-difluoroethyl)-3,6-dihydro-3-methyl-2,6-dioxo-1(2H)-pyrimidinyl]-4-fluorophenoxy]-2-pyrimidinyl]oxy]acetate (ethyl 2-[[3-[2-chloro-5-[4-(1,1-difluoroethyl)-3,6-dihydro-3-methyl-2,6-dioxo-1(2H)-pyrimidinyl]-4-fluorophenoxy]-2-pyridinyl]oxy]acetate)(CAS Registry No.: 2892260-46-5), 2,2,7-trifluoro-6-(perfluorophenyl)-4-(propa-2-in-1-yl)-2H-benzo[b][1,4]oxazine-3(4H)-one(2,2,7-trifluoro-6-(perfluorophenyl)-4-(prop-2-yn-1-yl)-2H-benzo[b][1,4]oxazin-3(4H)-one) (CAS Registry Number: 2919853-14-6), cyclopropylmethyl-(2-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidine-1(2H)-yl]phenoxy}phenoxy) acetate (cyclopropylmethyl-(2-{2-chloro-4-fluoro -5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl]phenoxy}phenoxy)acetate) (CAS Registry Number: 3035314-60-1), N-{2-[N-(ethoxycarbonyl)-N-(trifluoromethanesulfonyl)amino]benzyl}-3,4-dihydroisoquinoline-1(2H)-one (N-{2-[N-(Ethoxycarbonyl)-N-(trifluoromethanesulfonyl)ami 6-(1,1-dioxidothiochroman-5-yl)-1-methoxy-3-methyl-7-oxa-3,4-diazabicyclo[4.1.0]hept-4-en-2-one) (CAS Registry Number: 3007521-83-4), 6-(1,1-dioxidothiochroman-5-yl)-1-methoxy-3-methyl-7-oxa-3,4-diazabicyclo[4.1.0]hept-4-en-2-one) (CAS Registry Number :2636129-90-1), (S)-2-chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide ((S)-2-chloro-N-(5-methyl-1,3,4-oxadiazol-2-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide) (CAS Registry Number: 2833716-54-2), (S)-2-chloro-3-(cyclopropylsulfinyl)-N-(5-methyl-1,3,4-Oxadiazol-2-yl)-4-(trifluoromethyl)benzamide ((S)-2-chloro-3-(cyclopropylsulfinyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-4-(trifluoromethyl)benzamide) (CAS Registry Number: 2833716-50-8), N, 2 -(3-chloro-5,6-difluoro-2-methoxyphenyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine(N 2 -(3-chloro-5,6-difluoro-2-methoxyphenyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine) (CAS Registry No.: 2813322-23-3), 6-chloro-4-(2,7-dimethyl-1-naphthalenyl)-2-methyl-3,5(2H,4H)-pyridazinedione (CAS Registry No.: 2766998-36-9), AE-F-150944 (code number), 2, 4-bis(3-methoxypropylamino)-6-methylthio-s-triazine (CP17029), DMPA (CAS Registry Number: 299-85-4), IR-6396 (code number), MCPA-thioethyl, SYP-298 (code number), SYP-300 (code number), S-ethyldipropylthiocarbamate (EPTC), calcium methanearsonate (CAMA), S-metolachlor, monosodium methyl arsenate (MSMA), HW-02 (code number), S-523 (code number).

[0058] Plant growth regulator compounds: 1-naphthylacetamide, 1-methylcyclopropene, 1,3-diphenylurea, 2,3,5-triiodobenzoic acid 5-(trifluoromethyl)benzo[b]thiophen-2-carboxylate methyl (Methyl)(CPA), 2-(naphthalene-1-yl)acetamide, 2,6-diisopropylnaphthalene, 3-[(6-chloro-4-phenylquinazoline-2-yl)amino]propane-1-ol), 4-oxo-4-(2-phenylethyl)aminobutyric acid (chemical name, CAS registry number: 1083-55-2), 4-chlorophenoxyacetic acid (4-CPA), 5-aminolevulinic acid hydrochloride, 5-(trifluoromethyl)benzo[b]thiophen-2-carboxylate methyl (Methyl)(CPA), 2-(naphthalene-1-yl)acetamide, 2,6-diisopropylnaphthalene, 3-[(6-chloro-4-phenylquinazoline-2-yl)amino]propane-1-ol, 5-(trifluoromethyl)benzo[b]thiofen-2-carboxylate), AVG (aminoethoxyvinylglycine), n-decyl alcohol, anisiflupurin, abiglycine, abscisic acid, ancymidol, isoprothiolane, inabenfide, 3-indoleacetic acid, 3-indolebutyric acid, uniconazole, uniconazole-P, Ecolyst, etychlozate, ethephon, epocholeone, calcium chloride, choline chlorideChloride, oxine sulfate, opabactin, kinetin, calcium peroxide, carvone, calcium formate, quinabactin, cloxyfonac, cloxyfonac-potassium, cloprop, chlorpropham, chlormequat, chlormequat-chloride, choline, cytokinins, oxidized glutathione, cyanamide, sodium cyanate cyanate), cyclanilide, dichlorprop (containing salts of dimethylammonium, potassium, sodium, choline, etc., or esters such as butotyl ester, 2-ethylhexyl ester, isoctyl ester, methyl ester, etc.), dichlorprop-P (containing salts of sodium, potassium, dimethylammonium, etc., or 2-ethylhexyl ester), diquat, diquat dibromide, dikegulac, gibberellic acid, gibberellin A4, gibberellin A7, dimethipin, jasmone, cis-jasmone, jasmonic acid, methyl jasmonate Jasmonate, sintofen, streptomycin, calcium polysulfide, daminozide, calcium carbonateCarbonate, thidiazuron, decan-1-ol, triacontanol, tripenthenol, trinexapac, trinexapac-ethyl, tribufos, paclobutrazol, paraffin, bispyribac-sodium, hymexazol, pyraflufen-ethyl, butruarin, fluthiaset-methyl (f (luthiacet-methyl), flumetralin, flurprimidol, flurenol, pronitridine, prohydrojasmon, prohexadione-calcium, heptamaloxyloglucan, 6-benzylaminopurine, pendimethalin, forchlorfenuron, formononetin, maleate hydrazide (maleic Hydradise, mepiquat, mepiquat chloride, mefluidide, lipochitooligosaccharides (e.g., lipochitooligosaccharides SP104), calcium sulfate.

[0059] Next, examples of known pharmacokinetic mitigation compounds that may be mixed or used in combination are listed below.

[0060] Compounds that reduce drug-induced harm: Isoxadifen, isoxadifen-ethyl, oxabetrinil, octane-1,8-diamine, cumyluron, cloquintocet, cloquintcet-mexyl, dietholate, cyometrinil, dichlormid, dicyclonone, cyprosulfamide, dimepiperate, daimuron, 1,8-Naphthalic anhydride Anhydride), fenchlorazole, fenchlorazole-O-ethyl, fenchlorim, furilazole, fluxofenim, flurazole, benoxacor, metcamifen, mephenate, mefenpyr, mefenpyr-ethy l) Mefenpyr-diethyl, melatonin, lower alkyl-substituted benzoic acid, 2,2-dichloro-N-(1,3-dioxolan-2-ylmethyl)-N-(2-propenyl)acetamide (PPG-1292), 2-dichloromethyl-2-methyl-1,3-dioxane (MG-191), 2,4,6-trichlorophenoxyacetic acid, 3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine (R-29148), 4-dichloroacetyl-1-oxa-4-azaspiro[4.5] Decane (AD-67), 4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid (CL-304415, code number), MON4660 (code number) (CAS registry number: 71526-07-3), N1,N2-diallyl-N2-dichloroacetylglycinamide (DKA-24, code number), 1-bromo-4-[(chloromethyl)sulfonyl]benzene (CSB), 2-propenyl 1-oxa-4-azaspiro[4,5]decane-4-carboditioate (MG-838, code number), 3-(dichloroacetyl)-2,2-dimethyl-1,3-oxazolidine (R-28725, code number), R-29148 (code number), 1-(dichloroacetyl)azepane (TI-35, code number), methyl {[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate (methyl {[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetate) (CAS Registry No.: 2647923-10-0), 2-{[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid (2-{[5-(4-chloro-2-fluorophenyl)-1-(2,4-difluorophenyl)-1H-1,2,4-triazol-3-yl]oxy}acetic acid) 3-(2-ethoxyethoxy)benzo[e][1,4,2]dithiazine 1,1-dioxide (CAS Registry Number: 113887-92-6).

[0061] Next, examples of known insecticides (insecticidal active ingredients), acaricides (acaricidal active ingredients), nematicides (nematicidal active ingredients), and synergistic compounds (synergistic active ingredients) that may be mixed or used in combination are given below.

[0062] Insecticidal active ingredients, acaricidal active ingredients, nematicidal active ingredients, synergistic active ingredients: Acrin, azadirachtin, azamethiphos, acynonapyr, azinphos-ethyl, azinphos-methyl, acequinocyl, acetamiprid, acetoprole, acephate, azocyclotin, Abamectin, afidopyropen, afoxolaner, amidoflumet, amitraz, alanycarb, aldicarb, aldoxycarb, allethrin (including d-cis-trans and d-trans forms), isazophos, isamidofos ), isocarbophos, isoxathion, isocycloseram, isofenphos-methyl, isoflualanam, isoprocarb, epsilon-metofluthrin, epsilon-momfluorothrin, ivermectin n) Imicyafos, imidacloprid, imiprothrin, indazapyroxamet, indoxacarb, umifoxolaner, esfenvalerate, ethiofencarb, ethion, ethiprole, ethylenedibromideDibromide), etoxazole, etofenprox, etoprophos, etrimfos, emamectin, emamectin benzoate, endosulfan, empenthrin, oxazosulfyl, oxamyl, oxydemeton-methyl, oxydeprofos, omethoate, Nuclear polyhedrosis virus EnteroVirus), coumaphos, cryolite, clothianidin, clofentezine, chromafenozide, chlorantraniliprole, chlorethoxyfos, chlordane, chloropicrin, chlorpyrifos, chlorpyrifos-methyl, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroprallethrin, Iridovirus, Entomopoxvirus, Cytoplasmic polyhedrosis virus embedding Sigma virus, fenbutatin oxide, cyazypyr, cyanophos, cyanoflanilide, diafenthiuron, diamidaphos, cyantraniliprole, cyetpyrafen, dienochlor, cyenopyrafen, dioxabenzofos, diofenolan, Sigma virus(virus), cyclaniliprole, cycloxaprid, dicrotophos, diclofenthion, cyclobutrifluram, cycloprothrin, dichlorvos, dichloromezotiaz, dicofol, dicyclanil, disulfoton, dinotefuran, dinobuton, cyhalodiamide, cyhalothrin (including gamma- and lambda- forms), cyphenothrin (including (1R)-trans- form), cyfluthrin ( (including beta-isomer), diflubenzuron, cyflumetofen, diflovidazin, cyproflanilide, cyhexatin, cypermethrin (including alpha-, beta-, theta-, and zeta-isomers), cybenzoxasulfyl, dimpyrargyl, dimpropyridaz, dimethyl-2,2,2-trichloro-1-hydroxyethylphosphonate (DEP), dimethylvinphos, dimethoate, dimefluthrin, jasmone, cis-jasmone, jasmonic acid acid), methyl jasmonate, silafluofen, cyromazine, Steinernema carpocapsae, Steinernema kushidai, Steinernema glaceraiglaseri), spidoxamat, spinetoram, spinosad, spirodiclofen, spirotetramat, spiropidion, spirobudifen, spiromesifen, sulcofuron-sodium, sulfiflumin, sulfindoflufen, sulfluramid, sulfoxaflor, sulfoxamyl, sulfotep, calcium cyanamidecyanide), diazinon, thiacloprid, tiapyrachlor, thiamethoxam, tioxazafen, thiodicarb, thiocyclam, thiosultap, thionazin, thiofanox, thiometon, thiorantraniliprole, tyclopyrazoflor, tigolaner, tetrachlorantraniliprole, tetrachlorvinphos, tetradifon, tetraniliprole ( Tetraniliprole, tetramethylfluthrin, tetramethrin, tebupirimfos, tebufenozide, tebufenpyrad, tefluthrin, teflubenzuron, demeton-S-methyl, temephos, deltamethrin, terbufos, tralomethrin, transfluthrin, triazamate, triazophos, trioxyflanilide, trichlorfon, Trichoderma Trichoderma asperellum, Trichoderma paecilomyces, Trichoderma halcianumHarzianum), trifluenfuronate, triflumuron, triflumezopyrim, trimethacarb, tolfenpyrad, napoxametamide, naled, nicotine, nicofluprole, nitenpyram, Nemadectin, Denso virus, novaluron, noviflumuron, paecilomyces lilacinus, Burkholderia cepacia, Burkholderia rinojensis, Verticillium lecanii, hydroprene, Pasteuria nishizawae, Pasteuria penetrans, Bacillus amyloliquefaciens, Bacillus sphaericus, Bacillus subtillis, Bacillus Bacillus thuringiensis, the insect toxin produced by Bacillus thuringiensis, Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Israelensis, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis, Bacillus firmus, Bacillus popilliae, Bacillus licheniformis(licheniformis), vadescana, vamidothion, parathion, parathion-methyl, halfenprox, halofenozide, bioallethrin, bioallethrin S-cyclopentenyl S-cyclopentenyl), pioxaniliprole, bioresmethrin, bis-(2-chloro-1-methylethyl) ether (DCIP), bistrifluron, bisulflufen, hydramethylnon, vinylfluthrin, bifenazate, bifenthrin, pyflubumide, piperflanilide, piperonyl butoxide (piperonyl(butoxide), pymetrozine, pyraclofos, pyrafluprole, pyridaphenthion, pyridaben, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, pirimicarb, pyrimidifen, pyriminostrobin, pirimiphos-methyl, pyrethrine, famphur, f Fipronil, fenazaquin, fenamiphos, fenargimine, fenitrothion, fenoxycarb, fenothiocarb, phenothrin (including (1R)-trans-isomer), fenobucarb, fentiazoluron, fenthion, phenthoate, fenvalerate, fenpyroximate, fenbutatin oxide, fenpropathrin, fenmezoditiaz, fonofos, sulfuryl fluorideFluoride), butocarboxim, butoxycarboxim, buprofezin, furathiocarb, prallethrin, fluacrypyrim, fluazaindolizine, fluazuron, fluensulfone, fluopyram, sodium fluoroacetateFluoracetate), fluxametamide, fluchlordiniliprole, flucycloxuron, flucythrinate, flusulfamide, fluthrin, fluvalinate (including tau-isomer), flupymezotiaz, flupyradifurone, flupyrazofos, flupyrimin, flupyroxystrobin, flufiprole, flufenerim, flufenoxystrobin, flufenoxuron, fluhexafon, flubendiamide, flupe Flupentiofenox, flumetnicam, flumethrin, fluralaner, flurimfen, prothiofos, protrifenbute, flonicamid, propaphos, propargite, prohydrojasmon n) profenofos, broflanilide, brofluthrinate, profluthrin, propetamphos, propoxur, flometoquin, bromopropylate, hexythiazox, hexaflumuron, Paecilomyces tenuipes, Paecilomyces fumosoroceus, PaecilomycesLilacinus (Paecilomyces lilacinus), heptafluthrin, heptenophos, permethrin, benclothiaz, benzpyrimoxan, bensultap, benzoximate, bendiocarb, bentiolumin, benfuracarb, Beauveria tenella, Beauveria bassiana, Beauveria brongniartii, phoxim, Pochonia chlamydospria Chlamydosporia, phosalone, fosthiazate, fosthietan, phosphamidon, phosmet, polynactins, formetanate, phorate, machine oil, malathion, mivorilaner, milbemectin, mecarbam, mesulfenfos, methomyl, metaldehyde, metaflumizone, metamidophos, metam, methiocarb, methidathion, methyl isothiocyanate isothiocyanate, methyl bromide, methoxychlor, methoxyfenozide, methothrin, Metofluthrin, methoprene, metolcarb, mevinphos, meperfluthrin, modoflaner, Monacrosporium phymatophagum, monocrotophos, momfluorothrin, organotins, litlure-A, litlure-B, nicotine sulfate, zinc phosphide, aluminum phosphide Phosphide, hydrogen phosphine, lufenuron, rescalure, resmethrin, ledprona, lepimectin, rotenone, (Z)-11-tetradecenyl acetate, (Z)-11-hexadecenal, (Z)-11-hexadecenyl acetate, (Z)-9,12-tetradecadienyl acetate, (Z)-9-tetradecen-1-ol, (Z,E)-9,11-tetradecadienyl acetate, (Z,E)-9,12-tetradecadienyl acetate, 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT), 1,3-dichlorophenyl Lolopropene (1,3-dichloropropene), 2,4-dichloro-5-{2-[4-(trifluoromethyl)phenyl]ethoxy}phenyl-2,2,2-trifluoroethyl sulfoxide (chemical name, CAS registry number: 1472052-11-1), 2,4-dimethyl-5-[6-(trifluoromethylthio)hexyloxy]phenyl-2,2,2-trifluoroethyl sulfoxide (chemical name, CAS registry number: 1472050-34-2), 2-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenoxy}-5-(trifluoromethyl)pyridine (chemical name, CAS registry number: 1448758-62-0), 3-chloro-2-{2-fluoro-4-methyl-5-[(2,2,2-Trifluoroethyl)sulfinyl]phenoxy}-5-(trifluoromethyl)pyridine (chemical name, CAS registry number: 1448761-28-1), 4,6-dinitro-o-cresol (DNOC), 4-fluoro-2-methyl-5-(5,5-dimethylhexyloxy]phenyl 2,2,2-trifluoroethyl sulfoxide (chemical name, CAS registry number: 1472047-71-4), Bt protein (Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Ab1), methyl eugenol, 4-(p-acetooxyphenyl)-2-butanone, (Z)-10-tetradecenyl acetate, (E,Z)-4,10-tetradecadienyl acetate, (Z) -8-Dodecenyl acetate, (Z)-13-Icosen-10-one, 14-Methyl-1-octadecene, CL900167 (code number), O,O-Diethyl-O-[4-(dimethylsulfamoyl)phenyl]-phosphorothionate (DSP), O-Ethyl-O-4-(nitrophenyl)phenylphosphonothioate (EPN), 3,5-Xylylmethylcarbamate (XMC), NI-30 (code number).

[0063] Next, examples of known fungicides (fungicide-active ingredients) or disease control compounds that may be mixed or used in combination are listed below.

[0064] Bactericidal active ingredients or disease control compounds: Agrobacterium radiobacter, azaconazole, acibenzolar-S-methyl, azoxystrobin, anilazine, amisulbrom, aminotipyr, aminopyrifen, amfenamacril, ametoctradin, aldimorph, isotianil, isopyrazam, isofetamide, isoflucypram, isoproti Isoprothiolane, ipconazole, ipfentrifluconazole, ipflufenoquin, iprodione, iprovalicarb, iprobenfos, imazalil, iminoctadine-albesilate, iminoctadine-triacetate, imibenconazole, inpyrfluxam, imprimatin A A) Imprimatin B, edifenphos, etaconazole, etaboxam, ethirimol, ethoxyquin, etridiazole, enestroburin, enoxastrobin, epoxyconazole, erysichrona, enprocymid, organic oiloils), oxadixyl, oxazinylazole, oxathiapiprolin, oxycarboxin, oxine-copper, oxytetracycline, oxpoconazole-fumarate, oxolinic acid, copper octanoate Candida dioctanoate, octhilinone, ofurace, orysastrobin, o-phenylphenol, kasugamycin, captafol, galquin, carpropamid, carbendazim, carboxin, carvone, carmeconazole, Candida oleophila, Candida cytoana saitoana), quinaminoprole, quinoxyfen, quinofumelin, chinomethionate, captan, quinconazole, quintozene, guazatine, cufraneb, coumethoxystrobin, coumoxystrobin, Gliocladium catenulatum, Cryptococcus albidus, kresoxim-methyl, clozylacon, chlozolinate, Clonostachys rosearosea), chloroinconazide, chlorothalonil, chloroneb, Chaetomium cupreum, Coniothyrium minitans, cyazofamid, diethofencarb, diclocymet, cyclobunofen, dichlofluanid, diclobentiazox, diclomezine, dichloran, dichlorophen, dithianon, diniconazole, diniconazole-M, di Zineb, Dinocap, Dipymetitrone, Diphenylamine, Difenoconazole, Cyflufenamid, Diflumetorim, Cyproconazole, Cyprodinil, Cyprometoxazam, Simeconazole, Dimethirimol, Dimethyl disulfide disulfide), dimethomorph, cymoxanil, dimoxystrobin, Pseudozyma flocculosa, Pseudomonas aureofaciens, Pseudomonas chlororaphis, Pseudomonas syringae, Pseudomonas flurorescens, Pseudomonas rodesia HAI-0804 (PseudomonasRhodesiae HAI-0804), Ziram, Silthiofam, Zucchini yellow mosaic virus (attenuated strain), Streptomycin, Streptomyces griseoviridis, Streptomyces lydicus, Spiroxamine, Sedaxane, Seboctylamine, Zoxamide, Solatenol, Dazomet, Talaromyces flavus flavus), thiadinil, thiabendazole, thiuram, thiophanate, thiophanate-methyl, tifluzamide, tecnazene, tecloftalam, tetraconazole, debacarb, tebuconazole, tebufloquin, terbinafine, dodine, dodemorph, triadimenol, triadimefon, triazoxide, triclamide, triclopyricarb, Trichoderma aspereram Trichoderma asperellum, Trichoderma atroviride, Trichoderma gamsii, Trichoderma stromaticum, Trichoderma paecilomyces, Trichoderma harzianum, Trichoderma harzianumTrichoderma harzianum rifai, Trichoderma viride, Trichoderma virens, Trichoderma polysporum, Trichoderma lignolan Lignorum), tricyclazole, triticonazole, tridemorph, triflumizole, trifloxystrobin, triforine, tolylfluanid, tolclofos-methyl, tolnifanide, tolprocarb, nabam, natamycin, naftifine, nitrapyrin, nitrothal-isopropyl, nuarimol, copper nonylphenol sulfonate, Burkholderia cepacia, Burkholderia linogensis rinojensis), harpin protein, Paenibacillus polymyxa, Bacillus amyloliquefaciens, Bacillus simplex, Bacillus subtilis (strain:QST 713), Bacillus pumilus, Bacillus mycoides, Bacillus licheniformis, Variovorax paradoxus, validamycin, valifenalate, Pantoea agglomerans agglomerans), picarbutrazox, bixafen, picoxystrobin, Pythium oligandrum, pydiflumetofen, bitertanol, binapacryl, hinokitiol, non-pathogenic Erwinia carotovora, non-pathogenic Rhizobium vitisVitis), biphenyl, bifemetstrobin, piperalin, hymexazol, pyraoxystrobin, pyraclostrobin, pyraziflumid, pyrazophos, pyrapropoyne, pyrametostrobin, pyriophenone (p Pyriofenone, pyrisoxazole, pyridaclomethyl, pyrifenox, pyributicarb, pyribencarb, pyrimethanil, pyroquilon, vinclozolin, ferbam, famoxadone, phenazine oxide Fusarium oxide, fenamidone, fenaminstrobin, fenarimol, feneptamidoquin, fenoxanil, fenopyramid, ferimzone, fenpiclonil, fenpicoxamid, fenpyrazamine, fenbuconazole, fenfuram, fenpropidin, fenpropimorph, fenhexamid, folpet, phthalide, Fusarium oxysporumoxysporum), bupirimate, fuberidazole, blasticidin-S, furametpyr, furalaxyl, furancarboxylic acid fluazinam, fluindapyr, fluoxastrobin, fluoxapiprolin, fluoxytioconazole, fluopicolide, fluopimomide, fluopyram, fluoroimide, fluxapyroxad, fluquinometoate, fluquinconazole, furconazole, furconazole-cis -cis), fludioxonil, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, flufenoxadiazam, flufenoxystrobin, flubeneteram, flumetylsulforim, flumetover, flumorph, Phlebiopsis gigantea(gigantea), proquinazid, prochloraz, procymidone, prothiocarb, prothioconazole, bronopol, propamocarb-hydrochloride, propiconazole, propineb, probenazole, bromuconazole, flometoquin, florylpicoxamid, hexaconazole, benalaxyl, benalaxyl. M (benalaxyl-M), benodanil, benomyl, pefurazoate, penconazole, pencycuron, benzovindiflupyr, benthiazole, benthiavalicarb-isopropyl, penthiopyrad, penflufen, boscalid, fosetyl (containing salts of aluminum, calcium, sodium, etc.), polyoxin, polycarbamate, Bordeaux mixture mixture), mancopper, mancozeb, mandipropamid, mandestrobin, maneb, myclobutanil, mineral oiloils), mildiomycin, methasulfocarb, metam, metalaxyl, metalaxyl-M, metarylpicoxamide, metiram, methyltetraprole, metconazole, metcyclofenstrobin, metminostrobin, Metrafenone, mepanipyrim, mefentrifluconazole, meptyldinocap, mepronil, iodocarb, laminarin, ledprona, phosphorus and salts, copper oxychloride, silver, copper(II) acetate, cuprous oxide, copper hydroxide, potassium bicarbonate, sodium bicarbonate, sulfur, oxyquinoline sulfate, copper sulfate sulfate), BAG-010 (code number), UK-2A (code number), dodecylbenzenesulfonate bisethylenediamine copper complex [II] (DBEDC), triphenyltin acetate (TPTA), triphenyltine chloride (TPTC), triphenyltin hydroxide (TPTH), 6-chloro-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-3-[3-(trifluoromethyl)phenoxy]pyridazine-4-carboxamide (6-chloro-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-3-[3-(trifluoro methyl)phenoxy]pyridazine-4-carboxamide) (chemical name, CAS registry number: 2435594-93-5) (International Publication No. 2020 / 109391), 3-(3-(3-cyclopropyl-2-fluorophenoxy)-6-methylpyridazin-4-yl)-5-(2,4-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine(3-(3-(3-cyclopropyl-2-fluorophenoxy)-6-methylpyridazin-4-yl)-5-(2,4-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine) (Chemical name, CAS registry number: 2446124-49-6) (International Publication No. 2020 / 127780), racemi-3-[6-chloro-3-[3-(trifluoromethyl)phenoxy]pyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (rac-3-[6-chloro-3-[3-(trifluoromethyl)phenoxy]pyridazin-4-yl]-5-[(2,4-dimethylphenoxy l)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine) (chemical name, CAS registry number: 2446124-68-9) (International Publication No. 2020 / 127780), 3-(3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl)-5-(2-chloro-4-methylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine(3-(3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl)-5-(2- chloro-4-methylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine) (chemical name, CAS registry number: 2446129-82-2) (International Publication No. 2020 / 127780), 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-(2-(2,4-dimethylphenyl)-2,2-difluoroethyl)-5-methylpyridazine-4-carboxamide (6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-(2-(2 ,4-dimethylphenyl)-2,2-difluoroethyl)-5-methylpyridazine-4-carboxamide) (Chemical name, CAS registry number: 2435604-64-9) (International Publication No. 2020 / 109391), 6-chloro-N-[2-(2,4-dimethylphenyl)-2,2-difluoroethyl]-5-methyl-3-[3-(trifluoromethyl)phenoxy]pyridazine-4-carboxamide (6-chloro-N-[2-(2,4-dimethylphenyl)-2,6-chloro-N-[2-(2,4-dimethylphenyl)ethyl]-3-[3-(trifluoromethyl)phenoxy]pyridazine-4-carboxamide) (chemical name, CAS registry number: 2435603-06-6) (International Publication No. 2020 / 109391), 6-chloro-N-[2-(2,4-dimethylphenyl)ethyl]-3-[3-(trifluoromethyl)phenoxy]pyridazine-4-carboxamide) (chemical name, CAS registry number: 2435600-09-0) (International Publication No. 2020 / 109391), 6-chloro-N-[2-(2,4-dimethylphenyl)ethyl]-5-methyl-3-[3-(trifluoromethyl)phenoxy]pyridazine-4-carboxamide) (chemical name, CAS registry number: 2435600-09-0) (International Publication No. 2020 / 109391), 6-chloro-N-[2-(2,4-dimethylphenyl)ethyl]-5-methyl-3-[3-(trifluoromethyl)phenoxy] [6-chloro-N-[2-(2,4-dimethylphenyl)ethyl]-5-methyl-3-[3-(trifluoromethyl)phenoxy]pyridazine-4-carboxamide] (chemical name, CAS registry number: 2435603-15-7) (International Publication No. 2020 / 109391), racemi-3-[6-chloro-5-methyl-3-[3-(trifluoromethyl)phenoxy]pyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (rac-3-[6-chloro-5-methyl-3-[3-(trifluoromethyl)phenoxy]pyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine) (Chemical name, CAS registry number: 2446123-98-2) (International Publication No. 2020 / 127780), N'-(2-chloro-4-(2-fluorophenoxy)-5-methylphenyl)-N-ethyl-N-methylformimidamide (Chemical name, CAS registry number: 2055756-21-1) (Country International Publication No. 2016 / 202742 (abbreviated code: E1), 2-(difluoromethyl)-N-(1,1-dimethyl-3-propyl-2,3-dihydro-1H-inden-4-yl)nicotinamide (chemical name, CAS registry number: 1847460-05-2) (International Publication No. 2015 / 197530) (abbreviated) Formula code: E2), 2-(difluoromethyl)-N-[(3R)-2,3-dihydro-1,1-dimethyl-3-propyl-1H-inden-4-yl]nicotinamide (Chemical name, CAS registry number: 1952306-00-1) (International Publication No. 2016 / 096849) (Abbreviated code: E2'), 2 -(6-(4-chlorophenoxy)-2-(trifluoromethyl)pyridin-3-yl)-1-(1H-1,2,4-triazol-1-yl)propan-2-ol) (Chemical name, CAS registry number: 2082660-27-1) (International Publication No. 2017 / 029179) (Abbreviated code: E3).

[0065] Next, examples of known biopesticides that may be mixed or used in combination are listed below.

[0066] Biopesticides: Haplothrips brevitubus, Franklinothrips vespiformis, Diglyphus isaea, Encarsia formosa, Amblyseius cucumeris, Pseudaphycus malinus, Amblyseius womersleyi, Aphidius colemani, Eretmocerus eremicus, Aphidoletes aphidimyza, Amblyseius swirskii, Orius Phytoseiulus persimilis, Amblyseius degenerans, Phytoseiulus persimilis, Orius sauteri, Dacnusa sibirica, Amblyseius californicus, Chrysoperla nipponensis, Anicetus beneficus.

[0067] Next, examples of known agricultural materials that may be mixed or used in combination are given below.

[0068] Agricultural supplies: Ethylene, hypochlorous acid water (limited to that obtained by electrolysis of hydrochloric acid or potassium chloride aqueous solution), baking soda, vinegar, humic substances, humic acid, fulvic acid, seaweed extract, polysaccharides, amino acids, microbial materials, functional components derived from plants and animals, microbial metabolites, microbial activating materials, soil spreading agents, soil permeability adjusting materials, soil water retention materials, etc., and biostimulants.

[0069] Next, examples of known agricultural fertilizer components that may be mixed or used in combination are given below. Fertilizers include inorganic fertilizers and organic fertilizers, among others.

[0070] Agricultural fertilizer ingredients: Ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium dihydrogen phosphate, ammonium urea nitrate, urea, calcium cyanamide, potassium nitrate, superphosphate, triple superphosphate, potassium dihydrogen phosphate, potassium chloride, potassium sulfate, potassium carbonate, potassium silicate, potassium phosphite, oilseed meal, fish meal, rice bran, bat guano, fermented chicken manure.

[0071] In this invention, useful plants include field crops or paddy field crops, horticultural crops (vegetables, fruit trees), ornamental woody plants (flowering trees, street trees), grasses, flowers, ornamental plants, medicinal plants, and timber. Examples include, but are not limited to, the following.

[0072] Field crops or paddy field crops: Corn, rice, wheat, durum wheat, barley, rye, rye wheat, spelt wheat, club wheat, oats, sorghum, cotton, soybeans, alfalfa, peanuts, kidney beans, lima beans, adzuki beans, cowpeas, mung beans, urad beans, safflower beans, bamboo beans, moss beans, teparie beans, broad beans, peas, chickpeas, lentils, lupin, pigeon peas, buckwheat, sugar beets, rapeseed, canola, sunflowers, sugarcane, cassava, yams, oil palm, tuff, hemp, flax, quinoa, safflower, tea plant, mulberry, tobacco, camelina, teff, guayure, rubber tree, etc.

[0073] Horticultural crops (vegetables): Solanaceae vegetables (eggplant, tomato, bell pepper, chili pepper, potato, etc.), Cucurbitaceae vegetables (cucumber, pumpkin, zucchini, watermelon, melon, squash, etc.), Brassicaceae vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, mustard greens, broccoli, cauliflower, etc.), Asteraceae vegetables (burdock, garland chrysanthemum, artichoke, lettuce, etc.), Liliaceae vegetables (leek, onion, garlic, asparagus, etc.), Apiaceae vegetables (carrot, parsley, celery, angelica tree, etc.), Amaranthaceae vegetables (spinach, Swiss chard, etc.), Lamiaceae vegetables (perilla, mint, basil, lavender, etc.), strawberries, sweet potatoes, yams, taro, sesame, etc.

[0074] Horticultural crops (fruit trees): Pome fruits (apples, European pears, Japanese pears, Chinese pears, quince, marzipan, etc.), drupes (peaches, plums, nectarines, apricots, cherries, apricots, prunes, etc.), citrus fruits (Unshu mandarins, oranges, lemons, limes, grapefruit, etc.), nuts (chestnuts, walnuts, hazelnuts, almonds, hazelnuts, pistachios, cashews, macadamia nuts, pecans, etc.), berries (blueberries, cranberries, blackberries, raspberries, etc.), grapes, persimmons, olives, loquats, bananas, coffee, dates, coconuts, oil palms, etc.

[0075] Ornamental woody plants (flowering trees, street trees): Ash, birch, dogwood, eucalyptus, ginkgo, lilac, maple, oak, poplar, Judas tree, sweetgum, plane tree, zelkova, Japanese cypress, fir, hemlock, juniper, pine, spruce, yew, elm, horse chestnut, coral tree, Japanese yew, cedar, cypress, croton, spindle tree, photinia, etc.

[0076] Grasses: Grasses (Zoysia japonica, Zoysia japonica, etc.), Bermuda grasses (Zoysia japonica, etc.), bentgrasses (Poa annua, Poa crus-galli, Poa japonica, etc.), bluegrasses (Poa annua, Poa maximowiczii, etc.), fescue (Phesanthemum boreale, Poa japonica, Poa crus-galli, etc.), ryegrass (Ryegrass, Ryegrass, etc.), orchard grass, timothy grass, etc.

[0077] Flowering plants, ornamental plants: Roses, carnations, chrysanthemums, lisianthus, baby's breath, gerberas, marigolds, salvias, petunias, verbenas, tulips, asters, gentians, lilies, pansies, cyclamen, orchids, lilies of the valley, lavender, stocks, ornamental cabbages, primroses, poinsettias, gladiolus, cattleyas, daisies, verbenas, cymbidiums, begonias, etc.

[0078] Medicinal plants: Chamomile varieties, licorice, turmeric, Korean ginseng, Coptis japonica, peony, poppy, etc.

[0079] Timber: Fir trees, spruce trees, pine trees, cypress, cedar, Japanese cypress, eucalyptus, etc.

[0080] Furthermore, the term "useful plants" in this invention also includes plants that have been conferred resistance to herbicides such as 4-hydroxyphenylpyruvate dioxygenase (4-HPPD) inhibitors like isoxaflutol, acetolactic acid synthase (ALS) inhibitors like imazetapyr and thifensulfuron-methyl, 5-enolpyruvirshikimate-3-phosphate (EPSP) synthase inhibitors like glyphosate, glutamine synthase inhibitors like glufosinate, acetyl-CoA carboxylase (ACCace) inhibitors like cethoxydim, protoporphyrinogen oxidase (PPO) inhibitors like flumioxazine and epiriphenacil, photosystem II inhibitors like bromoxynil, and herbicides like dicamba and 2,4-D through classical breeding methods, genetic engineering, and genome editing.

[0081] Examples of "useful plants" that have been given resistance through classical breeding methods include rapeseed, wheat, sunflower, rice, and corn that are resistant to imidazolinone-based ALS inhibitor herbicides such as imazetapyr, and are already sold under the trade name Clearfield (registered trademark). Similarly, Cultivance has been developed as a soybean resistant to imidazolinone-based ALS inhibitor herbicides.

[0082] Similarly, soybeans resistant to sulfonylurea ALS inhibitors such as thifensulfuron-methyl, bred using classical methods, are already available under the trade name STS soybeans. Similarly, sorghum resistant to sulfonylurea acetolactate synthase (ALS) inhibitors, bred using classical methods, are already available. Similarly, sugar beets resistant to acetolactate synthase (ALS) inhibitors, resistant to thiencarbazone, bred using classical methods, are already available. Similarly, examples of useful plants resistant to acetyl-CoA carboxylase (ACCace) inhibitors such as trione oxime and aryloxyphenoxypropionic acid herbicides, bred using classical methods, include SR corn and quizalo hop-resistant wheat. Useful plants conferred resistance to acetyl-CoA carboxylase (ACCace) inhibitors have been described in the Proceedings of the National Academy of Sciences of the United States of America (Proc. Natl. Acad. Sci. USA), Vol. 87, pp. 7175-7179 (1990), among others. Furthermore, mutant acetyl-CoA carboxylase (ACCace) that is resistant to acetyl-CoA carboxylase (ACCace) inhibitors has been reported in Weed Science, Vol. 53, pp. 728-746 (2005), among others. Plants resistant to acetyl-CoA carboxylase inhibitors can be created by introducing such mutant acetyl-CoA carboxylase genes into plants using genetic engineering technology, or by introducing mutations related to resistance conferral into crop acetyl-CoA carboxylase (ACCace). Furthermore, by introducing nucleic acids with base substitution mutations, such as those produced by chimeric plasty (Gura T. 1999. Repairing the Genome's Spelling Mistakes. Science 285:316-318), into plant cells to induce site-directed amino acid substitution mutations in crop genes (acetyl-CoA carboxylase (ACCace) / herbicide target), it is possible to create plants resistant to acetyl-CoA carboxylase (ACCace) inhibitors / herbicides.

[0083] Examples of useful plants conferred with resistance through genetic modification include glyphosate-resistant varieties of corn, soybeans, cotton, rapeseed, sugar beet, and alfalfa, which are already sold under trade names such as Roundup Ready (registered trademark), Roundup Ready 2 (registered trademark), AgrisureGT (registered trademark), and GlyTol (registered trademark). Similarly, Optimum GAT is a soybean and corn variety resistant to both glyphosate and ALS inhibitors, achieved through genetic modification. Likewise, glufosinate-resistant varieties of corn, soybeans, cotton, and rapeseed, achieved through genetic modification, are already sold under trade names such as LibertyLink (registered trademark). Similarly, bromoxynil-resistant cotton, achieved through genetic modification, is already sold under the trade name BXN. Similarly, soybeans resistant to HPPD inhibitors, produced through genetic modification technology, are already sold under the trade name Herbicide-tolerant Soybean line as a variety resistant to mesotrione and glufosinate, and under the trade name Credenz (registered trademark), etc., as a variety resistant to HPPD inhibitors, glyphosate, and glufosinate. Similarly, corn, soybeans, and cotton resistant to 2,4-D or ACCase inhibitors, produced through genetic modification technology, are already sold under the trade name Enlist (registered trademark), etc. Similarly, soybean varieties resistant to 2,4-D, glyphosate, and glufosinate, produced through genetic modification technology, are already sold under the trade name Enlist E3. Similarly, soybeans resistant to dicamba, produced through genetic modification technology, are already sold under the trade name Roundup Ready 2 Xtend (registered trademark), etc., as a variety resistant to dicamba and glyphosate. Similarly, a soybean variety that is resistant to HPPD inhibitors such as isoxaflutol and also resistant to nematodes, due to genetic modification technology, has been registered in the United States as GMB151.

[0084] Further plants with modified resistance to herbicides are widely known, for example, alfalfa, apple, barley, eucalyptus, flax, grape, lentil, rapeseed, pea, potato, rice, sugar beet, sunflower, tobacco, tomato sedge and wheat (see, e.g., US5188642, US4940835, US5633435, US5804425, US5627061), and legumes and cotton with resistance to dicamba. Soybeans, peas, potatoes, sunflowers, tomatoes, tobacco, corn, sorghum and sugarcane (see, e.g., WO2008 / 051633, US7105724 and US5670454), soybeans, sugar beets, potatoes, tomatoes and tobacco resistant to glufosinate (see, e.g., US6376754, US5646024, US5561236), cotton, peppers, apples, tomatoes, sunflowers, tobacco resistant to 2,4-D, Potatoes, corn, cucumbers, wheat, soybeans, sorghum, and other cereals (see, for example, US6153401, US6100446, WO2005 / 107437, US5608147U, and US5670454), and canola, corn, barnyard millet, barley, cotton, mustard greens, lettuce, lentils, melon, foxtail millet, oats, cleavers, potatoes, and rice that are resistant to ALS inhibitor herbicides (e.g., sulfonylurea herbicides or imidazolinone herbicides). Rye, sorghum, soybeans, sugar beets, sunflowers, tobacco, tomatoes and wheat (see, for example, US5013659, WO2006 / 060634, US4761373, US5304732, US6211438, US6211439 and US6222100), particularly rice resistant to imidazolinone herbicides, is known to have specific mutations in the acetolactate synthase gene (e.g., S653N, S654K, A122T, S653(At)N, S654(At)K,Rice containing A122(At)T (see, e.g., US2003 / 0217381, WO2005 / 020673), barley, sugarcane, rice, maize, and tobacco resistant to HPPD inhibitor herbicides (e.g., isoxazole herbicides such as isoxaflutol, triketone herbicides such as sulcotrione and mesotrione, and pyrazole herbicides such as pyrazolinates) or diketonitrile, a degradation product of isoxaflutol. Examples include soybeans, cotton, rapeseed, sugar beets, wheat, and potatoes (see, for example, WO2004 / 055191, WO1996 / 38567, WO1997 / 049816, and US6791014), as well as wheat, soybeans, cotton, sugar beets, rapeseed, rice, maize, sorghum, sugarcane, and sugar beets resistant to PPO inhibitor herbicides (see, for example, US2002 / 0073443, US2008 / 0052798, Pest Management Science, 61, 2005, 277-285).

[0085] Plants that have been given herbicide resistance through conventional breeding techniques or genome breeding techniques include, for example, rice "Clearfield® Rice", wheat "Clearfield® Wheat", sunflower "Clearfield® Sunflower", lentils "Clearfield® lentils", and canola "Clearfield® canola", which are resistant to imidazolinone-based ALS inhibitor herbicides such as imazetapyr and imazamox; soybeans "STS soybean", which are resistant to sulfonylurea-based ALS inhibitor herbicides such as thifensulfuron-methyl; and corn "SR", which is resistant to acetyl-CoA carboxylase inhibitors such as trione oxime herbicides and aryloxyphenoxypropionic acid herbicides. Examples include corn (also known as "PoastProtected<registered trademark>corn"), sunflower "ExpressSun<registered trademark>" which is resistant to sulfonylurea herbicides such as tribeurone, rice "Provisia<registered trademark> Rice" which is resistant to acetyl-CoA carboxylase inhibitors such as quizalohop, canola "Triazine Tolerant Canola" which is resistant to photosystem II inhibitors, and sorghum "Igrowth<registered trademark>" which is resistant to imidazolinone herbicides.

[0086] One example of a plant conferred with herbicide resistance through genome editing technology is "SU Canola" (registered trademark), a canola variety resistant to sulfonylurea herbicides developed using Rapid Trait Development System (RTDS) (registered trademark). RTDS (registered trademark) is an oligonucleotide-directed mutational introduction technique of genome editing technology, which allows for the introduction of mutations in plants without cleaving the DNA, via Gene Repair Oligonucleotide (GRON), i.e., a chimeric oligonucleotide of DNA and RNA. Other examples include maize with reduced herbicide resistance and phytic acid content by deleting the endogenous gene IPK1 using zinc finger nuclease (see, e.g., Nature 459, 437-441 2009), and rice conferred with herbicide resistance using CRISPR-Cas9 (see, e.g., Rice, 7, 5 2014).

[0087] An example of a plant conferred with herbicide resistance through new breeding techniques is soybeans in which the properties of a GM rootstock have been conferred to the scion using grafting-based variety improvement techniques. Specifically, this includes soybeans in which glyphosate resistance has been conferred to non-transgenic soybean scions by using Roundup Ready™ soybeans, which have glyphosate resistance, as the rootstock (see Weed Technology 2013, 27, 412).

[0088] The above-mentioned "useful plants" also include plants that have been made capable of synthesizing selective toxins, such as those known from the Bacillus genus, using genetic engineering technology.

[0089] Examples of insecticidal toxins expressed in such genetically modified plants include: insecticidal proteins derived from Bacillus cereus and Bacillus popilliae; δ-endotoxins such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry14Ab-1, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C derived from Bacillus thuringiensis; insecticidal proteins such as VIP1, VIP2, VIP3, or VIP3A; insecticidal proteins derived from nematodes; toxins produced by animals such as scorpion venom, spider venom, wasp venom, or insect-specific neurotoxins; filamentous fungal toxins; plant lectins; aglutinin; protease inhibitors such as trypsin inhibitors, serine protease inhibitors, patain, cystatin, and papain inhibitors. Examples of agents include: ribosome inactivating proteins (RIP) such as lysine, maize-RIP, abrin, saporin, and briodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glucosyltransferase, and cholesterol oxidase; ecdysone inhibitors; HMG-CoA reductase; ion channel inhibitors such as sodium channel inhibitors and calcium channel inhibitors; juvenile hormone esterases; diuretic hormone receptors; stilbenzyl synthase; bibenzyl synthase; chitinase; glucanase, etc.

[0090] Furthermore, toxins expressed in such genetically modified plants include hybrid toxins of δ-endotoxin proteins such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry14Ab-1, Cry2Ab, Cry3A, Cry3Bb1, Cry9C, Cry34A, Cry34Ab, or Cry35Ab, and insecticidal proteins such as VIP1, VIP2, VIP3, or VIP3A, as well as toxins with partial deletions and modified toxins. Hybrid toxins are created using recombinant technology by novel combinations of different domains of these proteins. Among toxins with partial deletions, Cry1Ab, which has a partial deletion in its amino acid sequence, is known. Modified toxins have one or more amino acids substituted in the naturally occurring toxin.

[0091] Examples of these toxins and recombinant plants capable of synthesizing them are described in patent documents such as EP-A-0374753, WO93 / 07278, WO95 / 34656, EP-A-0427529, EP-A-451878, and WO03 / 052073. The toxins contained in these recombinant plants confer resistance to plants, in particular, to coleopteran, dipteran, and lepidopteran insect pests.

[0092] Furthermore, genetically modified plants containing one or more insecticidal pest resistance genes and expressing one or more toxins are already known, and some are commercially available. Examples of these genetically modified plants include YieldGard (a maize variety expressing Cry1Ab toxin), YieldGard Rootworm (a maize variety expressing Cry3Bb1 toxin), YieldGard Plus (a maize variety expressing both Cry1Ab and Cry3Bb1 toxins), Herculex I (a maize variety expressing phosphinotricin N-acetyltransferase (PAT) to confer resistance to Cry1Fa2 toxin and glufosinate), NuCOTN33B (a cotton variety expressing Cry1Ac toxin), Bollgard I (a cotton variety expressing Cry1Ac toxin), and Bollgard II (a cotton variety expressing Cry1Ac toxin). II) Examples include <Registered Trademark> (cotton varieties expressing Cry1Ac and Cry2Ab toxins), VIPCOT <Registered Trademark> (cotton varieties expressing VIP toxin), NewLeaf <Registered Trademark> (potato varieties expressing Cry3A toxin), NatureGard Agrisure GT Advantage (GA21 glyphosate resistance trait), Agrisure CB Advantage (Bt11 corn borer (CB) trait), Protecta <Registered Trademark>, Intacta <Registered Trademark>, SmartStax <Registered Trademark>, etc.

[0093] Examples of plants conferred with pest resistance using classical breeding methods or genetic modification technology include soybeans possessing the aphid resistance genes Rag1 (Resistance to Aphis glycines 1) or Rag2 (Resistance to Aphis glycines 2), soybeans resistant to soybean cyst nematodes (Heterodera glycines), cotton resistant to root-knot nematodes (Meloidogyne incognita), Kanto BPH1 rice resistant to brown planthoppers, and Fukuminori soybeans resistant to beet armyworms.

[0094] The above-mentioned useful plants include those that have been given resistance to nematodes using classical breeding methods or genetic engineering techniques. For example, RNA interference (RNAi) is a genetic engineering technique used to confer nematode resistance.

[0095] As plants conferred with pest resistance using RNAi, corn resistant to lepidopteran pests (e.g., corn borers, corn earworms, cutworms such as black cutworms, and fall armyworms) and coleopteran pests (corn rootworms) is commercially available or under development as SmartStax<registered trademark>, SmartStax<registered trademark> Pro, or Genuity<registered trademark> SmartStax Pro.

[0096] The above-mentioned useful plants include those that have been genetically modified to possess the ability to produce antipathogenic substances with selective action.

[0097] Examples of antipathogenic substances include PR proteins (PRPs, described in EP-A-0392225); ion channel inhibitors such as sodium channel inhibitors and calcium channel inhibitors (KP1, KP4, and KP6 toxins produced by viruses are known); stilbene synthase; vibenzyl synthase; chitinase; glucanase; peptide antibiotics; heterocyclic antibiotics; and substances produced by microorganisms, such as protein factors involved in plant disease resistance (called plant disease resistance genes, described in WO03 / 000906). Such antipathogenic substances and genetically modified plants that produce them are described in EP-A-0392225, WO95 / 33818, EP-A-0353191, etc.

[0098] The above-mentioned useful plants also include crops that have been genetically modified to confer useful traits such as modified oil content or enhanced amino acid content. Examples include VISTIVE (registered trademark) (low-linolenic soybeans with reduced linolenic content) and high-lysine (high oil) corn (corn with increased lysine or oil content).

[0099] The above-mentioned useful plants include crops that have been genetically modified to confer useful traits such as drought tolerance, thereby maintaining or increasing yield. Examples include DroughtGard (registered trademark), AGRISURE ARTESIAN (registered trademark), OPTIMUM (registered trademark), and AQUAMAX (registered trademark) (corn with conferred drought tolerance).

[0100] The herbicide of the present invention also exhibits control effects against the harmful organisms exemplified above that have acquired resistance to existing herbicides. Furthermore, the herbicide of the present invention can also be used on plants that have acquired characteristics such as pest resistance, disease resistance, and herbicide resistance through genetic modification, artificial crossbreeding, etc.

[0101] In this invention, "plants transformed through cultivation by breeding methods or genetic modification technology" includes not only plants that have acquired resistance through classical crossbreeding and genetic modification technology, but also plants that have acquired resistance through new plant breeding techniques (NBTs) that combine conventional crossbreeding techniques with molecular biological methods. New plant breeding techniques (NBTs) are described in the book "Understanding New Plant Breeding Techniques" (International Literature Co., Ltd., by Ryo Osawa and Hiroshi Emoto), the review article "Genome Editing Tools in Plants" (Genes 2017, 8, 399, by Tapan Kumar Mohanta, Tufail Bashir, Abeer Hashem, Elsayed Fathi Abd_Allah and Hanhong Bae), etc. Examples of the above-mentioned new plant breeding techniques include genome breeding technology and genome editing technology. Genome breeding technology is a technology for making breeding more efficient using genomic information, and includes DNA marker (also called genome marker or gene marker) breeding technology and genomic selection. For example, DNA marker breeding is a method of selecting offspring with the desired useful trait gene from a large number of crosses using DNA markers, which are DNA sequences that serve as markers for the location of a specific useful trait gene on the genome. By analyzing the cross offspring using DNA markers when they are still seedlings, this method has the advantage of effectively shortening the time required for breeding.

[0102] Furthermore, genomic selection is a technique that creates a prediction formula from previously obtained phenotypic and genomic information, and predicts characteristics from the prediction formula and genomic information without evaluating phenotypes, and is a technology that can contribute to the efficiency of breeding. New breeding techniques are a general term for plant breeding techniques that combine molecular biological methods. Examples include cisgenesis / intragenesis, oligonucleotide-directed mutagenesis, RNA-dependent DNA methylation, genome editing, grafting onto GM rootstock or scion, reverse breeding, agroinfiltration, and seed production technology (SPT). Genome editing technology is a technique that transforms genetic information in a sequence-specific manner, and can perform deletions of base sequences, substitutions of amino acid sequences, and introduction of foreign genes. Examples of such tools include zinc finger nucleases (ZFNs), TALEN, CRISPR / Cas9, CRISPR / Cpf1, and meganucleases, all of which are capable of sequence-specific cleavage. Additionally, there are sequence-specific genome modification technologies such as CAS9 nickase and Target-AID, which are created by modifying the aforementioned tools.

[0103] Furthermore, this also includes stacked varieties that combine multiple useful traits, such as the classic herbicide traits mentioned above, or herbicide resistance genes, insecticidal pest resistance genes, antipathogenic substance production genes, oilseed component modification, amino acid content enhancement traits, and drought tolerance traits.

[0104] Non-agricultural land as a setting for the use of the herbicide and agricultural chemical composition (a concept including the herbicide) of the present invention refers to, for example, non-agricultural land where it is necessary to control weed growth, such as the slopes of embankments, riverbeds, road shoulders and slopes, railway tracks, parks and green spaces, grounds, parking lots, airports, industrial facility sites such as factories and storage facilities, fallow land, or vacant land in urban areas, or orchards, pastures, forestry areas, rivers, waterways, canals, reservoirs, etc.

[0105] As described above, the herbicide and agricultural chemical composition (a concept including the herbicide) of the present invention have herbicidal activity against various weeds. Examples of such weeds are given below, but the invention is not limited to these examples.

[0106] Weeds of the Urticaceae family: Urtica urens.

[0107] Polygonaceae weeds: Buckwheat vine (Polygonum convolvulus), buckwheat vine (Polygonum lapathifolium), American buckwheat vine (Polygonum pensylvanicum), spring vine (Polygonum persicaria), Japanese buckwheat vine (Polygonum longisetum), roadside vine (Polygonum aviculare), dark roadside vine (Polygonum arenastrum), Japanese knotweed (Polygonum cuspidatum), dock (Rumex japonicus), long-leaved dock (Rumex crispus), Ezo dock (Rumex obtusifolius), sorrel (Rumex acetosa), dwarf sorrel (Rumex acetosella), and buckwheat vine (Persicaria nepalensis).

[0108] Portulacaceae (a type of weed): Portulaca oleracea.

[0109] Caryophyllaceae weeds: Stellaria media, Stellaria aquatica, Cerastium holosteoides, Cerastium glomeratum, Spergula arvensis, Silene gallica, Stellaria alsine.

[0110] Weeds of the Molluginaceae family: Mollugo verticillata (a type of lily).

[0111] Amaranthaceae weeds: Amaranthus retroflexus, Amaranthus viridis, Amaranthus lividus, Amaranthus spinosus, Amaranthus hybridus, Amaranthus palmeri, Amaranthus patulus, Water hemp (Amaranthus tuberculatus=Amaranthus rudis=Amaranthus tamariscinus), American amaranth (Amaranthus blitoides), dwarf amaranth (Amaranthus deflexus), Amaranthus quitensis, Amaranthus spinosus, Alternanthera philoxeroides), Alternanthera sessilis, Alternanthera tenella, Amaranthus powelii, Amaranthus rudis, Amaranthus albus, Amaranthus viridis, Amaranthus lividus, Amaranthus patulus, Chenopodium album, Chenopodium ambrosioides, Kochia scoparia, Salsola kali, Atriplex spp.

[0112] Papaveraceae (Papaveraceae family weeds): Common poppy (Papaver rhoeas), long-headed poppy (Papaver dubium), thistle poppy (Argemone mexicana).

[0113] Brassicaceae weeds: Radish (Raphanus raphanistrum), Radish (Raphanus sativus), Wild Mustard (Sinapis arvensis), Shepherd's Purse (Capsella bursa-pastoris), European Brassica (Brassica juncea), European Rapeseed (Brassica napus), Brassica rapa, Dwarf Whale Grass (Descurainia pinnata), Scallop (Rorippa islandica), Broccoli's Bush Grass (Rorippa sylvestris), Lapweed (Thlaspi arvense), Miyagarashi (Myagrum rugosum), Bean Lapweed (Lepidium virginicum), Coronopus didymus, Whale Grass (Descurarinia sophia), Dog Grass (Rorippa (Indica), Sisymnrium officinale, Cardamine flexuosa, Nasturtium officinale, Draba nemorosa.

[0114] Capparaceae (weeds): Cleome affinis.

[0115] Leguminous weeds (Fabaceae): Aeschynomene indica, Zigzag joint vetch (Aeschynomene enerudis), Aeschynomene denticulata, Aeschynomene rudis, Sesbania exaltata, Cassia obtusifolia, Cassia occidentalis, Desmodium tortuosum, Desmodium adscendens, Desmodium illinoense, White clover (Trifolium repens), Pueraria lobata, Vicia angustifolia, Indigofera hirsuta, Indigofera torxylenesis (Truxillensis), cowpea (Vigna sinensis), Crotalaria incana, Vicia sativa, Medicago lupulina, Vicia hirsuta; Kummerowia striata, Medicago polymorpha.

[0116] Oxalidaceae weeds: Oxalis corniculata, Oxalis strica, Oxalis oxyptera, and Oxalis debilis.

[0117] Geraniaceae weeds: American cranesbill (Geranium carolinense), Dutch cranesbill (Erodium cicutarium), Dove's Foot Crane's-bill (Geranium molle), Hedgerow Crane's-bill (Geranium pyrenaicum).

[0118] Euphorbiaceae (a type of weed): Euphorbia helioscopia, Euphorbia maculata, Euphorbia hum istrata, Euphorbia esula, Euphorbia heterophylla, Euphorbia brasiliensis, Acalypha australis, Croton glandulosus, Croton lobatus, Phyllanthus corcovadensis, Ricinus com m unis, Astraea lobata, Chamaesyce hirta, Chamaesyce hyssopifolia.

[0119] Malvaceae weeds: Abutilon theophrasti, Sida rhombiforia, Sida cordifolia, Sida spinosa, Sida glaziovii, Sida santaremnensis, Sida urens, Hibiscus trionum, Anoda cristata, Malvastrum corom andelianum, Triumfetta rhomboidea.

[0120] Onagraceae (a type of weed): Ludwigia epilobioides, Ludwigia octovalvis, Ludwigia decurre, Ludwigia leptocarpa, Oenothera biennis, and Oenothera laciniata.

[0121] Sterculiaceae weeds: Waltheria indica (a type of tree) Violaceae weeds: Viola arvensis, wild pansy (Viola tricolor).

[0122] Cucurbitaceae weeds: Wild cucumber (Sicyos angulatus), wild cucumber (Echinocystis lobata), bitter melon (Momordica charantia).

[0123] Lythraceae weeds: Ammannia multiflora, Ammannia auriculata, Ammannia coccinea, Lythrum salicaria, and Rotala indica.

[0124] Elatinaceae weeds: Elatine triandra, California water wort (Elatine californica).

[0125] Apiaceae family weeds: Japanese parsley (Oenanthe javanica), wild carrot (Daucus carota), poison hemlock (Coniumm aculatum), and pine celery (Cyclospermum leptophyllum).

[0126] Araliaceae weeds: Hydrocotyle sibthorpioides, Brazilian Hydrocotyle (Hydrocotyle ranunculoides).

[0127] Weeds of the hornwort family (Ceratophyllaceae): Hornwort (Ceratophyllum demersum).

[0128] Cabom baceae (a type of weed): Cabomba caroliniana (Japanese pygmy tree).

[0129] Haloragaceae (a type of weed): Examples include Myriophyllum aquaticum, Myriophyllum verticillatum, Myriophyllum matogrossense, and water millfoil species (Myriophyllum spicatum, Myriophyllum heterophyllum), etc.

[0130] Sapindaceae weeds: Balloon vine (Cardiospermum halicacabum).

[0131] Primulaceae weed: Blue pimpernel (Anagallis arvensis).

[0132] Milkweeds (Asclepiadaceae family): Asclepias syriaca (giant milkweed), honeyvine milkweed (Ampelamus albidus).

[0133] Rubiaceae weeds: Galium aparine, Galium spurium var. echinospermon, Spermacoce latifolia, Diodella teres, Richardia brasiliensis, and Borreria alata.

[0134] Convolvulaceae (morning glory family weeds): Morning glory (Ipomoea nil), American morning glory (Ipomoea hederacea), round-leaved morning glory (Ipomoea purpurea), round-leaved American morning glory (Ipomoea hederacea var. integriuscula), bean morning glory (Ipomoea lacunosa), star morning glory (Ipomoea triloba), field morning glory (Ipomoea acuminata), ivy vine (Ipomoea hederifolia), cypress vine (Ipomoea coccinea), cypress vine (Ipomoea quamoclit), Ipomoea grandifolia, Ipomoea aristolochiafolia, maple leaf-leaved morning glory (Ipomoea cairica), European morning glory (Convolvulus) arvensis), Calystegia hederacea, Calystegia japonica, Merremia hedeacea, Merremia aegyptia, Merremia cissoides, Jacquemontia tamnifolia.

[0135] Boraginaceae weeds: Forget-me-not (Myosotis arvensis), wild purple (Myosotis arvensis), dog purple (Lithospermum officinale), plant lily (Echium plantagineum), and sweet blue flower (Heliotropium indicum).

[0136] Lamiaceae (mint family weeds): Lamium purpureum, Lamium amplexicaule, Leonotis nepetaefolia, Hyptis suaveolens, Hyptis lophanta, Leonurus sibiricus, Stachys arvensis, Leonurus sibiricus, and Marsypianthes chamaedrys.

[0137] Solanaceae weeds: Datura stramonium, Solanum nigrum, Solanum americanum, Solanum ptycanthum, Solanum sarrachoides, Solanum rostratum, Solanum aculeatissimum, Solanum sisym briifolium, Solanum carolinense, Physalis angulata, Physalis subglabrata, Nicandra physaloides.

[0138] Linderniaceae weeds: Lindernia procumbens, Lindernia dubia, Lindernia angustifolia.

[0139] Plantaginaceae weeds: Plantago asiatica, Plantago lanceolata, Plantago major, Callitriche palustris, Limnophila sessiliflora, Dopatrium junceum, Gratiola japonica, Bacopa rotundifolia, Veronica hederaefolia, Veronica persica, Veronica arvensis, Veronica anagallis-aquatica, Plantago tomentosa.

[0140] Asteraceae weeds: Xanthium pensylvanicum, Xanthium occidentale, Xanthium italicum, Helianthus annuus, Matricaria chamomilla, Matricaria perforata, Chrysanthemum segetum, Matricaria matricarioides, Artemisia princeps, Artemisia vulgaris, Artemisia verlotorum, Solidago altissima, Taraxacum officinale, Galinsoga ciliata, Galinsoga Parviflora), Senecio vulgaris, Senecio brasiliensis, Senecio grisebachii, Conyza bonariensis, Conyza sumatrensis, Conyza canadensis, Ambrosia artemisiifolia, Ambrosia trifida, Bidens tripartita, Bidens pilosa, Bidens frondosa, Bidens subalternans, Cirsium arvense, Cirsium vulgare, Silybum marianum), musk lettuce (Carduus nutans), spiny lettuce (Lactuca serriola), sow thistle (Sonchus oleraceus), prickly sow thistle (SonchusAsper, Beach Creeping Oxeye (Wedeliaglauca), Perforated Blackfoot (Melampodium perfoliatum), Red Red Ixflower (Emilia sonchifolia), Southern Red Ixflower (Emilia fosbergii), Tagetes minuta, Paracles (Blainvillea latifolia), Blainvillea dichotoma, Kotobuki Chrysanthemum (Tridax procumbens), Yerbaporosa (Porophyllum ruderale), Paraguay Starbar (Acanthospermum australe), Bristle Starbar (Acanthospermum hispidum), Balloon Vine (Cardiospermum um halicacabum), Cuckoo Thistle (Ageratum conyzoides), Common Bone Set (Eupatorium) Eclipta perfoliatum, Eclipta alba, Erechtites hieracifolia, Gamochaeta spicata, Gnaphalium spicatum, Jaegeria hirta, Parthenium hysterophorus, Siegesbeckia orientalis, Soliva sessilis, Eclipta prostrata, Centipeda minima, Anthemis cotula, Cirsium setosum, Centurea cyanus, Coreopsis lanceolata, Rudbeckia hirta), Rudbeckia laciniata, Rudbeckia laciniata var. hortensis Bailey, Bidens svartemanssubaltemans), water sunflower (Gymnocoronis spilanthoides), Hypochaeris chillensis, Pluchea sagittalis.

[0141] Alisma ataceae (weed): Sagittaria pygmaea, Sagittaria trifolia, Sagittaria sagittifolia, Sagittaria montevidensis, Sagittaria aginashi, Alisma canaliculatum, and Alisma plantago- aquatica.

[0142] Limnocharitaceae (a type of weed): Yellow arrowhead (Limnocharis flava).

[0143] Hydrocharitaceae family weeds: Frogbit (Limnobium spongia), Hydrilla verticillata, Common Water Nymph (Najas guadalupensis), and Canadian Waterweed (Egeria densa).

[0144] Araceae family weeds: Pistia stratiotes.

[0145] Lemnaceae (a family of weeds): Blue duckweed (Lemna aoukikusa), duckweed (Spirodela polyrhiza), water flea (Wolffia globosa).

[0146] Potamogetonaceae weeds: Potamogeton distinctus, pondweeds (Potamogetoncrispus, Potamogeton illinoensis, Stuckenia pectinata, etc.).

[0147] Liliaceae weeds: Wild onion (Allium canadense), wild garlic (Allium vineale), and wild garlic (Allium macrostemon).

[0148] Pontederiaceae weeds: Water hyacinth (Eichhornia crassipes), American dwarf hyacinth (Heteranthera limosa), water hyacinth (Monochoria korsakowii), dwarf hyacinth (Monochoria vaginalis), and Heterandera reniformis.

[0149] Commelinaceae weeds: Commelina communis, Commelina bengharensis, Commelina erecta, Murdannia keisak, and Murdannia nudiflora.

[0150] Grass weeds (Poaceae): Barnyard grass (Echinochloa crus-galli), Echinochloa oryzicola, Echinochloa crus-galli var formosensis, Late watergrass (Echinochloa oryzoides), Small barnyard grass (Echinochloa colona), Gulf cockspur (Echinochloa crus-pavonis), Foxtail grass (Setaria viridis), Autumn foxtail grass (Setaria faberi), Golden foxtail grass (Setaria glauca), American foxtail grass (Setaria geniculata), Digitaria ciliaris, Large crabgrass (Digitaria sanguinalis), Jamaican crabgrass (Digitaria horizontalis), Japanese pampas grass (Digitaria insularis), Eleusine (Eleusine) Poa indica, Poa annua, Poa trivialis, Poa pratensis, Alospecurus aequalis, Alopecurus myosuroides, Avena fatua, Sorghum halepense, Sorghum vulgare, Sorghum arundinaceum, Agropyron repens, Lolium multiflorum, Lolium perenne, Lolium rigidum, Bromus catharticus, Bromus sterilis, Bromus japonicus), black tea lily (Bromus secalinus), horse tea lily (Bromus tectorum), narrow-leaved barley (Hordeum jubatum), goat barley (Aegilops cylindrica), grass reed (Phalaris)arundinacea), Phalaris minor, Apera spica-venti, Panicum dichotomiflorum, Panicum texanum, Panicum maximum, Brachiaria platyphylla, Brachiaria ruziziensis, Brachiaria plantaginea, Brachiaria decumbens, Brachiaria brizantha, Brachiaria humidicola, Urochloa mutica, Cenchrus echinatus, Cenchrus pauciflorus, Eriochloa villosa, Chloris gayana), Chlorisvirgata, Eragrostis pilosa, Eragrostis plana, Rhynchelitrum repens, Dactyloctenium aegyptium, Ischaem um rugosum, Isachne globosa, Oryza sativa, Paspalum notatum, Paspalum maritimum, Paspalum distichum, Pennisetum clandestinum, Pennisetum setosum, Rottboellia cochinchinensis, Leptochloa Leptochloa chinensis, Leptochloa fascicularis, Leptochloa panicea, Leptochloafiliformis), Amazon sprangling top (Leptochloa panicoides), Japanese oak (Leersia japonica), Taiwanese oak (Leersia hexandra), Leersia sayanuka, Ezo oyster oyster (Leersia oryzoides), floating grass (Glyceria leptorrhiza), six-leaved grass (Glyceria acutiflora), loach weed (Glyceria maxima), small rice grain (Agrostis gigantea), shallow rice grain (Agrostis stolonifera), Japanese grass (Cynodon dactylon), timothy grass (Dactylis glomerata), centipede grass (Eremochloa ophiuroides), giant oxtail grass (Festucaarun) Dinacea), Festuca rubra, Imperata cylindrica, Miscanthus sinensis, Panicum virgatum, Zoysia japonica, Luziola peruviana, Melinis repens, Spartina anglica.

[0151] Cyperaceae (sedge family weed): Cyperus microiria, Cyperus iria, Cyperus compressus, Cyperus difformis, Cyperus flaccidus, Cyperus globosus, Cyperus nipponics, Cyperus odoratus, Cyperus serotinus, Cyperus rotundus, Cyperus esculentus, Kyllinga gracillima, Kyllinga brevifolia, Fimbristylis miliacea, Fimbristylis Dichotoma, Eleocharis acicularis, Eleocharis kuroguwai, Schoenoplectiella hotarui, Schoenoplectiella juncoides, Schoenoplectiella wallichii, Schoenoplectiella mucronatus, Schoenoplectiella triangulatus, Schoenoplectiella nipponicus, Schoenoplectiella triqueter, Bolboschoenus koshevnikovii, Bolboschoenus fluviatilis, Scirpus tabernaemontani.

[0152] Equisetaceae (horsetail family weed): Horsetail (Equisetum arvense), Japanese horsetail (Equisetum umpalustre).

[0153] Salviniaceae family weeds: Salvinia natans (Japanese dwarf

[0154] Azollaceae family weeds: Large red duckweed (Azolla japonica), red duckweed (Azollaim bricata), Japanese bald waterweed (Salvinia natanas), Azolla cristata.

[0155] Marsileaceae weeds: Marsilea quadrifolia.

[0156] Ricciaceae (a type of weed): Ricciocarpus natans (a type of floating moss).

[0157] Rosaceae weeds: Alchemilla monticola.

[0158] Ranunculaceae (Japanese buttercup family weeds): Ranunculus muricatus (spiny buttercup), Ranunculus sardous (warty buttercup).

[0159] Fumarioidae weeds: Fumaria officinalis (a type of citrus fruit).

[0160] Chara family weeds: Chara (Chara braunii).

[0161] Eriocaulaceae (weeds): Eriocaulon cinereum.

[0162] Weeds of the family Zygnemataceae: Spirogyra arcla.

[0163] others: Suckers of filamentous algae (Pithophora, Cladophora), mosses, liverworts, hornworts, cyanobacteria, ferns, and perennial crops (pomes, stony fruits, berries, nuts, citrus fruits, hops, grapes, etc.).

[0164] The weeds mentioned above are not limited to intraspecies mutations. That is, they also include those that have reduced sensitivity to a particular herbicide (also called "showing resistance") (herbicide-resistant weeds). Reduced sensitivity may be due to mutations in the target site (site mutation) or due to factors other than site mutations (non-site mutation). Site mutations include those in which amino acid substitutions occur in the target site protein due to mutations in the nucleic acid sequence portion (open reading frame) corresponding to the amino acid sequence of the protein, and those in which the target site protein is expressed in excess or in reduced amounts due to mutations such as deletion of suppressor sequences in the promoter region, amplification of enhancer sequences, or increase or decrease in the copy number of the gene. Non-site mutations include increased metabolism, malabsorption, dysphagia, and excretion. Factors that increase metabolism include increased activity of metabolic enzymes such as cytochrome P450 monooxygenase, aryl acylamidase, esterase, and glutathione S-transferase. Outflow from the system includes transport to the vacuole by ABC transporters.

[0165] Examples of herbicide-resistant weeds include resistance to 5-enolpyruvirshikimic acid-3-phosphate (EPSP) synthase inhibitors such as glyphosate, resistance to hormone-disrupting herbicides such as 2,4-D and dicamba, resistance to acetolactate synthase (ALS) inhibitors, resistance to acetyl-CoA carboxylase (ACCace) inhibitors, resistance to protoporphyrinogen oxidase (PPO) inhibitors, resistance to auxin-based herbicides, and resistance to 4-hydroxyphenylpyruvate dioxygenase (4-HPPD) inhibitors. Resistances include resistance to photosystem II inhibitors, photosystem I electron converters, carotenoid biosynthesis inhibitors, glutamine synthase inhibitors, phytoene desaturation system (PDS) inhibitors, fatty acid biosynthesis inhibitors, very long-chain fatty acid elongation enzymes (VLCFAE) inhibitors, auxin transport inhibitors, dihydropteroic acid (DHP) synthase inhibitors, cellulose synthase inhibitors, microtubule polymerase inhibitors, and mitosis / microtubule formation inhibitors.

[0166] Even resistant weeds that possess resistance to two or more of the above groups (any two, any three, any four, any five, six, seven, or eight groups) (stacked) are effectively controlled. An example of a stacked resistant weed is water hemp (Amaranthus tuberculatus=Amaranthus rudis=Amaranthus tamariscinus), which is resistant to all of the following: acetolactate synthase (ALS) inhibitors, protoporphyrinogen oxidase (PPO) inhibitors, 4-hydroxyphenylpyruvate dioxygenase (4-HPPD) inhibitors, photosystem II inhibitors, and 2,4-D. This is also effectively controlled. The above stacking may be due to a combination of site-of-action mutations, a combination of non-site-of-action mutations, or a combination of site-of-action and non-site-of-action mutations.

[0167] The herbicide and the pesticide composition (a concept including the herbicide) of the present invention can be applied simultaneously or in stages to the above-mentioned useful plants (useful plants having agricultural, horticultural, or industrial uses), or to the place where the useful plants are to be grown (cultivation site), or to the place where the useful plants are growing, or to non-agricultural land. "Applying simultaneously or in stages" means applying the above-mentioned herbicide or pesticide composition in one or more stages. In this case, weeds may have already appeared on the useful plants or the cultivation site of the useful plants, or they may not have appeared yet.

[0168] Methods for simultaneously or in stages of treatment applied to useful plants, or to places where useful plants are intended to be grown or where useful plants are currently growing, or to non-agricultural land, include, for example, foliar treatment, soil treatment, root treatment, shower treatment, fumigation treatment, water surface treatment, seed treatment, and hydroponic solution treatment.

[0169] Examples of foliar treatment include applying the herbicide of the present invention or the pesticide composition of the present invention (which is a concept that includes the herbicide) to the surface of the stems, leaves, trunk, fruits, flowers (including before, during, and after flowering), spikes, or the entire plant.

[0170] Soil treatment methods include, for example, soil application, soil mixing, and chemical drenching of the soil. Locations for soil treatment include, for example, planting holes, rows, areas around planting holes, areas around rows, the entire cultivation area, the base of plants, between plants, under tree trunks, main ridges, hilling soil, seedling boxes, seedling trays, and seedbeds. Treatment timings include, for example, before sowing, at sowing, after sowing, during the seedling stage, before transplanting, at transplanting, and during the growth period after transplanting. Furthermore, in the above soil treatment, the herbicide and the pesticide composition (a concept including the herbicide) of the present invention may be mixed with irrigation solution, for example, by injection into irrigation equipment (irrigation tubes, irrigation pipes, sprinklers, etc.), mixing into inter-row flooding solution, or mixing into hydroponic solution. Alternatively, the irrigation solution and active ingredients can be mixed in advance, and treatment can be carried out using, for example, the above irrigation method or other appropriate irrigation methods such as sprinkling or flooding.

[0171] Examples of root treatments include immersing the roots of a useful plant in a chemical solution containing the herbicide of the present invention or the pesticide composition of the present invention (which includes the herbicide), and applying a solid formulation containing the herbicide of the present invention or the pesticide composition of the present invention (which includes the herbicide) to the roots of a useful plant.

[0172] One example of a shower treatment is a method of showering the stems and leaves of useful plants with a diluted solution of the herbicide of the present invention or the pesticide composition of the present invention (which is a concept that includes the herbicide).

[0173] As an example of fumigation treatment, one method is to disperse a diluted solution of the herbicide or agricultural chemical composition (which includes the herbicide) of the present invention into the air as a mist and allow it to adhere to the stems and leaves of useful plants.

[0174] As an example of surface treatment, one method is to spray a liquid or solid formulation containing the herbicide of the present invention or the pesticide composition of the present invention (which is a concept that includes the herbicide) onto a flooded rice paddy.

[0175] Seed treatments include, for example, treating seeds or vegetative reproductive organs with the herbicide or pesticide composition of the present invention (which is a concept that includes herbicides). Seed potatoes are a particularly good example of the vegetative reproductive organs mentioned above.

[0176] Examples of hydroponic solution treatments include mixing or adding a chemical solution or solid formulation containing the herbicide of the present invention or the pesticide composition of the present invention (which is a concept that includes the herbicide) to the hydroponic solution (hydroponic solution mixing treatment, hydroponic solution mixing treatment, etc.).

[0177] The herbicide and pesticide composition (a concept including the herbicide) of the present invention can also be applied by spot treatment. Spot treatment is a concept opposite to uniformly applying the herbicide or pesticide composition (a concept including the herbicide) of the present invention, and means selectively spraying the herbicide or pesticide composition (a concept including the herbicide) of the present invention on areas where weeds are present or where weeds are likely to appear. "Applying to a location" means applying to plants or soil where weeds are present or where weeds are likely to appear. Furthermore, spot treatment is not considered to occur only when all areas where weeds are present or where weeds are likely to appear in a continuous cultivated area are selectively treated. That is, even if a part of the cultivated area is treated as a whole, or if a part of the areas where weeds are present or where weeds are likely to appear are not treated with the herbicide or pesticide composition (a concept including the herbicide) of the present invention, if there are areas that have been spot-treated in a continuous cultivated area, it is included as spot treatment.

[0178] [Weed control methods] The weed control method of the present invention is a method of controlling weeds using the active ingredient amount of the pyrazole compound or salt thereof of the present invention.

[0179] In the weed control method of the present invention, the pesticide composition of the present invention (specifically, the herbicide) can be applied simultaneously or in stages to useful plants having agricultural, horticultural, or industrial uses, or to places where such useful plants are intended to grow or are currently growing.

[0180] For the purpose of controlling weeds, the herbicide containing the pyrazole compound of the present invention or a salt thereof may be applied to rice paddies, fields, lawns, orchards, non-agricultural land, greenhouses, seedling facilities, or plant factories, etc. [Examples]

[0181] Next, the method of producing the compound of the present invention, the formulation method, and the uses will be described in detail in the following examples, but the present invention is not limited in any way to these examples.

[0182] The melting point of the compound of the present invention, a physical property value, was measured using a Yanaco MP-500V micro-melting point analyzer. The refractive index was measured using an Atago Abbe refractometer. 1 The 1H NMR spectrum was measured using JEOL JNM-ECZL500R (500MHz), JNM-ECZL400S (400MHz), JNM-LA400 (400MHz), JNM-ECS300 (300MHz), or JNM-LA300 (300MHz) spectrometers, with tetramethylsilane (TMS) as the internal standard. Powder X-ray diffraction (XRD) analysis was performed at room temperature using a Rigaku SmartLab (tube: Cu, tube voltage: 40kV, tube current: 45mA). Cu-Kα light was used as the light source, and the measurement was performed using the transmission method. Fourier transform infrared spectroscopy (FT-IR) analysis was performed using a JASCO FT-IR-4700typeA (measurement method: Attenuated Total Reflection, number of integrations: 64, resolution: 2cm). -1 The measurements were taken using the following method: Differential scanning calorimetry (DSC measurement) was performed using a NETZSCH Japan DSC3500 Sirius (heating: 20-(10℃ / min)-250℃, atmosphere: nitrogen, control: empty container, container: aluminum, sampling: 300pts / min).

[0183] (Manufacturing Example 1-1) Preparation of 1-(3-bromo-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-5-(ethylamino)-1H-pyrazole-4-carbonitrile (Invention Compound No.: A-1) N-[1-(3-bromo-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-4-cyano-1H-pyrazole-5-yl]formamide (15.0 g, 44.8 mmol) synthesized according to the method described in International Patent Publication WO1998 / 03506 was dissolved in N,N-dimethylformamide (45 mL), and potassium carbonate (12.4 g, 89.7 mmol) and iodoethane (10.5 g, 67.3 mmol) were added sequentially, and the mixture was stirred at 60°C for 2 hours. Ethanol (10 mL), water (20 mL), and sodium hydroxide (2.69 g, 67.3 mmol) were added sequentially to the reaction solution, and the mixture was stirred at room temperature for 1 hour. Water (180 mL) was added to the reaction solution, the precipitated crystals were filtered off, washed with water, and dried under reduced pressure. The obtained crystals were recrystallized using ethanol (60 mL) to obtain 1-(3-bromo-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-5-(ethylamino)-1H-pyrazole-4-carbonitrile (11.8 g, yield 79%) as pale yellow crystals.

[0184] 1 H NMR(400MHz,CDCl3 / TMS)δ(ppm): 7.66(1H,s),6.46(1H,brs),4.10(2H,t),3.66-3.60(2H,m),2.75(2H,t),2.12-2.06(2H,m),1.96-1.92(2H,m),1.32(3H,t)

[0185] (Manufacturing Examples 1-2) Preparation of 1-(3-bromo-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-5-(ethylamino)-1H-pyrazole-4-carbonitrile (Invention Compound No.: A-1) A mixture of 5-amino-1-(3-bromo-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-1H-pyrazole-4-carbonitrile (200 mg, 0.651 mmol) synthesized according to the method described in International Patent Publication WO1993 / 10100 and triethyl orthoacetate (3.17 g, 19.5 mmol) was mixed with trifluoroacetic acid (74.2 mg, 0.651 mmol) and stirred at 120°C for 4 hours. After cooling to room temperature, the solvent was removed under reduced pressure, the residue was dissolved in ethanol (5 mL), sodium borohydride (100 mg, 2.64 mmol) was added, and the mixture was stirred under reflux for 2 hours. Further addition of sodium borohydride (100 mg, 2.64 mmol) was added, and the mixture was stirred under reflux for 30 minutes. After cooling to room temperature, water was added to the reaction solution, and the precipitated crystals were filtered off and dried under reduced pressure. The obtained crystals were purified by silica gel column chromatography (eluent, hexane:ethyl acetate = 2:1) to obtain 1-(3-bromo-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-5-(ethylamino)-1H-pyrazole-4-carbonitrile (70.0 mg, yield 32%) as colorless crystals.

[0186] (Manufacturing example 2) Preparation of 1-(3-bromo-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-5-(propylamino)-1H-pyrazole-4-carbonitrile (Invention Compound No.: A-2) N-[1-(3-bromo-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-4-cyano-1H-pyrazole-5-yl]formamide (23.8 g, 71.0 mmol), synthesized according to the method described in International Patent Publication WO1998 / 03506, was dissolved in N,N-dimethylformamide (68 mL). Potassium carbonate (19.6 g, 142 mmol) and 1-iodopropane (18.1 g, 107 mmol) were added sequentially, and the mixture was stirred at 60°C for 2 hours. Ethanol (40 mL), water (20 mL), and sodium hydroxide (4.26 g, 107 mmol) were added sequentially to the reaction solution, and the mixture was stirred at room temperature for 1 hour. Water (180 mL) was added to the reaction solution, the precipitated crystals were filtered off, washed with water, and dried under reduced pressure. The residue was purified by silica gel column chromatography (eluent, dichloromethane:ethyl acetate = 4:1), and the resulting crystals were recrystallized using ethanol (80 mL) to obtain 1-(3-bromo-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-5-(propylamino)-1H-pyrazole-4-carbonitrile (18.0 g, yield 73%) as pale yellow crystals.

[0187] 1 H NMR(400MHz,CDCl3 / TMS)δ(ppm): 7.65(1H,s),6.64(1H,brs),4.09(2H,t),3.57-3.52(2H,m),2.74(2H, t),2.12-2.06(2H,m),1.96-1.90(2H,m),1.76-1.66(2H,m)1.01(3H,t)

[0188] (Manufacturing Example 3) Preparation of 1-(3-bromo-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-5-(isopropylamino)-1H-pyrazole-4-carbonitrile (Invention Compound No.: A-3) 5-amino-1-(3-bromo-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-1H-pyrazole-4-carbonitrile (1.50 g, 4.88 mmol), synthesized according to the method described in International Patent Publication WO1993 / 10100, was dissolved in N,N-dimethylformamide (5 mL). 60% sodium hydride (0.390 g, 9.75 mmol) and 2-iodopropane (1.66 g, 9.77 mmol) were added sequentially, and the mixture was stirred at 60°C for 3 hours. After cooling to room temperature, ice was added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. Water (180 mL) was added to the reaction solution, and the mixture was extracted with dichloromethane. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography (eluent, hexane:ethyl acetate = 2:1) to obtain 1-(3-bromo-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-5-(isopropylamino)-1H-pyrazole-4-carbonitrile (1.30 g, yield 76%) as colorless crystals.

[0189] 1 H NMR(400MHz,CDCl3 / TMS)δ(ppm): 7.66(1H,s),6.37-6.35(1H,m),4.22-4.15(1H,m),4.10(2H,t),2.75(2H,t),2.12-2.06(2H,m),1.97-1.91(2H,m),1.31(6H,d)

[0190] (Manufacturing example 4) Preparation of 1-(3-bromo-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazole-2-yl)-5-(ethylamino)-1H-pyrazole-4-carbonitrile (comparative agent 4) (1) Preparation of 5-(3-chloropropyl)-3-hydrazinyl-1H-pyrazole 1,1,6-trichlorohexa-1-en-3-one (38.5 g, 191 mmol), synthesized according to the method described in Non-Patent Document ChemistrySelect (2017) (21), 5871-5876, was dissolved in isopropyl alcohol (200 mL), triethylamine (38.7 g, 382 mmol) was added, and hydrazine monohydrate (23.9 g, 477 mmol) was added dropwise at -20°C. The reaction solution was stirred at -10°C for 1 hour, the solvent was removed under reduced pressure, saturated saline solution was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain 5-(3-chloropropyl)-3-hydrazinyl-1H-pyrazole (26.5 g, yield 79%) as a brown liquid.

[0191] 1 H NMR(400MHz,CDCl3 / TMS)δ(ppm): 5.54(1H,s),5.40(2H,brs),3.55(2H,t),2.74(2H,t),2.10-2.03(2H,m)

[0192] (2) Preparation of 5-amino-5′-(3-chloropropyl)-1′H-[1,3′-bipyrazole]-4-carbonitrile 5-(3-chloropropyl)-3-hydrazinyl-1H-pyrazole (26.5 g, 152 mmol) was dissolved in isopropyl alcohol (150 mL), and 2-(ethoxymethylene)malononitrile (15.8 g, 129 mmol) was added. The mixture was stirred under reflux for 1 hour. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography (eluent, hexane:ethyl acetate = 1:1) to obtain 5-amino-5′-(3-chloropropyl)-1′H-[1,3′-bipyrazole]-4-carbonitrile (23.0 g, yield 60%) as brown crystals.

[0193] 1 H NMR(400MHz,CDCl3 / TMS)δ(ppm): 9.67(1H,brs),7.58(1H,s),6.39(1H,s),6.12(2H,brs),3.58(2H,t),2.91(2H,t),2.18-2.11(2H,m)

[0194] (3) Preparation of 5-amino-1-(5,6-dihydro-4H-pyrrolo[1,2-b]pyrazole-2-yl)-1H-pyrazole-4-carbonitrile 5-amino-5′-(3-chloropropyl)-1′H-[1,3′-bipyrazole]-4-carbonitrile (23.0 g, 91.7 mmol) was dissolved in isopropyl alcohol (150 mL), and potassium tert-butoxide (11.3 g, 101 mmol) was added little by little. The mixture was heated under reflux and stirred for 1 hour. After cooling to room temperature, the precipitated crystals were filtered off, washed with a 50% aqueous solution of isopropyl alcohol, and dried to obtain 5-amino-1-(5,6-dihydro-4H-pyrrolo[1,2-b]pyrazole-2-yl)-1H-pyrazole-4-carbonitrile (10.5 g, yield 53%) as pale yellow crystals.

[0195] 1 H NMR(400MHz,CDCl3 / TMS)δ(ppm): 7.57(1H,s),6.23(1H,s),6.08(2H,brs),4.14(2H,t),2.96(2H,t),2.66-2.58(2H,m)

[0196] (4) Preparation of 5-amino-1-(3-bromo-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazole-2-yl)-1H-pyrazole-4-carbonitrile A mixture of 5-amino-1-(5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-2-yl)-1H-pyrazole-4-carbonitrile (3.00 g, 14.0 mmol) and dichloromethane (20 mL) was added with N-bromosuccinimide (2.49 g, 14.0 mmol), and stirred at room temperature for 15 hours. The solvent was distilled off under reduced pressure, and the obtained crystals were washed with 50% aqueous ethanol solution and dried to obtain 5-amino-1-(3-bromo-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-2-yl)-1H-pyrazole-4-carbonitrile (1.28 g, yield 31%) as pale yellow crystals.

[0197] 1 H NMR(400MHz,CDCl3 / TMS)δ(ppm): 7.66(1H,s),5.55(2H,brs),4.22(2H,t),2.96(2H,t),2.69-2.62(2H,m)

[0198] (5) Preparation of N-[1-(3-bromo-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-2-yl)-4-cyano-1H-pyrazol-5-yl]formamide Acetic anhydride (840 mg, 8.23 mmol) and formic acid (500 mg, 10.9 mmol) were stirred at room temperature for 1 hour, and then this mixture was added to a mixture of 5-amino-1-(3-bromo-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-2-yl)-1H-pyrazole-4-carbonitrile (800 mg, 2.73 mmol) and acetonitrile (5 mL), and stirred at 65 °C for 2 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, and the precipitated crystals were washed with water and dried under reduced pressure to obtain N-[1-(3-bromo-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-2-yl)-4-cyano-1H-pyrazol-5-yl]formamide (800 mg, yield 91%) as pale yellow crystals.

[0199] 1 H NMR(400MHz,CDCl3 / TMS)δ(ppm): 9.52 - 7.87 (3H, m), 4.31 - 4.25 (2H, m), 2.99 - 2.97 (2H, m), 2.71 - 2.69 (2H, m)

[0200] (6) Preparation of 1-(3-Bromo-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-2-yl)-5-(ethylamino)-1H-pyrazole-4-carbonitrile (Comparative Agent 4) Dissolve N-[1-(3-Bromo-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-2-yl)-4-cyano-1H-pyrazol-5-yl]formamide (300 mg, 0.934 mmol) in N,N-dimethylformamide (5 mL), and sequentially add potassium carbonate (155 mg, 1.12 mmol) and iodoethane (160 mg, 1.03 mmol), then stir at 50 °C for 1 hour. Sequentially add ethanol (5 mL) and 0.1 N aqueous sodium hydroxide solution (8.4 mL) to the reaction solution, stir at room temperature for 1 hour, and filter the precipitated crystals. Wash the obtained crystals with water and dry under reduced pressure to obtain 1-(3-Bromo-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-2-yl)-5-(ethylamino)-1H-pyrazole-4-carbonitrile (280 mg, yield 93%) as pale orange crystals.

[0201] 1 H NMR (400 MHz, CDCl3 / TMS) δ (ppm): 7.66 (1H, s), 6.30 (1H, brs), 4.22 (2H, t), 3.66 - 3.59 (2H, m), 2.96 (2H, t), 2.68 - 2.61 (2H, m), 1.32 (3H, t)

[0202] (Production Example 5) Preparation of 1-(3-Bromo-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazol-2-yl)-5-(propylamino)-1H-pyrazole-4-carbonitrile (Comparative Agent 5) N-[1-(3-bromo-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazole-2-yl)-4-cyano-1H-pyrazole-5-yl]formamide (200 mg, 0.623 mmol) was dissolved in N,N-dimethylformamide (5 mL), and potassium carbonate (103 mg, 0.745 mmol) and 1-iodopropane (116 mg, 0.682 mmol) were added sequentially, and the mixture was stirred at 50°C for 1 hour. Ethanol (5 mL) and 0.1N sodium hydroxide aqueous solution (5.6 mL) were added sequentially to the reaction solution, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were filtered, washed with water, and dried under reduced pressure to obtain 1-(3-bromo-5,6-dihydro-4H-pyrrolo[1,2-b]pyrazole-2-yl)-5-(propylamino)-1H-pyrazole-4-carbonitrile (160 mg, yield 77%) as yellow crystals.

[0203] 1 H NMR(400MHz,CDCl3 / TMS)δ(ppm): 7.65(1H,s),6.45(1H,brs),4.22(2H,t),3.54-3.51(2H,m),2.96(2H,t),2.66-2.64(2H,m),1.72-1.68(2H,m),1.00(3H,t)

[0204] (Manufacturing example 6) Preparation of 1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-5-[(cyanomethyl)(methyl)amino]-1H-pyrazole-4-carbonitrile (comparative agent 9)

[0205] 1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-5-(methylamino)-1H-pyrazole-4-carbonitrile (200 mg, 0.723 mmol) synthesized according to the method described in International Patent Publication WO1994 / 08999 was dissolved in N,N-dimethylformamide (3 mL), and 60% sodium hydride (37.8 mg, 0.945 mmol) and 2-chloroacetonitrile (65.5 mg, 0.868 mmol) were added sequentially, and the mixture was stirred at room temperature for 5 minutes. Water was added to the reaction solution, and it was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography (eluent, hexane:ethyl acetate = 2:1) to obtain 1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-5-[(cyanomethyl)(methyl)amino]-1H-pyrazole-4-carbonitrile (100 mg, yield 44%) as a colorless liquid.

[0206] 1 H NMR(300MHz,CDCl3 / TMS)δ(ppm): 7.81(1H,s),4.13(2H,t),4.04(2H,s),3.14(3H,s),2.75(2H,t),2.12-2.00(2H,m),1.98-1.84(2H,m)

[0207] (Manufacturing example 7) Preparation of ethyl 1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-5-(methylamino)-1H-pyrazole-4-carboxylate (comparative agent 10) Ethyl 5-amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-1H-pyrazole-4-carboxylate (300 mg, 0.969 mmol), synthesized according to the method described in International Patent Publication WO1993 / 10100, was dissolved in triethyl orthoformate (3 mL), trifluoroacetic acid (30.0 mg, 0.263 mmol) was added, and the mixture was stirred under reflux for 2 hours. After cooling to room temperature, the solvent was removed under reduced pressure, the residue was dissolved in ethanol (3 mL), sodium borohydride (44.0 mg, 1.16 mmol) was added, and the mixture was stirred at 90°C for 30 minutes. After cooling to room temperature, water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography (eluent, hexane:ethyl acetate = 2:1) to obtain ethyl 1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-5-(methylamino)-1H-pyrazole-4-carboxylate (171.0 mg, yield 55%) as white crystals.

[0208] 1 H NMR(400MHz,CDCl3 / TMS)δ(ppm): 7.81(1H,s),6.46(1H,brs),4.26(2H,q),4.13(2H,t),2.76(2H,t),2.70(3H,d),2.12-2.00(2H,m),1.98-1.84(2H,m),1.33(3H,t)

[0209] (Manufacturing example 8) Manufacturing of methyl [1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-2-yl)-4-cyano-1H-pyrazole-5-yl]glycinate (comparative agent 11) N-[1-(3-Chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)-4-cyano-1H-pyrazol-5-yl]formamide (500 mg, 1.72 mmol) synthesized according to the method described in the specification of International Publication Patent Gazette WO1998 / 03506 was dissolved in N,N-dimethylformamide (5 mL), and potassium carbonate (285 mg, 2.06 mmol) and methyl bromoacetate (263 mg, 1.58 mmol) were sequentially added, followed by stirring at 50 °C for 1 hour. Ethanol (5 mL) and 0.1 N aqueous sodium hydroxide solution (17.2 mL) were sequentially added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain methyl [1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)-4-cyano-1H-pyrazol-5-yl]glycinate (34.3 mg, yield 6%) as colorless crystals.

[0210] 1 H NMR (300 MHz, CDCl3 / TMS) δ (ppm): 7.67 (1H, s), 7.33 (1H, t), 4.39 (2H, d), 4.11 (2H, t), 3.83 (3H, s) 2.77 (2H, t), 2.11 - 2.05 (2H, m), 1.97 - 1.91 (2H, m)

[0211] Physical property values of the compounds [A-1], [A-2], [A-3] of the present invention and Comparative Agents 4 - 5, 9 - 11 synthesized according to the above Production Example are shown in Table 1 below. In addition, the compound numbers and symbols in the table represent the same meanings as described above.

[0212]

Table 1

[0213] As a result of powder X-ray diffraction (XRD) measurement of the compound [A-1] of the present invention synthesized according to the above Production Example 1-1, it had diffraction peaks shown in Table 2. These values were generated using an average wavelength of 1.5418 Å with a 2θ step width of 0.010°. The powder X-ray diffraction pattern is shown in FIG. 1. Further, as a result of measuring Fourier transform infrared spectroscopy (FT-IR), peaks as shown in FIG. 2 were shown. Typical specific peaks included 3313 cm -1 、2208 cm -1 、1583 cm -1 、1559 cm -1 、1526 cm -1 、1451 cm -1 、1336 cm -1 、944 cm -1 、880 cm -1 、691 cm -1 、622 cm -1 and 512 cm -1 had peaks, but were not limited thereto. As a result of differential scanning calorimetry (DSC measurement), peaks as shown in FIG. 3 were shown, and the melting point was 154.9 °C.

[0214]

Table 2

[0215] As a result of powder X-ray diffraction (XRD) measurement of the compound [A-2] of the present invention synthesized according to the above Production Example 2, it had diffraction peaks shown in Table 3. These values were generated using an average wavelength of 1.5418 Å with a 2θ step width of 0.010°. The powder X-ray diffraction pattern is shown in FIG. 4. Further, as a result of measuring Fourier transform infrared spectroscopy (FT-IR), peaks as shown in FIG. 5 were shown. Typical specific peaks included 3303 cm -1 、2955 cm -1 、2210 cm -1 、1591 cm -1 [[ID=​​​​​​​​​​​, 692cm -1 and 475cm -1 While a peak was observed, it is not limited to this point. Differential scanning calorimetry (DSC measurement) revealed the peaks shown in Figure 6, and the melting point was 126.9°C.

[0216] [Table 3]

[0217] Powder X-ray diffraction (XRD) measurements of compound [A-3] of the present invention, synthesized according to manufacturing example 3 above, showed the diffraction peaks shown in Table 4. These values ​​were generated using an average wavelength of 1.5418 Å with a 2θ step size of 0.010°. The powder X-ray diffraction pattern is shown in Figure 7. Furthermore, Fourier transform infrared spectroscopy (FT-IR) measurements showed the peaks shown in Figure 8. A typical specific peak was at 3280 cm⁻¹. -1 , 2951cm -1 , 2207cm -1 , 1590cm -1 , 1559cm -1 , 1521cm -1 , 1340cm -1 , 1175cm -1 , 942cm -1 , 852cm -1 , 691cm -1 and 508cm -1 While a peak was observed, it is not limited to this point. Differential scanning calorimetry (DSC measurement) revealed the peaks shown in Figure 9, and the melting point was 136.6°C.

[0218] [Table 4]

[0219] Next, specific examples of formulations of the herbicide of the present invention using the pyrazole compound or salt thereof manufactured as described above will be explained. However, the type of compound, additive component, and mixing ratio are not limited to these and can be changed within a wide range. Also, in the following explanation, "parts" means parts by mass.

[0220] (Example of formulation 1) Emulsion 10 parts of the present invention's compound [A-1], [A-2], or [A-3] Cyclohexanone 30 parts Polyoxyethylene alkylaryl ether 11 parts Alkylbenzenesulfonate calcium 4 parts Methylnaphthalene 45 parts The above ingredients were uniformly dissolved to form an emulsion.

[0221] (Formulation example 2) Wettable powder 10 parts of the present invention's compound [A-1], [A-2], or [A-3] 0.5 parts of sodium salt of formalin condensate of naphthalene sulfonic acid 0.5 parts of polyoxyethylene alkylaryl ether Diatomaceous earth 24 parts Clay 65 The above ingredients were uniformly mixed and ground to form a wettable powder.

[0222] (Formulation example 3) Powder Two parts of the present invention's compound [A-1], [A-2], or [A-3] Diatomaceous earth (5 parts) Clay 93 The above ingredients were uniformly mixed and ground to obtain a powder.

[0223] (Formulation example 4) Granules Five parts of the compound [A-1], [A-2], or [A-3] of the present invention. Sodium salt of lauryl alcohol sulfate 2 parts Sodium lignin sulfonate 5 parts Carboxymethylcellulose 2 parts Clay 86 The above ingredients were uniformly mixed and ground. This mixture was then mixed with an amount equivalent to 20 parts water, processed into granules of 14-32 mesh using an extrusion granulator, and then dried to obtain the granular material.

[0224] (Formulation example 5) Flowable formulation 20 parts of the present invention's compound [A-1], [A-2], or [A-3] Polyoxyethylene styrene-phenyl ether sulfate 4 parts Ethylene glycol 7 parts Silicone AF-118N (manufactured by Asahi Kasei Corporation) 0.02 parts Wednesday 68.98 parts The above ingredients were mixed in a high-speed agitator for 30 minutes, and then pulverized in a wet pulverizer to obtain a flowable formulation.

[0225] (Formulation example 6) Granular wettable powder 10 parts of the present invention's compound [A-1], [A-2], or [A-3] Sodium lignin sulfonate 5 parts Polyoxyethylene alkylaryl ether (1 part) Sodium polycarboxylate 3 parts White carbon 5 parts Pregelatinized starch (part 1) Calcium carbonate 65 units 10 parts water The above ingredients were mixed, kneaded, and pressed into granules. The resulting granular material was dried in a fluidized bed dryer to obtain a wettable powder granule.

[0226] Next, the herbicidal activity of the herbicide of the present invention using a formulation containing the compounds [A-1], [A-2], and [A-3] or their salts, manufactured as described above, as active ingredients will be specifically explained. In the following, the compound [A-1] used was synthesized according to Production Example 1-1.

[0227] (Example 1: Herbicidal effect on paddy field weeds before emergence) Paddy field soil was filled into 1 / 20000 are pots, fertilized, and after puddling, seeds of barnyard grass, bulrush, and Monochoria vaginalis were sown, and the area was flooded to a depth of 3 cm. For the compounds of the present invention [A-1], [A-2], [A-3] and comparative agents 1-12, a predetermined amount of wettable powder, prepared according to Formulation Example 2, was diluted with water and applied to the water surface. The plants were then grown while maintaining a water depth of 3 cm, and the herbicidal effect was visually evaluated on the 25th day after treatment. The results are shown in Table 5. The amount of active ingredient is shown per 10 ares, and the herbicidal effect is shown on an index from 0 to 10 (0: no effect ~ 10: complete killing).

[0228] Regarding the criteria for evaluation, an index of 1-2 indicates that there is a slight effect on the growth or emergence of the test weeds compared to the untreated area, but the herbicidal activity is unclear. An index of 3-10 indicates that the growth or emergence of the test weeds is significantly worse compared to the untreated area, and the herbicidal activity is clearly evident.

[0229] (Example 2: Safety and phytotoxicity evaluation for transplanted rice) Paddy field soil was filled into 1 / 20000 are pots, fertilized, and after puddling, rice plants at the 2.1-leaf stage were transplanted, and the fields were flooded to a depth of 3 cm. For the compounds of the present invention [A-1], [A-2], [A-3] and comparative agents 1-12, a predetermined amount of wettable powder, prepared according to Formulation Example 2, was diluted with water and applied to the water surface. The fields were then grown while maintaining a flood depth of 3 cm, and the degree of phytotoxicity was visually evaluated on the 25th day after treatment. The results are shown in Table 5. The amount of active ingredient is shown per 10 ares, and the herbicidal effect is shown on a scale from A to D.

[0230] Regarding the criteria for the objective evaluation, a rating of A was given to those in which no effect on the growth state of the test crop was observed compared to the untreated area. A rating of B was given to those in which an effect on the growth state of the test crop was observed compared to the untreated area, but the risk to the final crop growth and yield was judged to be small. A rating of C was given to those in which the growth state of the test crop was significantly worsened compared to the untreated area, and the risk to the final crop growth and yield was judged to be large. A rating of D was given to those in which a severe effect leading to crop death was observed.

[0231] [Table 5]

[0232] In Table 5, comparative agent 1 is Example 1.41 described in Table 1 of the International Patent Publication WO1998 / 03506, and has the following structure. TIFF0007905560000010.tif30147

[0233] In Table 5, comparative agent 2 is Example 1.42 described in Table 1 of the International Patent Publication WO1998 / 03506, and has the following structure. TIFF0007905560000011.tif34147

[0234] In Table 5, comparative agent 3 is Example 1.43 described in Table 1 of the International Patent Publication WO1998 / 03506, and has the following structure. TIFF0007905560000012.tif30147

[0235] Comparator 4 in Table 5 has the following structure. TIFF0007905560000013.tif30148

[0236] Comparator 5 in Table 5 has the following structure. TIFF0007905560000014.tif34146

[0237] In Table 5, comparative agent 6 is Example 4.57 described in the International Patent Publication WO1994 / 08999, and has the following structure. TIFF0007905560000015.tif33147

[0238] In Table 5, comparative agent 7 is Example 4.58 described in the International Patent Publication WO1994 / 08999, and has the following structure. TIFF0007905560000016.tif31147

[0239] In Table 5, comparative agent 8 is Example 4.68 described in the International Patent Publication WO1994 / 08999, and has the following structure. TIFF0007905560000017.tif40147

[0240] Comparator 9 in Table 5 has the following structure. TIFF0007905560000018.tif35148

[0241] Comparator 10 in Table 5 has the following structure. TIFF0007905560000019.tif25146

[0242] Comparator 11 in Table 5 has the following structure. TIFF0007905560000020.tif39147

[0243] In Table 5, comparative agent 12 is Example 4.278 described in the International Patent Publication WO1994 / 08999, and has the following structure. TIFF0007905560000021.tif36147

[0244] As shown in Table 5, the compounds [A-1], [A-2], and [A-3] of the present invention exhibit excellent weed control effects and safety for transplanted rice plants.

[0245] (Example 3: Residual effect on barnyard grass) Paddy field soil was filled into 1 / 10000 are pots, fertilized, and after puddling, the fields were flooded to a depth of 4 cm. A predetermined amount of wettable powder, prepared according to Formulation Example 2, containing the compounds [A-1], [A-2], [A-3] of the present invention and pyraclonil, was diluted with water and applied to the water surface. After 1, 3, and 5 days, the water was removed from the top of the pots from a depth of 4 cm to 2 cm, and then immediately flooded again to 4 cm to alter the water environment. The flooded depth was then maintained at 4 cm, and barnyard grass was oversown on the soil surface 5 and 10 days after treatment. The herbicidal effect was visually evaluated 21 days after each oversowing. The results are shown in Table 6. The amount of active ingredient is shown per 10 ares, and the herbicidal effect is shown on an index from 0 to 100 (0: no effect ~ 100: complete killing).

[0246] Regarding the criteria for objective evaluation, an index of 1-20 indicates that there is a slight effect on the growth of the test weeds compared to the untreated area, but the herbicidal activity is unclear. An index of 21-100 indicates that the growth or emergence of the test weeds is significantly worse compared to the untreated area, and the herbicidal activity is clearly evident.

[0247] [Table 6]

[0248] TIFF0007905560000023.tif39147

[0249] As shown in Table 6, the compounds [A-1], [A-2], and [A-3] of the present invention exhibit excellent residual efficacy even under conditions of water fluctuation.

Claims

1. A pyrazole compound represented by any one of the formulas [A-1], [A-2], and [A-3], or a salt thereof.

2. A pesticide composition containing the pyrazole compound or a salt thereof as described in claim 1 as an active ingredient.

3. The pesticide composition according to claim 2, further containing a surfactant.

4. A herbicide containing the pyrazole compound or a salt thereof as described in claim 1 as an active ingredient.

5. The herbicide according to claim 4, further containing a surfactant.

6. The herbicide according to claim 4, which has herbicidal activity against weeds occurring in fields, paddy fields, orchards, lawns, non-agricultural land, greenhouses, seedling facilities, or plant factories where useful plants for agricultural, horticultural, or industrial purposes are cultivated.

7. The herbicide according to claim 6, wherein the useful plant is a plant that has been transformed in cultivation by breeding methods or genetic modification technology.

8. A method for controlling weeds using the amount of the active ingredient of the pyrazole compound or salt thereof described in claim 1.

9. A method for controlling weeds, comprising applying the pesticide composition described in claim 2 or 3 simultaneously or in stages to useful plants having agricultural, horticultural, or industrial uses, or to the place where such useful plants are intended to grow or are currently growing.

10. A method for controlling weeds, comprising applying the herbicide described in any one of claims 4 to 7 simultaneously or in stages to useful plants having agricultural, horticultural, or industrial uses, or to places where such useful plants are intended to grow or are currently growing.

11. The method for controlling weeds according to claim 9, wherein the pesticide composition is applied in a paddy field, field, lawn, orchard, non-agricultural land, greenhouse, seedling facility, or plant factory.

12. The method for controlling weeds according to claim 10, wherein the herbicide is applied in a paddy field, cultivated field, lawn, orchard, non-agricultural land, greenhouse, seedling facility, or plant factory.

13. A method for using a herbicide, comprising using the herbicide described in any one of claims 4 to 7 to control weeds on useful plants having agricultural, horticultural, or industrial uses.

14. A crystal of a pyrazole compound represented by formula [A-1], wherein the crystal has diffraction peaks at least 2θ = 8.8°±0.2°, 12.0°±0.2°, 19.0°±0.2°, 24.0°±0.2°, 25.0°±0.2° and 26.8°±0.2° in powder X-ray diffraction.

15. A pesticide composition containing the crystal described in claim 14 as an active ingredient.

16. A herbicide containing the crystal described in claim 14 as an active ingredient.

17. A method for controlling weeds using a pesticide composition containing the crystals described in claim 14.

18. Use of the crystals according to claim 14 as a herbicide.

19. A crystal of a pyrazole compound represented by formula [A-2], wherein the crystal has diffraction peaks at least 2θ = 8.3°±0.2°, 12.0°±0.2°, 12.9°±0.2°, 15.5°±0.2°, 21.8°±0.2°, 23.1°±0.2°, 24.4°±0.2° and 26.3°±0.2° in powder X-ray diffraction.

20. A pesticide composition containing the crystal described in claim 19 as an active ingredient.

21. A herbicide containing the crystal described in claim 19 as an active ingredient.

22. A method for controlling weeds using a pesticide composition containing the crystals described in claim 19.

23. Use of the crystals according to claim 19 as a herbicide.

24. A crystal of a pyrazole compound represented by formula [A-3], wherein the crystal has diffraction peaks at least 2θ = 7.8°±0.2°, 10.5°±0.2°, 12.7°±0.2°, 16.8°±0.2°, 17.1°±0.2°, 18.7°±0.2°, 21.9°±0.2°, 23.6°±0.2° and 28.0°±0.2° in powder X-ray diffraction.

25. A pesticide composition containing the crystal described in claim 24 as an active ingredient.

26. A herbicide containing the crystal described in claim 24 as an active ingredient.

27. A method for controlling weeds using a pesticide composition containing the crystals described in claim 24.

28. Use of the crystals according to claim 24 as a herbicide.

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