Crystal structure and polymorphisms of phenoxasulfone

Abstract

This invention provides novel crystalline forms of phenoxasulfone and pesticide compositions containing them. [Solution] The present invention relates to a pesticide composition that is a herbicide for rice cultivation and is a control agent for grasses, including a rice herbicide, comprising a compound of formula [I], i.e., a novel crystalline form of phenoxasulfone, having a powder X-ray diffraction pattern including 2θ angle values ​​such as 7.4°±0.2°, 8.2°±0.2°, 12.3°±0.2°, 13.0°±0.2°, 17.5°±0.2°, 19.5°±0.2°, and 20.3°±0.2°, and a solid form of phenoxasulfone having the crystalline form and a carrier or excipient. JPEG2026113945000005.jpg4173

Description

[Technical Field]

[0001] The present invention relates to phenoxasulfone in solid form, pesticide compositions containing these solid forms, and methods of using these as pest control agents for the cultivation of grasses, including herbicides for rice. [Background technology]

[0002] Patent documents 1 and 2 relate to a mixture in which an isoxazoline derivative represented by general formula [X] is mixed with at least one conventionally used herbicide, thereby exhibiting not only an additive effect but also a synergistic effect of their individual herbicidal effects. [ka] Among them, [I] phenoxasulfone (3-(2,5-dichloro-4-ethoxybenzylsulfonyl)-5,5-dimethyl-2-isoisoxazosin) is disclosed as a representative example of isoxazoline derivatives. [ka]

[0003] Patent documents 3 and 4 disclose the herbicidal effect of a mixture of phenoxasulfone with other active ingredients of pesticides.

[0004] Patent documents 6 and 7 disclose pesticide compositions containing phenoxasulfone and methods for producing them.

[0005] Thus, while the herbicidal effect of phenoxasulfone mixtures, the pesticide compositions they contain, and their manufacturing methods are disclosed, the crystalline structure of phenoxasulfone is not disclosed. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-002324 [Patent Document 2] Japanese Patent Application Laid-Open No. 2005-145958 [Patent Document 3] International Publication No. 2010-145992 [Patent Document 4] Japanese Patent Application Laid-Open No. 2011-201792 [Patent Document 5] International Publication No. 2016 / 114200 Specification [Patent Document 6] International Publication No. 2017 / 065015 Specification [Summary of the Invention] [Means for Solving the Problems]

[0007] The solid form of this phenoxysulfone, its composition, and methods for its preparation and use have now been discovered.

[0008] The present invention is characterized by having the following gist. [1] A crystalline form of phenoxysulfone having a powder X-ray diffraction pattern including at least four selected from the group consisting of the following 2θ angular values: 7.4° ± 0.2°, 8.2° ± 0.2°, 12.3° ± 0.2°, 13.0° ± 0.2°, 17.5° ± 0.2°, 19.5° ± 0.2°, 20.3° ± 0.2°, 21.5° ± 0.2°, 24.1° ± 0.2°, 24.8° ± 0.2°, 31.4° ± 0.2°, and 44.5° ± 0.2°. [2] The following infrared absorption spectrum: 2978 cm -1 , -1 , -1 , -1 , -1 , -1 , -1 , -1 , -1 , -1 , -1 ±2 cm -1 , 2921 cm -1 ±2 cm -1 , 1600 cm -1 ±2 cm -1 , 1565 cm -1 ±2 cm -1 , 1497 cm -1 ±2 cm -1 , 1473 cm -1 ±2 cm -1 , 1438 cm -1 ±2 cm -1、1369cm -1 ±2cm -1 、1322cm -1 ±2cm -1 、1306cm -1 ±2cm -1 、1257cm -1 ±2cm -1 、1169cm -1 ±2cm -1 、1149cm -1 ±2cm -1 、1133cm -1 ±2cm -1 、1119cm -1 ±2cm -1 、1081cm -1 ±2cm -1 、1041cm -1 ±2cm -1 、972cm -1 ±2cm -1 、945cm -1 ±2cm -1 、918cm -1 ±2cm -1 、906cm -1 ±2cm -1 、877cm -1 ±2cm -1 、839cm -1 ±2cm -1 、807cm -1 ±2cm -1 、780cm -1 ±2cm -1 、749cm -1 ±2cm -1 、715cm -1 ±2cm -1 、699cm -1 ±2cm -1 、650cm -1 ±2cm -1 、634cm -1 ±2cm -1 、588cm -1 ±2cm -1 、553cm -1 ±2cm -1 、530cm -1 ±2cm -1 、500cm -1 ±2cm -1 、431cm -1±2cm -1 The crystal form according to 1, having at least four selected from the group. [3] The crystal form described in 1 above, having a melting point of 157.5 to 159.5°C. [4] An agricultural composition comprising the crystalline form described in any one of items 1 to 3 above, and at least one agriculturally acceptable carrier or excipient. [5] The composition according to item 4, which is concentrated in any one of the crystalline forms described in item 1 to 3 above. [6] The composition according to 4, comprising at least one further active ingredient of a pesticide. [Modes for carrying out the invention]

[0009] The present invention relates to a novel crystalline form of phenoxasulfone, crystalline form A. This crystalline form A can be characterized by a powder X-ray diffraction pattern expressed in terms of 2θ angles or d intervals. Thus, in another embodiment of the present invention, the crystalline form has a powder X-ray diffraction pattern that includes at least four, at least six, at least eight, or all of the 2θ angle values ​​selected from 7.4°±0.2°, 8.2°±0.2°, 12.3°±0.2°, 13.0°±0.2°, 17.5°±0.2°, 19.5°±0.2°, 20.3°±0.2°, 21.5°±0.2°, 24.1°±0.2°, 24.8°±0.2°, 31.4°±0.2°, and 44.5°±0.2°. These peak values, along with the corresponding d interval values, are shown in Table 1.

[0010] [Table 1]

[0011] These 2θ angle values ​​are derived from the polymorphic powder X-ray diffraction patterns obtained using the method of Example 1. These values ​​are generated using an average wavelength of 1.5418 Å with a 2θ step size of 0.01°.

[0012] Crystal morphology A also has a wave number (cm -1) can be characterized by the infrared absorption spectrum represented thereby. Thus, the crystal form A has 2978 cm -1 ±2 cm -1 , 2921 cm -1 ±2 cm -1 , 1600 cm -1 ±2 cm -1 , 1565 cm -1 ±2 cm -1 , 1497 cm -1 ±2 cm -1 , 1473 cm -1 ±2 cm -1 , 1438 cm -1 ±2 cm -1 , 1369 cm -1 ±2 cm -1 , 1322 cm -1 ±2 cm -1 , 1306 cm -1 ±2 cm -1 , 1257 cm -1 ±2 cm -1 , 1169 cm -1 ±2 cm -1 , 1149 cm -1 ±2 cm -1 , 1133 cm -1 ±2 cm -1 , 1119 cm -1 ±2 cm -1 , 1081 cm -1 ±2 cm -1 , 1041 cm -1 ±2 cm -1 , 972 cm -1 ±2 cm -1 , 945 cm -1 ±2 cm -1 , 918 cm -1 ±2 cm -1 , 906 cm -1 ±2 cm -1 , 877 cm -1 ±2 cm -1 , 839 cm -1 ±2 cm -1 , 807 cm -1 ±2 cm -1 , 780 cm -1 ±2 cm -1 , 749 cm -1 ±2 cm<​-1 ±2cm -1 , 699cm -1 ±2cm -1 , 650cm -1 ±2cm -1 , 634cm -1 ±2cm -1 , 588cm -1 ±2cm -1 , 553cm -1 ±2cm -1 , 530cm -1 ±2cm -1 , 500cm -1 ±2cm -1 , 431cm -1 ±2cm -1 It has an infrared absorption spectrum that includes at least 3, at least 6, at least 9, at least 12, at least 15, or all fractions selected from the group consisting of , , , .

[0013] Crystal morphology A also has a melting point of 157.5–159.5°C. This melting point is obtained using differential scanning calorimetry (DSC) with a heating rate of 10°C / min.

[0014] In relation to the present invention, a polymorph is a specific crystalline form of a compound that can exist in two or more crystalline forms in the solid state. The crystalline form of a compound contains constituent molecules arranged in an ordered, repeating pattern that extends across all three spatial dimensions (in contrast, amorphous solids do not have long-range order within the molecular positions). Different polymorphs of a compound have different arrangements of atoms and / or molecules in their crystalline structure. If the compound is a biologically active compound, including herbicidal activity, differences in crystalline structure can result in different polymorphs having different chemical, physical, and biological properties. Properties that may be affected include crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspension properties, dissolution rate, and bioavailability. Thus, a particular polymorph may have properties that are more advantageous in a particular use compared to another polymorph of the same compound. In particular, the physical, chemical, and biological properties listed above can significantly influence the development of manufacturing methods and formulations in which the compound can be readily combined in formulations with other active ingredients and formulation components of pesticides, as well as the quality and efficacy of plant treatment agents, including herbicides. It should be noted that it is not possible to predict whether a compound may exist in two or more polymorphic solid states, nor is it possible to predict the properties of any of these crystalline forms.

[0015] In particular, the use of specific polymorphs can enable the use of new formulations compared to existing polymorphic / amorphous forms of a compound. This can be advantageous for several reasons. For example, because suspension concentrate (SC) formulations do not contain solvents, SC formulations are often expected to have reduced plant toxicity compared to suspension concentrate (EC) formulations. However, if the existing form of a compound is not stable in the SC formulation, polymorphic conversion may occur, leading to undesirable crystal growth. Such crystal growth can lead to, for example, thickening and potentially solidification of the formulation, which can lead to clogging of application equipment, such as spray nozzles on agricultural sprayers, thus hindering the provision of preferred SC formulations. Therefore, the use of stable polymorphic forms can overcome these problems.

[0016] Assays of the presence of crystals in the solid phase can be performed by conventional methods known in the art. For example, powder X-ray diffraction is a convenient and common technique. Other techniques that may be used include differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and Raman spectroscopy or infrared spectroscopy.

[0017] The polymorphs of the present invention can be applied in their original form, but more preferably they can be incorporated into a pesticide composition by conventional means. Accordingly, in a further embodiment, the present invention provides a pesticide composition comprising the polymorphs of the present invention as defined above and at least one agrochemically acceptable carrier or diluent.

[0018] Furthermore, the compositions of the present invention may comprise two or more polymorphs. In particular, these may be concentrated with respect to crystalline form A. "Concentrated" means that the molar ratio of crystalline form A, compared to the total amount of phenoxasulfone, is greater than 50%, for example, at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, or at least 99%.

[0019] As used herein, the term “harmful plant” means a plant that competes with crops in cultivation and may hinder their growth.

[0020] A pesticide composition comprising one or more polymorphs of the present invention is a beneficial active ingredient in the field of controlling harmful plants even at low application rates, possesses a favorable herbicidal spectrum, and exhibits good tolerance by warm-blooded animal species, fish, and grasses including rice, wheat, barnyard grass, oats, rye, millet, foxtail millet, barnyard grass, corn, finger millet, and sorghum. The composition of the present invention not only exhibits herbicidal effects on annual weeds including barnyard grass, Monochoria vaginalis, Lindernia procumbens, Eleocharis acutiloba, and Cyperus rotundus, but also shows high efficacy against weeds that have developed resistance to existing tablets.

[0021] Therefore, a pesticide composition comprising one or more polymorphs of the present invention can be used to control harmful plants growing in fields where several grasses are cultivated.

[0022] Therefore, the present invention also provides a method for controlling weeds in the cultivation of grasses, comprising the step of treating a field in which grasses are cultivated with an amount of the agricultural composition of the present invention that is effective in controlling harmful plants.

[0023] It should be understood that crops may be naturally occurring, obtained through conventional breeding methods, or obtained through genetic modification. These include crops that possess so-called output traits (e.g., improved storage stability, higher nutritional value, and improved flavor).

[0024] It should be understood that crops also include crops that have been given resistance to herbicides such as bromoxynil or classes of herbicides including ALS-, EPSPS-, GS-, HPPD-, and PPO- inhibitors. An example of a crop given resistance to imidazolinone, e.g., imazamox, through conventional breeding methods is Clearfield® summer canola. Examples of crops given resistance to herbicides through genetic modification include glyphosate- and glufosinate-resistant maize varieties, commercially available under the trademarks RoundupReady®, Herculex I®, and LibertyLink®.

[0025] It should also be understood that crops are either naturally occurring or have been given resistance to harmful insects. This includes plants transformed by the use of recombinant DNA technology that makes it possible to synthesize, for example, one or more selectively acting toxins, including those known to be derived from toxin-producing fungi. Examples of toxins that may be expressed include δ-endotoxins, plant insecticidal proteins (Vip), insecticidal proteins of bacterial colony-forming nematodes, and toxins produced by scorpions, arachnids, wasps, and fungi.

[0026] An example of a crop modified to express Bacillus thuringiensis toxin is Bt maize KnockOut® (Syngenta Seeds). An example of a crop containing two or more genes encoding insecticide resistance and therefore expressing two or more toxins is VipCot® (Syngenta Seeds). Crops or their seed material may also be resistant to multiple pests (so-called stacked transgenic events when formed by genetic modification). For example, a plant may be herbicide resistant and at the same time express insecticidal proteins, such as Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

[0027] The amount of the pesticide composition of the present invention applied depends on the specific type of harmful plant to be controlled, the required degree of control, and the timing and method of application, and can be easily determined by those skilled in the art. Generally, the composition of the present invention can be applied at a rate of 0.005 kilograms / hectare (kg / ha) to about 5.0 kg / ha, based on the total amount of the active ingredient in the composition (wherein "active ingredient" means one or more polymorphs of the present invention). A rate of about 0.1 kg / ha to about 1.5 kg / ha is preferred, and a rate of about 0.3 kg / ha to 0.8 kg / ha is particularly preferred.

[0028] In practice, a pesticide composition comprising one or more polymorphs of the present invention is applied as a formulation containing various auxiliary agents and carriers known or used in the art.

[0029] These formulations may be in various physical forms, such as powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifying concentrates, microemulsifying concentrates, oil-in-water emulsions, oil-flowable formulations, aqueous dispersions, oily dispersions, suspend emulsions, capsule suspensions, emulsifying granules, soluble liquids, water-soluble concentrates (containing water or water-miscible organic solvents as a carrier), impregnated polymer films, or other forms known from, for example, the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations may be used directly or diluted before use. Dilution may be carried out, for example, with water, liquid fertilizers, micronutrients, bioorganisms, oils, or solvents.

[0030] Formulations may be prepared, for example, by mixing one or more polymorphs ("active ingredient") with formulation adjuvants to obtain formulations in the form of a finely ground solid, granules, solution, dispersion, or emulsion. The active ingredient may also be formulated with other adjuvants such as a finely ground solid, mineral oil, plant or animal oil, modified plant or animal oil, organic solvent, water, surfactant, or combination thereof.

[0031] The active ingredient may also be contained in fine microcapsules. Microcapsules contain the active ingredient in a porous carrier. This allows the active ingredient to be released into the environment in a controlled amount (e.g., sustained release). Microcapsules typically have a diameter of 0.1 to 500 μm. They contain the active ingredient in an amount of about 25 to 95% by weight of the capsule weight. The active ingredient may be in the form of a monolithic solid, fine particles in a solid or liquid dispersion, or a suitable solution. The encapsulation membrane may include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymers and starch xanthate or other polymers known to those skilled in the art. Alternatively, fine microcapsules may be formed in which the active ingredient is contained in the form of finely ground particles in a solid matrix of the substrate, but the microcapsule itself is not encapsulated.

[0032] Pharmaceutical additives suitable for the preparation of the formulation according to the present invention are known in themselves. The following can be used as liquid carriers: water, toluene, o-xylene, m-xylene, p-xylene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetophenone, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, butyl acetate, isobornyl acetate, alkyl esters of acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-Heptanone, α-Pinene, d-Limonene, Ethyl Lactate, Ethylene Glycol, Ethylene Glycol Butyl Ether, Ethylene Glycol Methyl Ether, γ-Butyrolactone, Glycerol, Glycerol Acetate, Glycerol Diacetate, Glycerol Triacetate, Hexadecane, Hexylene Glycol, Isooctane, Isophorone, Isopropylbenzene, Isopropyl Myristate, Lactic Acid, Laurylamine, Mesityl Oxide, Methoxypropanol, Methyl Isoamyl Ketone, Methyl Isobutyl Ketone, Methyl Laurate, Methyl Octanoate, Methyl Oleate, Methylene Chloride, m-Xylene, n-Hexane, n-Octylamine, Octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol methyl ether, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols with higher molecular weights, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, etc.

[0033] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, crushed walnut shells, lignin, and similar materials.

[0034] Numerous surfactants can be advantageously used in both solid and liquid formulations, particularly in formulations that may be diluted with a carrier before use. Surfactants may be anionic, cationic, nonionic, or polymeric, and they may be used as emulsifiers, wetting agents, or suspending agents, or for other purposes. Typical surfactants include, for example, salts of alkyl sulfates, e.g., diethanolamine lauryl sulfate; salts of alkylaryl sulfonates, e.g., calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide addition products, e.g., nonylphenol ethoxylate; alcohol / alkylene oxide addition products, e.g., tridecyl alcohol ethoxylate; soaps, e.g., sodium stearate; salts of alkylnaphthalene sulfonates, e.g., sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, e.g., sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, e.g., sorbitol oleate; quaternary amines, e.g., lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids, e.g., polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphate esters; and further, e.g., McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Further substances are listed in Jersey (1981).

[0035] Further auxiliary agents that may be used in formulations according to the present invention include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoaming agents, complexing agents, neutralizing agents or pH adjusting substances and buffering agents, corrosion inhibitors, fragrances, wetting agents, uptake promoters, micronutrients, plasticizers, lubricants, dispersants, thickeners, antifreeze agents, fungicides, and liquid and solid fertilizers.

[0036] The formulations according to the present invention may include additives comprising plant or animal-derived oils, mineral oils, alkyl esters of such oils, or mixtures of such oils and oil derivatives. The amount of oil additives in the formulations according to the present invention is generally 0.01 to 10% based on the mixture to be applied. For example, oil additives may be added to a spray tank at a desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oils or plant-derived oils, such as rapeseed oil, olive oil, or sunflower oil, emulsified vegetable oils, alkyl esters of plant-derived oils, such as methyl derivatives, or animal-derived oils, such as fish oil or beef tallow. Preferred oil additives include alkyl esters of C8-C22 fatty acids, particularly methyl derivatives of C12-C18 fatty acids, such as methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th Edition, Southern Illinois University, 2010.

[0037] The formulations of the present invention generally contain 0.1 to 99% by weight, particularly 0.1 to 95% by weight, of the polymorph of the present invention and 1 to 99.9% by weight of formulation adjuvants, the formulation adjuvants preferably contain 0 to 25% by weight of a surfactant. Commercial products may preferably be formulated as concentrates, but end users will typically use diluted formulations.

[0038] The application rate varies over a wide range and depends on soil properties, application method, crop, pests being controlled, current climatic conditions, and other factors that depend on the application method, timing, and target crop. As a general guideline, the polymorph of the present invention can be applied in amounts of 1 to 2000 l / ha, particularly 10 to 1000 l / ha.

[0039] A preferred formulation may have the following composition (by weight): Emulsifiable concentrate: Active ingredient: 1-95%, preferably 60-90% Surfactants: 1-30%, preferably 5-20% Liquid carrier: 1-80%, preferably 1-35%

[0040] Powder: Active ingredient: 0.1-10%, preferably 0.1-5% Solid carrier: 99.9-90%, preferably 99.9-99%

[0041] Suspension concentrate: Active ingredient: 5-75%, preferably 10-50% Water: 94-24%, preferably 88-30% Surfactants: 1-40%, preferably 2-30%

[0042] Wettable powder: Active ingredient: 0.5-90%, preferably 1-80% Surfactants: 0.5-20%, preferably 1-15% Solid support: 5-95%, preferably 15-90%

[0043] Granules: Active ingredient: 0.1-30%, preferably 0.1-15% Solid carrier: 99.5-70%, preferably 97-85%

[0044] The following formulation examples further illustrate the present invention, but do not limit it.

[0045] Wettable powder example 1: Active ingredient: 25% Sodium lignosulfonate: 5% Sodium lauryl sulfate: 3% Highly dispersed silicic acid: 5% Kaolin: 62% Mix the combination thoroughly with the auxiliary agent, grind the mixture thoroughly in a suitable mill, and add the wettable powder. This can then be diluted with water to obtain a suspension of the desired concentration.

[0046] Wettable powder example 2: Active ingredient: 50% Sodium lignosulfonate: 5% Sodium dibutylnaphthalene sulfonate: 6% Phenol-polyethylene glycol ether (7-8 mol of ethylene oxide): 2% Highly dispersed silicic acid: 10% Kaolin: 27% Mix the combination thoroughly with the auxiliary agent, grind the mixture thoroughly in a suitable mill, and add the wettable powder. This can then be diluted with water to obtain a suspension of the desired concentration.

[0047] Wettable powder example 3: Active ingredient: 75% Sodium lauryl sulfate: 5% Sodium dibutylnaphthalene sulfonate: 10% Highly dispersed silicic acid: 10% Mix the combination thoroughly with the auxiliary agent, grind the mixture thoroughly in a suitable mill, and add the wettable powder. This can then be diluted with water to obtain a suspension of the desired concentration.

[0048] Example 1 of powder formulations for treating dried seeds: Active ingredient: 25% Diesel fuel: 5% Highly dispersed silicic acid: 5% Kaolin: 65% The combination can be thoroughly mixed with the auxiliary agent, the mixture can be thoroughly ground in a suitable mill to obtain a powder, which can then be used directly for seed treatment.

[0049] Example 2 of powder formulations for treating dried seeds: Active ingredient: 50% Diesel fuel: 5% Highly dispersed silicic acid: 5% Kaolin: 40% The combination can be thoroughly mixed with the auxiliary agent, the mixture can be thoroughly ground in a suitable mill to obtain a powder, which can then be used directly for seed treatment.

[0050] Example 3 of powder formulations for treating dried seeds: Active ingredient: 75% Diesel fuel: 5% Kaolin: 20% The combination can be thoroughly mixed with the auxiliary agent, the mixture can be thoroughly ground in a suitable mill to obtain a powder, which can then be used directly for seed treatment.

[0051] Examples of emulsifiable concentrates: Active ingredient: 10% Octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide): 3% Calcium dodecylbenzenesulfonate: 3% Castor oil polyglycol ether (35 mol of ethylene oxide): 4% Cyclohexanone: 30% Xylene mixture: 50% Any emulsion of the required dilution that can be used in the control of harmful plants can be obtained from this concentrate by dilution with water.

[0052] Powder example 1: Active ingredient: 5% Talcum: 95% Ready-to-use powders are obtained by mixing the combination with a carrier and grinding the mixture in a suitable mill. Such powders can also be used for drying and coating seeds.

[0053] Powder example 2: Active ingredient: 6% Kaolin: 94% Ready-to-use powders are obtained by mixing the combination with a carrier and grinding the mixture in a suitable mill. Such powders can also be used for drying and coating seeds.

[0054] Powder example 3: Active ingredient: 4% Inorganic filler: 96% Ready-to-use powders are obtained by mixing the combination with a carrier and grinding the mixture in a suitable mill. Such powders can also be used for drying and coating seeds.

[0055] Examples of extruded granules: Active ingredient: 15% Sodium lignosulfonate: 2% Carboxymethylcellulose: 1% Kaolin: 82% The combination is mixed, ground together with the auxiliary agent, and the mixture is moistened with water. The mixture is then extruded and dried in an airflow.

[0056] Examples of coated granules: Active ingredient: 8% Polyethylene glycol (molecular weight 200): 3% Kaolin: 89% The finely ground mixture is mixed in a blender with kaolin moistened with polyethylene glycol. Apply uniformly. A dust-free coated granule is obtained in this manner.

[0057] Examples of suspension concentrates: Active ingredient: 40% Propylene glycol: 10% Nonylphenol polyethylene glycol ether (15 mol of ethylene oxide): 6% Sodium lignosulfonate: 10% Carboxymethylcellulose: 1% Silicone oil (in the form of an emulsion at 75% in water): 1% Water: 32% The finely ground combination is thoroughly mixed with an auxiliary agent to obtain a suspension concentrate, which can then be used as is or diluted with water to obtain a suspension of any desired dilution. Weed control can be achieved by using such a suspension concentrate or its diluted solution to treat living plants by spraying, pouring, or immersion, or by treating seeds by spraying, pouring, or immersion, and then sowing the seeds.

[0058] Examples of flowable concentrates for seed treatment: Active ingredient: 40% Propylene glycol: 5% Copolymer Butanol PO / EO: 2% Tristyrenephenol containing 10-20 mol of EO: 2% 1,2-Benzisothiazolin-3-one (in the form of a 20% solution in water): 0.5% Monoazo pigment calcium salt: 5% Silicone oil (in the form of an emulsion at 75% in water): 0.2% Water: 45.3% The pulverized mixture is homogeneously mixed with an auxiliary agent to obtain a suspension concentrate, from which a suspension of any desired dilution can be obtained by dilution with water. Using such a diluted solution, seeds can be treated by spraying, pouring, or dipping to achieve weed control at the time of sowing.

[0059] Examples of sustained-release capsule suspensions: 28 parts of the active ingredient are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of an antifoaming agent, and 51.6 parts of water until the desired particle size is obtained. A mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water is added to this emulsion. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% of the active ingredient. The median capsule diameter is 8-15 μm. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for the relevant purpose.

[0060] Each of the above formulations may be prepared as a package containing one or more polymorphs of the present invention together with other components of the formulation (diluents, emulsifiers, surfactants, etc.). The formulations may also be prepared by a tank-mix method, in which the components are obtained separately and combined at the grower's site.

[0061] These formulations can be applied to areas where control is needed by conventional methods. For example, powders and liquid formulations can be applied using power sprayers, brushes, and manual sprayers and sprayers. The formulations can also be applied from an airplane as powder or spray, or by rope wick application. Both solid and liquid formulations can be applied to the soil of the habitat of the treated plants to allow the active ingredient to penetrate the plants through the roots.

[0062] The polymorphs and compositions thereof of the present invention are also suitable for protecting seeds, e.g., fruits, tubers or grains, or seedlings from the above-mentioned types of harmful plants. The propagating material can be treated with the polymorph before planting; for example, seeds can be treated before sowing. Alternatively, the polymorph can be applied (coated) to the seeds by immersing them in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the composition to the site of application of the propagating material, for example, when planting in a sowing furrow between furrow planting. These treatment methods for seeds, and the seeds thus treated, are further subjects of the present invention. Typical treatment rates depend on the plant to be controlled and are generally 1 to 200 grams per 100 kg of seeds, preferably 5 to 150 grams per 100 kg of seeds, for example, 10 to 100 grams per 100 kg of seeds.

[0063] The present invention also includes seeds coated, treated, or containing the polymorph of the present invention. The term “coated, treated, and / or containing” generally indicates that at the time of application, the majority of the active ingredient is on the surface of the seed, but depending on the method of application, a larger or smaller portion of the ingredient may penetrate into the seed material. When the seed product is (re)planted, the seed product may absorb the active ingredient. In one embodiment, the present invention provides seeds to which the compound of formula [II] is adhered. Furthermore, this provides a composition comprising seeds treated with the compound of formula [II].

[0064] Seed treatment includes all suitable seed treatment techniques known in the art, such as seed coating, seed covering, seed spraying, seed dipping, and seed pelletizing. The application of the compound of formula [I] to seed treatment can be done by any known method, such as spraying or by distributing the seeds, before sowing or during sowing / planting of seeds.

[0065] Ideally, the agricultural compositions and formulations of the present invention are applied before the emergence of harmful plants. The proportion and frequency of use of the formulations are those conventionally used in the art.

[0066] The activity of compositions comprising the compounds and polymorphs according to the present invention can be greatly broadened and adapted to a wide range of commonly occurring situations by including other active substances. The active substances may be of a chemical or biological type, and if biological, they can be further modified from naturally occurring biological species. Active substances include herbicides similar to those of the compounds and polymorphs according to the present invention, as well as substances that control, repel, or attract pests that damage or harm useful plants, substances that improve the growth of useful plants, such as plant growth disruptors, and substances that improve the performance of active substances, such as synergists. Examples include insecticides, acaricides, nematicides, molluskicides, algicidal agents, virusicides, rodenticides, fungicides, disease control agents, chemical sterilizers, and anthelmintics. Examples of biologically active substances include baculoviruses, plant extracts, and bacteria.

[0067] Accordingly, the present invention provides the use of the compositions according to the present invention in combination with one or more pest control agents, plant nutrients, or plant fertilizers. This combination may also include specific plant traits incorporated into plants by any means, such as conventional breeding or genetic modification.

[0068] Mixtures of the polymorph of the present invention with other active substances may also have further unexpected advantages, which may be described more broadly as synergistic activity. For example, these may include better tolerance by plants, reduced plant toxicity, control of insects at different developmental stages, or better behavior related to manufacturing, e.g., grinding or mixing, storage or use.

[0069] Individual active substances may occur in two or more groups or classes, and in two or more locations within one group or class: information on active substances, their spectra, sources, and classifications can be found in the Compendium of Pesticide Common Names (see http: / / www.alanwood.net / pesticides / index.html) or in the Pesticide Manual compiled by the British Crop Production Council (see http: / / bcpcdata.com / pesticide-manual.html).

[0070] One or more preferred polymorphs are shown below, where the polymorph of phenoxasulfone according to the present invention is indicated as "I".

[0071] Non-limiting examples of compositions containing auxiliary agents include compounds selected from the group of substances consisting of I+ petroleum.

[0072] Non-limiting examples of compositions containing herbicides include I+ Ioxynil, I+ Acronifen, I+ Acrolein, I+ Azaphenidine, I+ Acifluorphen, I+ Azimusulfuron, I+ Ashram, I+ Acetochrol, I+ Atrazine, I+ Anisifluprin, I+ Anilofos, I+ Amicarbazone, I+ Amidosulfuron, I+ Amitrol, I+ Aminocyclopyrachlor, I+ Aminopyralide, I+ Amiprophos-methyl, I+ Ametrin, I+ Alachlor, I+ Aloxidim, I+ Asinmidol, I+ Icaphorin-methyl, I+ Isouron I+Isoxachlortol, I+Isoxafenacil, I+Isoxaflutol, I+Isoxaben, I+Isodecyl alcohol ethoxylate, I+Isoproturone, I+Isotriazopiride, I+Ipfencarbazone, I+Imazaquin, I+Imazapic, I+Imazapyr, I+Imazametabenz-methyl, I+Imazamox, I+Imazetapir, I+Imazosulfuron, I+Indadiflame, I+Indanophan, I+Indlauxypyr-cyanomethyl, I+Eglinadin-ethyl, I+Esprocarb, I+Etamethosulfuron-methyl I+Ethalfluralin, I+Ethidimuron, I+Ethoxysulfuron, I+Ethoxyphene ethyl, I+Etofmesate, I+Etobenzanide, I+Epiriphenacil, I+Endotal disodium salt, I+Oxadiazone, I+Oxaziargyl, I+Oxadiclomefone, I+Oxasulfuron, I+Oxyfluorphen, I+Oryzalin, I+Orthosulfamuron, I+Olbencarb, I+Oleic acid, I+Cafenstrol, I+Carfentrazone ethyl, I+Carbutyrate, I+Carbetamide, I+Quizalofop ethyl I+Quizalofop-P-ethyl, I+Quizalofop-P-tefuryl, I+Quinoclamin, I+Quinclolac, I+Kimmelac, I+Cumiluron, I+Clasifos, I+Glyphosate, I+Glufosinate, I+Glufosinate-P-sodium salt, I+Cretodym, I+Clodinahop-propargyl, I+Clopyrald, I+Chromazon, I+Clomemethoxyfen, I+Clomeprop, I+Chloransulam-methyl, I+Chloranben, I+Chloridazone, I+Chlorimuron-ethyl, I+Chlorsulfuron, I+Chlortal-dimethyl,I+Chlorthiamide, I+Chlorphthalim, I+Chlorflurenol-methyl, I+Chlorprofam, I+Chlorbromulone, I+Cloxurone, I+Chlorotolone, I+Ketospiradox, I+Saflufenacil, I+Salmentin, I+Cyanazine, I+Cyanamide, I+Diurone, I+Dietatyl-ethyl, I+Dioxopyritrone, I+Dicamba, I+Cycloate, I+Cycloxidium, I+Diclolam, I+Cyclosulfamurone, I+Cyclopyranil, I+Cyclopyrimolate, I+Diclobenyl, I+Diclohop-P-methyl Chil, I+ Diclofop-methyl, I+ Dichlorprop, I+ Dichlorprop-P, I+ Diquat, I+ Dithiopyr, I+ Siderone, I+ Dinitramine, I+ Synidone-ethyl, I+ Synosulfurone, I+ Dinozeb, I+ Dinoterb, I+ Cyhalofop-butyl, I+ Cypirafluone, I+ Diphenamide, I+ Diphenzocort, I+ Diflufenican, I+ Diflufenzopyr, I+ Simazine, I+ Dimesulfazet, I+ Dimethachlor, I+ Dimethametrin, I+ Dimethenamide, I+ Dimethenamide-P, I+ Simetrin, I+ Dimepiperey I+ Dimeflon, I+ Synfluproline, I+ Synmethine, I+ Suep, I+ Sulcotrione, I+ Sulfiflumin, I+ Sulfentrazone, I+ Sulfosulfuron, I+ Sulfomethron-methyl, I+ Cethoxydim, I+ Terbasil, I+ Daimuron, I+ Takistmin-A, I+ Darapon, I+ Thiazopyr, I+ Thiafenasil, I+ Thiencarbazone, I+ Thiocarbasil, I+ Thiobencarb, I+ Thidiazimine, I+ Thidiazuron, I+ Thifensulfuron-methyl, I+ Desmedifam, I+ Desmethrin I+ Tetoflupyrrolimet, I+ Tenylchlor, I+ Tebutam, I+ Tebuthiurone, I+ Tepraloxidim, I+ Tefuryltrione, I+ Tembotrione, I+ Terbutyrazine, I+ Terbutrin, I+ Terbumetone, I+ Tempotrione, I+ Topramezon, I+ Tolacoxidim, I+ Triaziflame, I+ Triasulfurone, I+ Triafamone, I+ Trialate, I+ Trietadine, I+ Triclopyr, I+ Triclopyr-Butotyl, I+ Tritosulfurone, I+ Tripyrasulfone, I+ Trifludimoxazine, I+ TritosulfuroneI+ Triflusulfuron-methyl, I+ Trifluralin, I+ Trifloxysulfuron sodium salt, I+ Trivenuron-methyl, I+ Tolpyralate, I+ Naptalum, I+ Naproanilide, I+ Napropamide, I+ Napropamide-M, I+ Nicosulfuron, I+ Nebulon, I+ Norflurazone, I+ Vernalate, I+ Paraquat, I+ Haruxifen-benzyl, I+ Haruxifen-methyl, I+ Haloxyhop, I+ Haloxyhop-P, I+ Haloxyhop-ethotyl, I+ Halosaphen, I+ Halosulfuron-methyl, I+ Bixlo I+ Pichloram, I+ Picolinafen, I+ Bicyclopyrone, I+ Bispiribac sodium salt, I+ Pinoxadene, I+ Bipirazone, I+ Bifenox, I+ Piperofos, I+ Pyraculinate, I+ Pyraclonil, I+ Pyrasulfolol, I+ Pyrazoxyfen, I+ Pyrazosulfuron ethyl, I+ Pyrazolinate, I+ Biranaphos, I+ Pyrafurfen ethyl, I+ Pyridafol, I+ Pyrithiobac sodium salt, I+ Pyridate, I+ Pyriphthalide, I+ Pyributicarb, I+ Pyribenzoxime, I+ Pyrimisulfan, I+ Pyriminovac-methyl, I+ Pyroxasulfone, I+ Piroxulam, I+ Phenifam, I+ Fenuron, I+ Phenoxaprop, I+ Phenoxaprop-P, I+ Phenopoxydime, I+ Fenquinotrione, I+ Fentiaprop-ethyl, I+ Phentrazamide, I+ Fenpirazone, I+ Fenmedifam, I+ Butachlor, I+ Butaphenacil, I+ Butamiphos, I+ Butyrate, I+ Butenachlor, I+ Butralin, I+ Butroxidime, I+ Flazasulfuron, I+ Flamprop, I+ Flamprop-M, I +Primisulfuron-methyl, I+Fluadifop-butyl, I+Fluadifop-P-butyl, I+Fluazolate, I+Fluomethurone, I+Fluoroglycofen-ethyl, I+Flucarbazone-sodium salt, I+Fluchloraminopyr, I+Fluchloralin, I+Flusulfinum, I+Flucetosulfuron, I+Flutiaset-methyl, I+Flupirsulfuron-methyl-sodium salt, I+Fluphenacet, I+Fluphenoximasil, I+Flufenpyr-ethyl, I+Flupropanate, I+Flupoxam, I+Flumioxazine,I+ Flumicrolac pentyl, I+ Flumetsuram, I+ Flulidone, I+ Flulutamone, I+ Fluroxypyr, I+ Flurochloridone, I+ Pretilachlor, I+ Procarbazone sodium salt, I+ Broclozone, I+ Prodiamine, I+ Prosulfuron, I+ Prosulfocarb, I+ Propaxafop, I+ Propacrol, I+ Propazine, I+ Propanyl, I+ Propysamide, I+ Propisochlor, I+ Propyrisulfuron, I+ Profam, I+ Profluazole, I+ Prohexadione calcium salt, I+ Propoxycarbazone I+ Propoxycarbazone sodium salt, I+ Profoxidim, I+ Bromacil, I+ Brompyrazone, I+ Promethrin, I+ Prometon, I+ Bromoxynyl, I+ Bromophenoxime, I+ Bromobutide, I+ Floraslam, I+ Florpyrauxifen, I+ Florpyrauxifen benzyl, I+ Hexazinone, I+ Petoxamide, I+ Benazoline, I+ Penoxslam, I+ Heptamalloxyloglucan, I+ Beflubutamide, I+ Beflutamide-M, I+ Pebrate, I+ Pelargonic acid, I+ Bencarbazone, I+ Benkitrione, I +Pendimethalin, I+Benzufenzizone, I+Benslid, I+Bensulfuron-methyl, I+Benzobicyclon, I+Benzofenap, I+Bentazone, I+Pentanochlor, I+Pentoxazone, I+Benfluralin, I+Benfresate, I+Hosamine, I+Homesaphen, I+Foramsulfuron, I+Forchlorfenuron, I+Mecoprop, I+Mecoprop-P-potassium salt, I+Mesosufuron-methyl, I+Mesotrione, I+Metazachlor, I+Metazosulfuron, I+Metabenzuthiazuron, I+Metamitron, I+Me Tamihop, I+ Metam, I+ Disodium Methanearsone (DSMA), I+ Methiozoline, I+ Methyldimuron, I+ Methoxrone, I+ Methoslam, I+ Methosulfuron-methyl, I+ Metobromulone, I+ Metobenzuron, I+ Metrachlor, I+ Metrivudine, I+ Mepicort-chloride, I+ Mefenacet, I+ Monosulfuron, I+ Monolinuron, I+ Molinate, I+ Iodosulfuron, I+ Iodosulfuron-methylsodium salt, I+ Iofensulfuron, I+ Iofensulfuron-sodium salt, I+ LactofenI+ Lancotrione, I+ Linuron, I+ Limisoxaphene, I+ Limusulfuron, I+ Renacyl, I+ 2,2,2-Trichloroacetic acid (TCA), I+ 2,3,6-Trichlorobenzoic acid (2,3,6-TBA), I+ 2,4,5-Trichlorophenoxyacetic acid (2,4,5-T), I+ 2,4-Dichlorophenoxyacetic acid (2,4-D), I+ 2-Amino-3-Chloro-1,4-Naphthoquinone (ACN), I+ 2-Methyl-4-chlorophen Examples include methyl-4-chlorophenoxybutyrate (MCPA), 2-methyl-4-chlorophenoxybutyrate (MCPB), 4-(2,4-dichlorophenoxy)butyrate (2,4-DB), 4,6-dinitro-O-cresol (DNOC), AE-F-150944, IR-6396, MCPA-thioethyl, SYP-298, SYP-300, S-ethyldipropylthiocarbamate (EPTC), and S-metholol.

[0073] Non-limiting examples of compositions containing disease control agents include: I+ acibenzol, I+ aldimorph, I+ ampropylphos, I+ andprim, I+ azaconazole, I+ azoxystrobin, I+ venalaxyl, I+ benomyl, I+ bialaphos, I+ blastosidine-S, I+ Bordeaux mixture, I+ bromconazole, I+ bupirimate, I+ carpropamide, I+ captahol, I+ captan, I+ carbendazim, I+ chlorphenazole, I+ chloroneb, I+ chloropicrin, I+ chlorothalonil, I+ clozolinate, I+ copper oxychloride, I+ copper salt, I+ Cyflufenamide, I+Cymoxanil, I+Cyproconazole, I+Cyprodinil, I+Ciproflam, I+RH-7281, I+Diclosimet, I+Diclobutrazol, I+Diclobentiazox, I+Diclomedin, I+Dichloran, I+Difenoconazole, I+RP-407213, I+Dimethomorph, I+Dimoxystrobin, I+Diniconazole, I+Diniconazole-M, I+Dodin, I+Edifenfos, I+Epoxyconazole, I+Famoxadone, I+Phenamidon, I+Phenalimol, I+Fenbuconazole, I+Fen Calamide, I+ Fenpiclonil, I+ Fenpropidine, I+ Fenpropimorph, I+ Fentin acetate, I+ Fluazinam, I+ Fludioxonil, I+ Flumetova, I+ Flumorph / Fulmorlin, I+ Fentin hydroxide, I+ Fluoxastrobin, I+ Fluquinconazole, I+ Flusilazole, I+ Flutolanil, I+ Flutriafoll, I+ Holpet, I+ Fosetylaluminum, I+ Flalaxil, I+ Flamethopir, I+ Hexaconazole, I+ Ipconazole, I+ Iprobenphos, I+ Iprodione, I+ Isopropyl I+Isothianil, I+Kasugamycin, I+Kresoximmethyl, I+Mancozeb, I+Maneb, I+Mefenoxam, I+Mepronil, I+Metalaxyl, I+Metconazole, I+Metominostrobin / Phenominostrobin, I+Metraphenone, I+Mycrobutanil, I+Neoasodine, I+Nicovifen, I+Orysastrobin, I+Oxadixyl, I+Penconazole, I+Pencyclon, I+Probenazole, I+Prochloraz, I+Propamocarb, I+Propioconazole, I+Proquinazide, I+Prothioconazole,Examples include I+ pyrifenox, I+ pyraclostrobin, I+ pyrimethanil, I+ pyroquilon, I+ quinoxyfen, I+ spiroxamine, I+ sulfur, I+ tebuconazole, I+ teconazole, I+ thiabendazole, I+ tifluzamide, I+ thiophanate-methyl, I+ thyram, I+ thiadinyl, I+ triadimefone, I+ triadimenol, I+ tricyclazole, I+ trifloxystrobin, I+ triticonazole, I+ validamycin, and I+ vinclozine.

[0074] Non-limiting examples of compositions containing acaricides include: I+1,1-bis(4-chlorophenyl)-2-ethoxyethanol, I+2,4-dichlorophenylbenzenesulfonate, I+2-fluoro-N-methyl-N-1-naphthylacetamide, I+4-chlorophenylphenylsulfone, I+abamectin, I+acequinosyl, I+acetoprol, I+acrinatrin, I+aldicarb, I+aldoxycarb, I+α-cypermethrin, I+amidithion, I+amidoflumeth, I+amidothioate, I+amiton, I+amiton hydrogen oxalate, I+amitraz, I+aramite, I+arsenic trioxide, I+AVI 382, I+AZ60541, I+Adinphos-ethyl, I+Adinphos-methyl, I+Azobenzene, I+Azocyclotin, I+Azothoate, I+Benomyl, I+Benoxaphos, I+Benzoximate, I+Benzyl benzoate, I+Bifenazate, I+Bifenthrin, I+Binapacril, I+Profenvalerate, I+Bromosicren, I+Bromos, I+Bromos-ethyl, I+Bromopropylate, I+Buprofezin, I+Butocarboxime, I+Butoxycarboxime, I+Butylpyridabene, I+Calcium polysulfide, I+Camfechlor, I+Carbanolate, I+Carbaryl, I+Carbofuran, I+Carbophenothion, I+CGA 50'439, I+ Quinomethionato, I+ Chlorbenside, I+ Chlordimeform, I+ Chlordimeform hydrochloride, I+ Chlorfenapyr, I+ Chlorphenetol, I+ Chlorfensone, I+ Chlorfensulfide, I+ Chlorfenvinphos, I+ Chlorobenzylate, I+ Chloromebform, I+ Chloromethirone, I+ Chloropropylate, I+ Chlorpyrifos, I+ Chlorpyrifos-methyl, I+ Chlorthiofos, I+ Synerin I, I+ Syneri I+Synerin, I+Clofentezine, I+Closantel, I+Coumaphos, I+Crotamiton, I+Clotoxyphos, I+Cufraneb, I+Cyanthoate, I+Cyflumetofen, I+Cyhalotrin, I+Cyhexatin, I+Cypermethrin, I+DCPM, I+DDT, I+Demefion, I+Demefion-O, I+Demefion-S, I+Demeton, I+Demeton-methyl, I+Demeton-O, I+Demeton-O-methyl, I+Demeton-S,I+ Demeton-S-methyl, I+ Demeton-S-methylsulfone, I+ Diafenthiurone, I+ Dialiphos, I+ Diazinon, I+ Diclofluanide, I+ Dichlorvos, I+ Dicriphos, I+ Dicofor, I+ Diclotophos, I+ Dienochlor, I+ Dimehox, I+ Dimethoate, I+ Dinactin, I+ Dinex, I+ Dinex-dicrexin, I+ Dinobutone, I+ Dinocup, I+ Dinocup-4, I+ Dinocup-6, I+ Dinoctone, I+ Dinopenton, I+ Dinosulfone, I+ Dinoterbone, I+ Dioxathion, I+ Diphenylsulfone, I+ Disulfiram, I+ Disulfone, I+ DNOC, I+ Dofenapine, I+ Doramectin, I+ Endosulfan, I+ Endothion, I+ EPN, I+ Eprinomectin, I+ Ethion, I+ Ethoate-methyl, I+ Ethoxazole, I+ Etrimphos, I+ Phenazaflor, I+ Phenazakine, I+ Fenbutasin oxide, I+ Phenothiocarb, I+ Fenpropathrin, I+ Fenpyrad, I+ Fenpyroximate, I+ Fenson, I+ Fentriphalin, I+ Fenvalerate, I+ Fipronil, I+ Fluacrypyrim, I+ Fluazuron, I+ Flubendimin, I+ Flucycloxuron, I+ Flucitrinate, I+ Fluenetil, I+ Flufenoxuron, I+ Flumethrin, I+ Fluolbenside, I+ Fluvalinate, I+ FMC 1137, I+ Formetanate, I+ Formetanate hydrochloride, I+ Formothione, I+ Formparanate, I+ γ-HCH, I+ Gliodin, I+ Halfenprox, I+ Heptenofos, I+ Hexadecylcyclopropanecarboxylate, I+ Hexythiazox, I+ Iodomethane, I+ Isocarbophos, I+ Isopropyl O-(methoxyaminothiophosphoryl) salicylate, I+ Ivermectin, I+ Jasmolin I, I+ Jasmolin I I, I+ Iodofenphos, I+ Lindan, I+ Lufenulon, I+ Malathion, I+ Malonoben, I+ Mecarbam, I+ Mephosphoran, I+ Mesulfen, I+ Methacryphos, I+ Methamidophos, I+ Methidathion, I+ Methiocarb, I+ Methomyl, I+ Methyl bromide, I+ Metolcarb, I+ Mevinphos, I+ Mexacalbate, I+ Milbemectin, I+ Milbemycin oxime, I+ Mipahox, I+ Monoclotophos, I+ Morphothion,I+ Moxidectin, I+ Nared, I+ NC-184, I+ NC-512, I+ Niflulidide, I+ Nicomycin, I+ Nitrilacarb, I+ Nitrilacarb 1:1 zinc chloride complex, I+ NNI-0101, I+ NNI-0250, I+ Omethoate, I+ Oxamyl, I+ Oxideprophos, I+ Oxydisulfon, I+ pp'-DDT, I+ Parathion, I+ Permethrin, I+ Petroleum, I+ Fencapton, I+ Fenthoate, I+ Phorate, I+ Phosalon, I+Phospholane, I+Fosmet, I+Phosphamidone, I+Foxim, I+Pyrimifos-methyl, I+Polychloroterpene, I+Polynactin, I+Proclonol, I+Profenofos, I+Promacil, I+Propargit, I+Propetamphos, I+Propoxar, I+Protidathion, I+Protoate, I+Pyrethrin I, I+Pyrethrin II, I+Pyrethrin, I+Pyridaben, I+Pyridafenthion, I+Pyrimidifen I+ Pyrimitate, I+ Quinalphos, I+ Quinthiokis, I+ R-1492, I+ RA-17, I+ Rotenone, I+ Shlardan, I+ Sebuphos, I+ Selamectin, I+ SI-0009, I+ Sofamide, I+ Spirodiclofen, I+ Spiromesifen, I+ SSI-121, I+ Sulfiram, I+ Sulfuramide, I+ Sulfotep, I+ Sulfur, I+ SZI-121, I+ τ-Fulvalinate, I+ Tebufenpyrad, I+ TEPP, I+ Telba Examples include I+tetrachlorvinphos, I+tetradiphon, I+tetranactin, I+tetrasul, I+thiaphenox, I+thiocarboxim, I+thiophanox, I+thiometon, I+thioquinox, I+turingiencin, I+triamiphos, I+triaten, I+triazophos, I+triazurone, I+trichlorfon, I+triphenophos, I+triactin, I+bamidthione, I+vaniliprole, and I+YI-5302.

[0075] Non-limiting examples of compositions containing biological control agents include I+ Adoxophyes orana GV, I+ Agrobacterium radiobacter, I+ Amblyseius spp., I+ Anagrapha falcifera NPV, I+ Anagrus atomus, I+ Aphelinus abdominalis, I+ Aphidius colemani, I+ Aphidoletes aphidimyza, I+ Autographa californica NPV, I+ Bacillus firmus, I+ Bacillus sphericus neide sphaericus Neide), I+ Bacillus thuringiensis Berliner, I+ Bacillus thuringiensis subsp. aizawai, I+ Bacillus thuringiensis subsp. israelensis, I+ Bacillus thuringiensis subsp. japonensis, I+ Bacillus thuringiensis subsp. kurstaki, I+ Bacillus thuringiensis subsp. tenebrionisI+ tenebrionis, I+ Beauveria bassiana, I+ Beauveria brongniartii, I+ Chrysoperla carnea, I+ Cryptolaemus montrouzieri, I+ Cydia pomonella GV, I+ Dacnusa sibirica, I+ Diglyphus isaea, I+ Encarsia formosa, I+ Eretmocerus eremicus, I+ Helicoverpa zea NPV, I+ Heterorhabditis bacteriophora bacteriophora) and H. megidis, I+ Hippodamia convergens, I+ Leptomastix dactylopii, I+ Macrolophus caliginosus, I+ Mamestra brassicae NPV, I+ Metaphycus helvolus, I+ Metarhizium anisopliae var. acridum, I+ Metarhizium anisopliae var. anisopliae, I+ Neodiprion N. sertifer) NPV and N. lecontei NPV, I+ Orius spp.), I+ Paecilomyces fumosoroseus, I+ Phytoseiulus persimilis, I+ Spodoptera exigua polycapsid nucleus polyhedrosis virus, I+ Steinernema bibionis, I+ Steinernema carpocapsae, I+ Steinernema feltiae, I+ Steinernema glaseri, I+ Steinernema riobrave, I+ Steinernema riobravis, I+ Steinernema scapteris Examples include *Trichogramma* spp., *Typhlodromus occidentalis*, and *Verticillium lecanii*.

[0076] Non-limiting examples of compositions containing soil sterilizers include I+ iodomethane and methyl bromide.

[0077] Non-limiting examples of compositions containing sterilizing agents include I+ aphorates, I+ bisadil, I+ busulfan, I+ diflubenzuron, I+ dimatif, I+ hemel, I+ hempa, I+ metepa, I+ methiotepa, I+ methyl aphorates, I+ molzide, I+ penflurone, I+ tepa, I+ thiohempa, I+ thiotepa, I+ tretamine, and I+ uredepa.

[0078] Non-limiting examples of compositions containing insect pheromones include I+(E)-deca-5-en-1-yl acetate and (E)-deca-5-en-1-ol, I+(E)-trideca-4-en-1-yl acetate, I+(E)-6-methylhepta-2-en-4-ol, I+(E,Z)-tetradeca-4,10-dien-1-yl acetate, I+(Z)-dodeca-7-en-1-yl acetate, I+(Z)-hexadeca-11-enal, and I+(Z)-hexadeca-11-en-1-yl Luacetate, I+(Z)-Hexadeca-13-en-11-in-1-Ilacetate, I+(Z)-Icosa-13-en-10-on, I+(Z)-Tetradeca-7-en-1-ar, I+(Z)-Tetradeca-9-en-1-all, I+(Z)-Tetradeca-9-en-1-Ilacetate, I+(7E,9Z)-Dodeca-7,9-dien-1-Ilacetate, I+(9Z,11E)-Tetradeca-9,11-dien-1-Ilacetate, I+(9Z,12E)-Tetra Deca-9,12-dien-1-yl acetate, I+14-methyloctadeca-1-ene, I+4-methylnonan-5-ol and 4-methylnonan-5-one, I+α-multistriatin, I+brevicomin, I+chodrelua, I+chodremon, I+curua, I+disparua, I+dodeca-8-en-1-yl acetate, I+dodeca-9-en-1-yl acetate, I+dodeca-8, I+10-dien-1-yl acetate, I+dominicalua, I+4-methylocta Ethyl phosphate, I+ Eugenol, I+ Frontalin, I+ Gossiplua, I+ Grandlua, I+ Grandlua I, I+ Grandlua II, I+ Grandlua III, I+ Grandlua IV, I+ Hexalua, I+ Ipsdienol, I+ Ipsenol, I+ Japonilua, I+ Lineatin, I+ Littleua, I+ Luluua, I+ Medlua, I+ Megatomoic acid, I+ Methyl eugenol, I+ Muscarua, I+ Octadeca-2,13-dien-1-yl acetate, I+ Octadeca-3,Examples include 13-diene-1-ylacetate, I+olflurua, I+orictalua, I+ostramon, I+siglua, I+solzidine, I+sulcatol, I+tetradeca-11-ene-1-ylacetate, I+trimedrua, I+trimedrua A, I+trimedrua B1, I+trimedrua B2, I+trimedrua C, and I+trunk-chol.

[0079] Non-limiting examples of compositions containing insect repellents include I+2-(octylthio)ethanol, I+butopyronoxyl, I+butoxy(polypropylene glycol), I+dibutyl adipate, I+dibutyl phthalate, I+dibutyl succinate, I+diethyltoluamide, I+dimethyl carbate, I+dimethyl phthalate, I+ethylhexanediol, I+hexaamide, I+methquin-butyl, I+methylneodecanamide, I+oxamate, and I+picaridin.

[0080] Non-limiting examples of compositions containing insecticides include I+1-dichloro-1-nitroethane, I+1,1-dichloro-2,2-bis(4-ethylphenyl)ethane, I+, I+1,2-dichloropropane, I+1,2-dichloropropane and 1,3-dichloropropene, I+1-bromo-2-chloroethane, I+2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate, and I+2,2-dichlorovinyl 2-ethylsulfinylethylmethyl phosphate. I+2-(1,3-dithiolan-2-yl)phenyldimethylcarbamate, I+2-(2-butoxyethoxy)ethylthiocyanate, I+2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate, I+2-(4-chloro-3,5-xylyloxy)ethanol, I+2-chlorovinyldiethyl phosphate, I+2-imidazolidone, I+2-isovalerylindan-1,3-dione, I+2-methyl(propa-2-inyl) ) Aminophenylmethylcarbamate, I+2-thiocyanatoethyl laurate, I+3-bromo-1-chloropropa-1-ene, I+3-methyl-1-phenylpyrazole-5-yldimethylcarbamate, I+4-methyl(propa-2-inyl)amino-3,5-xylylmethylcarbamate, I+5,5-dimethyl-3-oxocyclohexa-1-enyldimethylcarbamate, I+abamectin, I+acephate, I+acetamiprid, I+acetylone, I+ Acetoprol, I+ Acrinatrin, I+ Acrylonitrile, I+ Aranicarb, I+ Aldicarb, I+ Aldoxycarb, I+ Aldrin, I+ Arethrin, I+ Allosamidin, I+ Alixicarb, I+ α-Cypermethrin, I+ α-Ecdysone, I+ Aluminum phosphide, I+ Amidithione, I+ Amidothioate, I+ Aminocarb, I+ Amiton, I+ Amiton Hydroxalate, I+ Amitraz, I+ Anabacin, I+ Atidathion, I+ AVI 382, I+AZ 60541, I+Azadirachtin, I+Azamethiphos, I+Adinphos-ethyl, I+Adinphos-methyl, I+Azothoate, I+Bacillus thuringiensis delta-endotoxin, I+Barium hexafluorosilicate, I+Barium polysulfide, I+Bartholin,I+Bayer 22 / 190, I+Bayer 22408, I+benziocarb, I+benfuracarb, I+bensultap, I+β-cyfluthrin, I+β-cypermethrin, I+bifenthrin, I+biorethrin, I+biorethrin S-cyclopentenyl isomer, I+bioethanomethrin, I+biopermethrin, I+biorethmetrin, I+bis(2-chloroethyl) ether, I+bistriflurone, I+borax, I+bromfenvalerate, I+bromfenbinphos, I+bromocy Clen, I+ Bromo-DDT, I+ Bromophos, I+ Bromophos-ethyl, I+ Bufencarb, I+ Buprofezin, I+ Butacarb, I+ Butathiophos, I+ Butocarboxime, I+ Butonate, I+ Butoxycarboxime, I+ Butylpyridabene, I+ Kazusaphos, I+ Calcium arsenate, I+ Calcium cyanide, I+ Calcium polysulfide, I+ Camphechlor, I+ Carbanolate, I+ Carbaryl, I+ Carbofuran, I+ Carbon disulfide, I+ Tetrachloride Carbon, I+Carbophenothione, I+Carbosulfan, I+Cartap, I+Cartap hydrochloride, I+Sevadin, I+Chlorubicyclene, I+Chlordan, I+Chlordecone, I+Chlordimeform, I+Chlordimeform hydrochloride, I+Chlorethoxyphos, I+Chlorfenapir, I+Chlorfenbinphos, I+Chlorfluazuron, I+Chlormephos, I+Chloroform, I+Chloropicrin, I+Chlorphoxime, I+Chlorprazophos, I+ Chlorpyrifos, I+Chlorpyrifos-methyl, I+Chlorthiofos, I+Chromafenozide, I+Synerin I, I+Synerin II, I+Synerin, I+Cis-resmethrin, I+Cismethrin, I+Crocitrin, I+Chloetocarb, I+Closantel, I+Clotianidin, I+Copper acetoarsenite, I+Copper arsenate, I+Copper oleate, I+Coumaphos, I+Cumithoate, I+Crotamiton, I+Clotoxyphos, I+Curufomate, I+Cryolite, I+CS 708, I+cyanophenphos, I+cyanophos, I+cyanthoate, I+ciclethrin, I+cycloprothrin, I+cyfluthrin, I+cyhalothrin, I+cypermethrin, I+cyphenothrin, I+cyromazine, I+cythioate, I+d-limonene, I+d-tetramethrin, I+DAEP, I+dazomet, I+DDT,I+ Decarbofuran, I+ Deltamethrine, I+ Demephyone, I+ Demephyone-O, I+ Demephyone-S, I+ Demeton, I+ Demeton-methyl, I+ Demeton-O, I+ Demeton-O-methyl, I+ Demeton-S, I+ Demeton-S-methyl, I+ Demeton-S-methylsulfone, I+ Diafenthiurone, I+ Dialiphos, I+ Diamidaphos, I+ Diazinon, I+ Dicapton, I+ Diclofenthion, I+ Dichlorvos, I+ Dicriphos, I+ Diclesyl, I+ Diclotophos, I+ Dicyclanil, I+ Dierdrin, I+ Diethyl 5- Methylpyrazole-3-yl phosphate, I+ diflubenzuron, I+ dilol, I+ dimefluthrin, I+ dimehox, I+ dimethane, I+ dimethoate, I+ dimethrin, I+ dimethylvinphos, I+ dimethilane, I+ dynex, I+ dynex-dicrexin, I+ dinoprop, I+ dynosam, I+ dynoseb, I+ dinotefuran, I+ diophenolane, I+ dioxabenzophos, I+ dioxacarb, I+ dioxathion, I+ disulfonate, I+ diticlophos, I+ DNOC, I+ doramectin, I+ DSP, I+ ecdysterone, I+ EI 1642, I+ Emamectin, I+ Emamectin benzoate, I+ EMPC, I+ Empenthrin, I+ Endosulfan, I+ Endothion, I+ Endrin, I+ EPBP, I+ EPN, I+ Epophenonane, I+ Eprinomectin, I+ Esfenvalerate, I+ Etaphos, I+ Ethiofencarb, I+ Ethion, I+ Ethiprole, I+ Ethoate-methyl, I+ Etoprophos, I+ Ethyl formate, I+ Ethyl-DDD, I+ Dibromide, I+ Dichloride, I+ Ethylene oxide, I+ Etofenprox, I+ Etrimphos, I+ EX D, I+Fanfar, I+Phenamifos, I+Phenazaflor, I+Fenchlorfos, I+Phenetacarb, I+Fenfluthrin, I+Fenitrothion, I+Phenobucarb, I+Phenoxacrim, I+Phenoxycarb, I+Fenpyritrin, I+Fenpropathrin, I+Fenpyrad, I+Fensulfothione, I+Fenthion, I+Fenthion-ethyl, I+Fenvalerate, I+Fipronil, I+Flonicamide, I+Flubendiamide, I+Flucoflon, I+Flucycloxlon, I+Flucitrinate, I+Fluenetil,I+ Flufenelim, I+ Flufenoxuron, I+ Flufenprox, I+ Flumethrin, I+ Fluvalinate, I+ FMC 1137, I+ Honofos, I+ Formetanate, I+ Formetanate hydrochloride, I+ Formothione, I+ Formparanate, I+ Fosmethilane, I+ Fosspire, I+ Fosthiazate, I+ Fosthiethane, I+ Frathiocarb, I+ Frethrin, I+ γ-Cyhalotrin, I+ γ-HCH, I+ Guazatin, I+ Guazatin acetate, I+ GY-81, I+ Halfenprox, I+ Halofenozide, I+ HCH, I+ HEOD, I+ Heptachlor, I+ Heptenofos, I+ Heterofos, I+ Hexaflumuron, I+ HHDN, I +Hydramethylnon, I+Hydrogen cyanide, I+Hydroprene, I+Hykincarb, I+Imidacloprid, I+Imiprothrin, I+Indoxacarb, I+Iodomethane, I+IPSP, I+Isazofos, I+Isobenzane, I+Isocarbos, I+Isodrine, I+Isofenphos, I+Isolane, I+Isoprocarb, I+Isopropyl O-(methoxyaminothiophosphoryl) salicylate, I+Isoprothiolane, I+Isothioate, I+Ixathion, I+Ivermectin, I+Jasmolin I, I+Di Jasmolin II, I+ Iodophenphos, I+ Juvenile Hormone I, I+ Juvenile Hormone II, I+ Juvenile Hormone III, I+ Kereban, I+ Quinoprene, I+ λ-Cyhalothrin, I+ Lead Arsenate, I+ Lepimectin, I+ Leptophos, I+ Lindan, I+ Lilimphos, I+ Lufenuron, I+ Litidathion, I+ m-Cumenylmethylcarbamate, I+ Magnesium Phosphide, I+ Malathion, I+ Malonoben, I+ Magidox, I+ Mecarbam, I+ Mecarphone, I+ Menazone, I+ Mephosphoran, I+ Mercurous Chloride, I+ Meth Rufenphos, I+ Metaflumizone, I+ Metam, I+ Metam-potassium, I+ Metam-sodium, I+ Methacryphos, I+ Methamidophos, I+ Methanesulfonyl fluoride, I+ Methidathion, I+ Methiocarb, I+ Metoclotophos, I+ Methomyl, I+ Methoprene, I+ Methquin-butyl, I+ Methotrin, I+ Methoxychloride, I+ Methoxyphenozide, I+ Methyl bromide, I+ Methylisothiocyanate, I+ Methylchloroform, I+ Methylene chloride, I+ Metofluthrin, I+ Metolcarb, I+ Methoxadiazone,I+ Mevinphos, I+ Mexacarbate, I+ Milbemectin, I+ Milbemycin oxime, I+ Mipahox, I+ Milex, I+ Monoclotophos, I+ Morphothion, I+ Moxidectin, I+ Naphthalophos, I+ Nared, I+ Naphthalene, I+ NC-170, I+ NC-184, I+ Nicotine, I+ Nicotine sulfate, I+ Niflulidide, I+ Nitenpyram, I+ Nichiazine, I+ Nitrilacarb, I+ Nitrilacarb 1:1 zinc chloride complex, I+ NNI-0101, I+ NNI-0250, I+ Nornicotine, I+ Novalon, I+ Noviflumuron, I+ O-5-Dichloro-4-iodophenyl O-ethylethyl phosphonothioate I+O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-ylphosphorothioate, I+O,O-diethyl O-6-methyl-2-propylpyrimidine-4-ylphosphorothioate, I+O,O,O',O'-tetrapropyldithiopyrophosphate, I+oleic acid, I+omethoate, I+oxamyl, I+oxydemeton-methyl, I+oxydeprophos, I+oxydisulfonate, I+pp'-DDT, I+para-dichlorobenzene, I+parathion, I+parathion-methyl, I+penflurone, I+pentachlorophenol, I+pentachlorophenyl laurate, I+permethrin, I+petroleum, I+PH 60-38, I+ Fencapton, I+ Phenothrin, I+ Phenthoate, I+ Phorate+TX, I+ Phosalone, I+ Phosphane, I+ Phosmet, I+ Phosnikrol, I+ Phosphamidone, I+ Phosphine, I+ Phoxime, I+ Phoxime-methyl, I+ Pyrimetaphos, I+ Pyrimicarb, I+ Pyrimiphos-ethyl, I+ Pyrimiphos-methyl, I+ Polychlorodicyclopentadiene isomer, I+ Polychloroterpene, I+ Potassium arsenite, I+ Potassium thiocyanate I+ Prallethrin, I+ Precosen I, I+ Precosen II, I+ Precosen III, I+ Primidophos, I+ Profenofos, I+ Profluthrin, I+ Promasil, I+ Promecarb, I+ Propaphos, I+ Propetamphos, I+ Propoxar, I+ Protidathion, I+ Prothiofos, I+ Protoate, I+ Protrefenbute, I+ Pymetrozine, I+ Piraclofos, I+ Pirazofos, I+ Pyrethmetrin, I+ Pyrethrin I, I+ Pyrethrin II,I+ Pyrethrin, I+ Pyridaben, I+ Pyridaryl, I+ Pyridafenthion, I+ Pyrimidifen, I+ Pyrimitate, I+ Pyriproxyfen, I+ Quassia, I+ Quinalphos, I+ Quinalphos-methyl, I+ Quinothion, I+ Quinthiokis, I+ R-1492, I+ Lafoxanide, I+ Resmethrin, I, +Rotenone, I+RU 15525, I+RU 25475, I+Lianya, I+Ryanodine, I+Sabajila, I+Shlardan, I+Cebuphos, I+Selamectin, I+SI-0009, I+SI-0205, I+SI-0404, I+SI-0405, I+Silafluofen, I+SN 72129, I+Sodium arsenite, I+Sodium cyanide, I+Sodium fluoride, I+Sodium hexafluorosilicate, I+Sodium pentachlorophenoxide, I+Sodium selenite, I+Sodium thiocyanate, I+Sofamide, I+Spinosad, I+Spiromesifen, I+Spirotetramato, I+Sulcoflon, I+Sulcoflon-sodium, I+Sulfuramide, I+Sulfotep, I+Sulfuryl fluoride, I+ Sulprophos, I+ Tar oil, I+ τ-fluvalinate, I+ Tadimucarb, I+ TDE, I+ Tebufenozide, I+ Tebufenpyrad, I+ Tebupyrimphos, I+ Teflubenzuron, I+ Tefluthrin, I+ Temephos, I+ TEPP, I+ Terarethrin, I+ Terbam, I+ Terbuphos, I+ Tetrachloroethane, I+ Tetrachlorvinphos, I+ Tetramethrin, I+ θ-Cypermethrin, I+ Thiacloprid, I+ Thiafenox, I+ Thiamethoxam, I+Cyclophos, I+Thiocarbox, I+Thiocarbox, I+Thiocarbox, I+Thiocarbox, I+Thiometon, I+Thionazine, I+Thiosultap, I+Thiosultap-sodium, I+Turingiencin, I+Torfenpyrad, I+Tralomethrin, I+Transfluthrin, I+Transpermethrin, I+Triamiphos, I+Triazamate, I+Triazophos I+ Triazurone, I+ Trichlorfon, I+ Trichlormetaphos-3, I+ Trichloronate, I+ Triphenophos, I+ Triflumulone, I+ Trimetacarb, I+ Triplene, I+ Bamidthione, I+ Vaniliprole, I+ Veratridine, I+ Veratrine, I+ XMC, I+ Xylylcarb, I+ YI-5302, I+ ζ-Cypermethrin, I+ Zetamethrin, I+ Zinc Phosphate, I+ Zolaprophos and ZXIExamples include 8901, I+cyantraniliprole, I+chlorantraniliprole, I+cyenopyrafen, I+cyflumetofen, I+pyrifluquinazone, I+spinetram, I+spirotetramato, I+sulfoxaflor, I+flufiprole, I+meperfluthrin, I+tetramethylfluthrin, and I+triflumesopyrim.

[0081] Non-limiting examples of compositions containing molluscicides include I+ bis(tributyltin) oxide, I+ bromoacetamide, I+ calcium arsenate, I+ chloetocarb, I+ copper acetoarsenite, I+ copper sulfate, I+ fentin, I+ ferric phosphate, I+ metaldehyde, I+ methiocarb, I+ niclosamide, I+ niclosamide-olamine, I+ pentachlorophenol, I+ sodium pentachlorophenoxide, I+ tadimucarb, I+ thiodicarb, I+ tributyltin oxide, I+ triphenmorph, I+ trimetacarb, I+ triphenyltin acetate and triphenyltin hydroxide, and I+ pyriprole.

[0082] Non-limiting examples of compositions containing nematicides include I+AKD-3088, I+1,2-dibromo-3-chloropropane, I+1,2-dichloropropane, I+1,2-dichloropropane and 1,3-dichloropropene, I+1,3-dichloropropene, I+3,4-dichlorotetrahydrothiophene 1,1-dioxide, I+3-(4-chlorophenyl)-5-methylrhodanine, I+5-methyl-6-thioxo-1,3,5-thiadiadinan-3-ylacetic acid, I+6-isopentenylaminopurine, I+abamectin, I+acetoprole, I+alanicarb, I+aldicarb, I+aldoxycarb, I+AZ 60541, I+ Bencrotiaz, I+ Benomyl, I+ Butylpyridaben, I+ Cazusaphos, I+ Carbofuran, I+ Carbon disulfide, I+ Carbosulfan, I+ Chloropicrin, I+ Chlorpyrifos, I+ Chloetocarb, I+ Cytokinin, I+ Dazomet, I+ DBCP, I+ DCIP, I+ Diamidaphos, I+ Diclofenthion, I+ Dicrifos, I+ Dimethoate, I+ Doramectin, I+ Emamectin, I+ Emamectin benzoate, I+ Eprinomectin, I+ Etoprofos, I+ Dibromide Ethylene, I+ Phenamiphos, I+ Fenpyrad, I+ Phensulfothion, I+ Fosthiazate, I+ Fosthiethane, I+ Furfural, I+ GY-81, I+ Heterophos, I+ Iodomethane, I+ Isamidophos, I+ Isazofos, I+ Ivermectin, I+ Kinetin, I+ Mecarphone, I+ Metam, I+ Metam-potassium, I+ Metam-sodium, I+ Methyl bromide, I+ Methylisothiocyanate, I+ Milbemycin oxime, I+ Moxidectin, I+ Mulberry dark spot disease fungus (Myrothecium) Examples of verrucaria compositions include I+NC-184, I+oxamyl, I+phorate, I+phosphamidone, I+phosphocarb, I+cebuphos, I+selamectin, I+spinosad, I+terbam, I+terbuphos, I+tetrachlorothiophene, I+thiafenox, I+thionazine, I+triazophos, I+triazurone, I+xylenol, I+YI-5302, and zeatin and I+fluensulfone.

[0083] Non-limiting examples of compositions containing synergens include I+2-(2-butoxyethoxy)ethyl piperonylate, I+5-(1,3-benzodioxol-5-yl)-3-hexylcyclohexa-2-enone, I+farnesol and nerolidol, I+MB-599, I+MGK 264, I+piperonyl butoxide, I+piprotal, I+propyl isomer, I+S421, I+sesamex, I+sesamolin and I+sulfoxide.

[0084] Non-limiting examples of compositions containing animal repellents include I+ anthraquinone, I+ chloralose, I+ copper naphthenate, I+ copper oxychloride, I+ diazinon, I+ dicyclopentadiene, I+ guazatin, I+ guazatin acetate, I+ methiocarb, I+ pyridine-4-amine, I+ thyram, I+ trimethacarb, I+ zinc naphthenate, and I+ ziram.

[0085] Further non-limiting examples of compositions include I+ proflutrinate, I+ cycloxapride, I+ diflovidazine, I+ flomethquin, I+ fluhexaphon, I+ guadipyr, I+ diamondback moth (Plutella xylostella) granuloma virus, I+ codling moth (Cydia pomonella) granuloma virus, I+ harpin, I+ imisiafos, I+ false tobacco budworm (Heliothis virescens) nuclear polyhedrosis virus, I+ heliothis punctigera nuclear polyhedrosis virus, I+ tobacco budworm (Helicoverpa armigera) nuclear polyhedrosis virus, I+ tobacco budworm (Helicoverpa zea) nuclear polyhedrosis virus, I+ fall armyworm (Spodoptera frugiperda) nuclear polyhedrosis virus, I+ diamondback moth (Plutella Examples include xylostella (nuclear polyhedrosis virus), I+ Pasteuria nishizawae, I+ p-cymene, I+ piflubumide, I+ pyrafuruprole, I+ pyrethrum, I+ QRD 420, I+ QRD 452, I+ QRD 460, I+ terpenoid blend, I+ terpenoid, I+ tetraniliprole, and I+ α-terpinene.

[0086] The composition is I+ code AE ​​1887196 (BSC-BX60309), I+ code NNI-0745 GR, I+ code IKI-3106, I+ code JT-L001, I+ code ZNQ-08056, I+ code IPPA152201, I+ code HNPC-A9908 (CAS:[660411-21-2]), I+ code HNPC-A2005 (CAS:[860028-12-2]), I+ code JS118, I+ code ZJ0967, I+ code ZJ2242, I+ code JS7119 (CAS:[929545-74-4]), I+ code SN-1172, I+ code HNPC-A9835, I+ code HNPC-A9955, I+ code HNPC-A3061, I+ code Chuanhua This also includes mixtures of one or more polymorphs of the present invention with active substances referenced by their codes, such as 89-1, I+code IPP-10, I+code ZJ3265, I+code JS9117, I+code SYP-9080, I+code ZJ3757, I+code ZJ4042, I+code ZJ4014, I+code ITM-121, I+code DPX-RAB55 (DKI-2301), I+code Me5382, I+code NC-515, I+code NA-89, I+code MIE-1209, I+code MCI-8007, I+code BCS-CL73507, I+code S-1871, I+code DPX-RDS63 and I+code AKD-1193.

[0087] Compositions comprising one or more polymorphs and other pesticides, plant disease control agents and / or insecticides of the present invention are clearly disclosed above, but those skilled in the art will understand that the present invention extends to a further number of combinations comprising three components and the above two-component mixtures.

[0088] The weight ratios of the polymorphs and other harmful plant control agents, plant disease control agents and / or insecticides of the present invention are generally 1000:1 to 1:100, more preferably 500:1 to 1:100, for example, 250:1 to 1:66, 125:1 to 1:33, 100:1 to 1:25, 66:1 to 1:10, 33:1 to 1:5 and 8:1 to 1:3.

[0089] The polymorphs of the present invention can be used alone or in combination with one or more other biologically active ingredients.

[0090] In one embodiment, the present invention provides a combination product comprising a component A effective amount for controlling harmful plants and a component B effective amount for controlling harmful organisms, wherein component A is a polymorph of the present invention, and component B is a compound as described below.

[0091] The polymorphs of the present invention can be used in combination with other ectoparasitic agents; for example, fipronil; pyrethroids; organic phosphates; insect growth disruptors, for example, lufenuron; ecdysone agonists, for example, tebufenozide; neonicotinoids, for example, imidacloprid.

[0092] The polymorphs of the present invention can be used in combination with terpene alkaloids, for example, those described in International Publication No. 95 / 19363 or International Publication No. 04 / 72086, in particular the compounds disclosed therein.

[0093] Other examples of such biologically active compounds in which the polymorphs of the present invention can be used in combination include, but are not limited to, the following:

[0094] Organic phosphates: Acephate, Azamethiphos, Adinphos-ethyl, Adinphos-methyl, Bromophos, Brumophos-ethyl, Kazusaphos, Chlorethoxyphos, Chlorpyrifos, Chlorfenbinphos, Chlormephos, Demeton, Demeton-S-methyl, Demeton-S-methylsulfone, Dialiphos, Diazinon, Dichlorvos, Diclotophos, Dimethoate, Disulfon, Ethion, Etoprophos, Etrimophos, Fanfar, Phenamiphos, Fenitrothion, Fensulfothion, Fenthion, Flupyrazophos, Honophos, Formothion, Fothiazate, Heptenophos, Isazofos, Isothioate, Isooxy Sachion, Malathion, Methacryfos, Methamidophos, Methidathion, Methylparathion, Mevinphos, Monoclotophos, Nared, Omethoate, Oxidemeton-methyl, Paraoxone, Parathion, Parathion-methyl, Fenthoate, Phosalon, Phosphorane, Phosphocarb, Phosmeth, Phosphamidone, Phorate, Foxim, Pirimiphos, Pirimiphos-methyl, Profenophos, Propaphos, Proethanphos, Prothiophos, Pyraclophos, Pyridafenthion, Quinalphos, Sulprophos, Temephos, Terbuphos, Tebupirimiphos, Tetrachlorvinphos, Thiometon, Triazophos, Trichlorfon, Bamidthion.

[0095] Carbamates: Alanicarb, Aldicarb, 2-sec-butylphenylmethylcarbamate, Benfuracarb, Carbaryl, Carbofuran, Carbosulfan, Chloetocarb, Ethiophenecarb, Phenoxycarb, Phenothiocarb, Frathiocarb, HCN-801, Isoprocarb, Indoxacarb, Methiocarb, Methomyl, 5-Methyl-m-cumenylbutyryl(methyl)carbamate, Oxamyl, Pyrimicab, Propoxul, Thiodicarb, Thiofanox, Triazamate, UC-51717.

[0096] Pyrethroids: Acrinatrin, Arethrin, Alphamethrin, 5-Benzyl-3-furylmethyl(E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolane-3-ylidenemethyl)cyclopropanecarboxylate, Bifenthrin, Beta-cyfluthrin, Cyfluthrin, α-cypermethrin, Beta-cypermethrin, Bioalethrin, Bioalethrin ((S)-cyclopentyl isomer), Biorethrin, Bifenthrin, NCI-85193, Cycloprotrin, Cyhalothrin, Citrin, Cypheno Thrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucitrinate, flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrin (natural product), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, t-fluvalinate, tefluthrin, tralomethrin, zeta-cypermethrin.

[0097] Arthropod growth disruptors: a) Chitin synthesis inhibitors: Benzoylureas: Chlorfluazurone, diflubenzuron, fluazurone, flucycloxurone, flufenoxurone, hexaflumurone, lufenuron, novaron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentazine; b) Ecdysone antagonists: Halofenozide, methoxyfenozide, tebufenozide; c) Juvenoids: Pyriproxyfen, methoprene (including S-methoprene), phenoxycarb; d) Lipid biosynthesis inhibitors: Spirodiclofen.

[0098] Other antiparasitic drugs: Asequinosyl, Amitraz, AKD-1022, ANS-118, Azadirachtin, Bacillus thuringiensis, Bensultap, Bifenazate, Binapcryl, Bromopropylate, BTG-504, BTG-505, Campechlor, Cartap, Chlorbenzylate, Chlordimeform, Chlorfenapyr, Chromafenozide, Clothianidin, Cyromazine, Diacloden, Diafenthiuron, DBI-3204, Dinactin, Dihydroxymethyldihydroxypyrrolidine, Dinobutone, Dinocap, Endosulfa, Ethiprole, Etofenprox, Phenazaquin, MTI-800, Fenpyroximate, Fluacrypyrim, Flubendimine, Flubrocitrinate, Flufenzin, Flufenprox, Fluproxyfen, Halofenprox Cus, hydramethylnon, IKI-220, NC-196, neem kernel extract oil, didinorterfuran, nitenpyram, SD-35651, WL-108477, pyridaryl, propargit, protrifenbut, pymetrozine, pyridaben, pyrimidifen, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen, cyromazine, spinosad, tebufenpyramid, tetradiphon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyramid, triazamate, triethoxyspinosine, trinactin, berbutin, Verticillium lecanii, YI-5301.

[0099] Fungicides: Acibenzoral, Aldimorph, Ampropylphos, Andoprim, Azaconazole, Azoxystrobin, Benalaxyl, Benomyl, Vialaphos, Blastocydin-S, Bordeaux mixture, Bromuconazole, Bupirimate, Carpropamide, Captahol, Captan, Carbendazim, Chlorphenazole, Chloroneb, Chloropicrin, Chlorthalonil, Clozolinate, Copper oxychloride, Copper salts, Cyflufenamid, Cymoxanil, Cyproconazole, Cyprodinil, Cyproflam, RH-7281, Diclos Met, diclobutrazol, diclomezin, dichloran, difenoconazole, RP-407213, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dozin, edifenfos, epoxyconazole, famoxadone, phenamidon, phenalimol, fenbuconazole, phencalamide, fenpiclonil, fenpropidine, fenpropimorph, fentin acetate, fluazinam, fludioxonil, flumethova, flumorph / flumollin, fentin hydroxide, fluo Xasastrobin, fluquinconazole, flucilazole, flutolanil, flutriafol, folpet, fosetylaluminum, flaraxyl, flametopyr, hexaconazole, ipconazole, iprobenphos, iprodione, isoprothiolane, kasugamycin, kresoximmethyl, mancozeb, maneb, mefenoxam, mepronil, metalaxyl, metconazole, metminostrobin / phenominostrobin, metraphenone, mycrobutanil, neoasodine, nicobifen, orysastrobin, oxadix Sil, penconazole, pencyclon, probenazole, prochloraz, propamocarb, propioconazole, proquinazide, prothioconazole, pyrifenox, pyraclostrobin, pyrimethanil, pyroquilon, quinoxyfen, spiroxamine, sulfur, tebuconazole, teconazole, thiabendazole, tifluzamide, thiophanate-methyl, thyram, thiadinyl, triadimephon, triadimenol, tricyclazole, trifloxystrobin, triticonazole, validamycin, vinclozine.

[0100] Biological agents: Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic fungi, viruses and fungi.

[0101] Those skilled in the art will recognize that, under environmental and physiological conditions, salts of compounds are in equilibrium with their corresponding unsalted forms, and therefore salts share the biological utility of their unsalted forms.

[0102] The polymorphs of the present invention can be applied without other auxiliaries, but in most cases, application is of a formulation containing one or more active ingredients, sometimes combined with food, with appropriate carriers, excipients, and surfactants, depending on the intended end use. One method of application involves spraying an aqueous dispersion or refined oil formulation of the combination product. Compositions having spray oils, spray oil concentrates, spreading agents, auxiliaries, other solvents, and synergists often enhance the effectiveness of the compound. Such sprays can be applied from a spray container, such as a can, bottle, or other container, by using a pump or by discharging them from a pressurized container, such as a pressurized aerosol spray can. Such spray compositions can take various forms, such as sprays, mists, foams, fumes, or mist. Thus, such spray compositions may further include propellants, foaming agents, etc. It is noteworthy that a spray composition contains an amount of the compound and carrier of the present invention effective for pest control. One embodiment of such a spray composition contains an amount of the compound and propellant of the present invention effective for pest control. Typical propellants include, but are not limited to, methane, ethane, propane, butane, isobutane, butene, pentane, isopentane, neopentane, pentene, hydrofluorocarbons, chlorofluorocarbons, dimethyl ether, and mixtures thereof.

[0103] The present invention will now be described with reference to the following non-limiting examples and figures. [Brief explanation of the drawing]

[0104] [Figure 1] This shows the powder X-ray diffraction pattern of phenoxasulfone in crystalline form A. [Figure 2] This shows the IR spectral pattern of phenoxasulfone in crystalline form A. [Figure 3] The DSC trace of phenoxasulfone crystal form A is shown. [Examples]

[0105] Example 1: Preparation of Form A 3-(2,5-dichloro-4-ethoxybenzylthio)-5,5-dimethyl-2-isoisoxazosin (48.4g), acetonitrile (220.3g), and sodium tungstate dihydrate (1.4g), prepared according to the description in Japanese Patent Publication No. 2005-145958, were added to a 1L reactor, and the reactor was purged with nitrogen. The reactor was heated, and 35% hydrogen peroxide (38.0g) was added dropwise while maintaining a temperature of 60-80°C, and the mixture was aged for 4 hours to obtain the reaction solution. After cooling the reaction solution to 20-40°C, water (160.9g), 17% sodium sulfite aqueous solution (29.8g), and 25% sodium hydroxide aqueous solution (7.0g) were added to precipitate crystals. The crystals were then filtered and dried under reduced pressure to obtain 3-(2,5-dichloro-4-ethoxybenzylsulfonyl)-5,5-dimethyl-2-isoisoxazosine (phenoxasulfone, 49.0g), which is crystalline form A of the present invention.

[0106] Analysis of polymorphism: After preparation, the samples were subjected to analysis by powder X-ray diffraction and / or differential scanning calorimetry and / or infrared spectroscopy, as detailed above. The methods used for these analytical techniques are detailed below.

[0107] Powder X-ray diffraction analysis of solid materials was performed at room temperature using a SmartLab (Rigaku) ​​powder diffractometer. Cu-Kα rays were used as the light source, and measurements were performed using the transmission method.

[0108] Differential scanning calorimetry was performed using Thermo plus EV02 DSCvesta (Rigaku). Approximately 2 mg of sample was used and heated from approximately 25°C to approximately 250°C at a rate of 10°C / min.

[0109] Infrared spectroscopy was performed using the FT / IR-4700 (Nippon Branch Co., Ltd.). An ATR PRO ONE total internal reflection measurement unit and a diamond prism were used.

[0110] Although the present invention has been described with reference to its preferred embodiments and examples, the scope of the invention is not limited to those embodiments described. As will be apparent to those skilled in the art, modifications and alterations to the invention described above can be made without departing from the spirit and scope of the invention as defined and limited by the appended claims. All publications referenced herein are incorporated herein by reference in whole for any purpose to the same extent as each individual publication is specifically and individually indicated to be incorporated by reference.

Claims

1. Compound of formula [I], That is, a crystalline form of phenoxasulfone having a powder X-ray diffraction pattern comprising at least four selected from the group consisting of the following 2θ angle values: 7.4°±0.2°, 8.2°±0.2°, 12.3°±0.2°, 13.0°±0.2°, 17.5°±0.2°, 19.5°±0.2°, 20.3°±0.2°, 21.5°±0.2°, 24.1°±0.2°, 24.8°±0.2°, 31.4°±0.2°, and 44.5°±0.2°.

2. The following infrared absorption spectrum: 2978 cm －１ ± 2 cm －１ , 2921 cm －１ ± 2 cm －１ , 1600 cm －１ ± 2 cm －１ , 1565 cm －１ ± 2 cm －１ , 1497 cm －１ ± 2 cm －１ , 1473 cm －１ ± 2 cm －１ , 1438 cm －１ ± 2 cm －１ , 1369 cm －１ ± 2 cm －１ , 1322 cm －１ ± 2 cm －１ , 1306 cm －１ ± 2 cm －１ , 1257 cm －１ ± 2 cm －１ , 1169 cm －１ ± 2 cm －１ , 1149 cm －１ ± 2 cm －１ , 1133 cm －１ ± 2 cm －１ , 1119 cm －１ ± 2 cm －１ , 1081 cm －１ ± 2 cm －１ , 1041 cm －１ ± 2 cm －１ , 972 cm －１ ± 2 cm －１ , 945 cm －１ ± 2 cm －１ , 918 cm －１ ± 2 cm －１ , 906 cm －１ ± 2 cm －１ , 877 cm －１ ± 2 cm －１ , 839 cm －１ ± 2 cm －１ , 807 cm －１ ± 2 cm －１ , 780 cm －１ ± 2 cm －１ , 749 cm －１ ± 2 cm －１ , 715 cm －１ ± 2 cm －１ , 699cm －１ ±2cm －１ , 650cm －１ ±2cm －１ , 634cm －１ ±2cm －１ , 588cm －１ ±2cm －１ 553cm －１ ±2cm －１ , 530cm －１ ±2cm －１ , 500cm －１ ±2cm －１ , 431cm －１ ±2cm －１ The crystal form according to claim 1, having at least four selected from the group consisting of ,

3. The crystal form according to claim 1, having a melting point of 157.5 to 159.5°C.

4. An agricultural composition comprising the crystalline form described in any one of claims 1 to 3, and at least one agriculturally acceptable carrier or excipient.

5. The composition according to claim 4, which is concentrated in any one of the crystalline forms described in claims 1 to 3.

6. The composition according to claim 4, comprising at least one further active ingredient of a pesticide.

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