Agrochemical compositions

Abstract

The present invention provides a co-crystal of sulfentrazone and a triazone herbicide and a preparation method thereof. The present invention also provides an agricultural chemical composition comprising the co-crystal, a preparation method of the agricultural chemical composition, and a method for controlling weeds using the composition.

Description

Technical Field

[0001] The present invention relates to an agricultural chemical composition, and more particularly to an agricultural chemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide. Background Art

[0002] A eutectic is a multi-component crystalline system formed by intermolecular interactions without the transfer of hydrogen ions. A eutectic or crystalline complex of an organic compound is a multi-component system consisting of at least two different organic compounds. Cocrystals are manifestations of directed self-assembly of different components.

[0003] Agrochemical cocrystals can be defined as crystalline materials composed of two or more different active ingredients or one or more actives in combination with other coformers. These compounds can form through intermolecular forces such as hydrogen bonding, π-stacking and van der Waals forces. Cocrystals can alter or enhance several important physicochemical properties of a substance such as solubility, bioavailability, stability, hygroscopicity, surface free energy, zeta potential, crystal hardness, filterability, filtration and flowability. These properties have a significant impact on agrochemical formulations.

[0004] The use of agrochemical combinations is a common and documented practice in the agricultural community. These agrochemical combinations offer significant advantages over individual applications, including improved and prolonged control, reduced application rates and costs, shortened contact times for better results, less stringent restrictions on use, improved selectivity, improved range against controlled fungi, insects, weeds, etc., and reduced residue problems.

[0005] However, the combined use of multiple active substances can sometimes lead to phenomena of physical and biological incompatibility, such as lack of physical stability of the co-formulation, decomposition of the active substances, or antagonism of the active substances, and therefore needs to be handled with caution.

[0006] Triazinones are heterocyclic compounds with potential biological activity. Their main mode of action is to inhibit electron transport in photosystem II (Hill reaction).

[0007] Sulfonamide is a phenyl triazone (also known as aryl triazone) herbicide that acts by inhibiting the enzyme protoporphyrinogen oxidase (protox). Sulfonamide mimics one half of the tetrapyrrole ring of protoporphyrinogen (substrate of Protox) and competes for the catalytic site on the enzyme. The active compound sulfonamide has also long been known (U.S. Pat. No. 4,818,275), which is taken up by roots and leaves, transported mainly in the apoplast, with limited movement in the phloem. It is used to control annual broadleaf weeds, some grasses, and Cyperus Variety. Incorporate it into the application before emergence or before planting.

[0008] Metribuzin is a triazone herbicide that inhibits photosynthesis in susceptible plants by binding to proteins of the photosystem II complex, leading to a chain of events in which plant lipids and proteins are attacked and oxidized by highly reactive free radicals. The active compound metribuzin has long been known (U.S. Pat. No. 3,905,801) and can be used both pre-emergence and post-emergence and has been shown to be useful for selective control of weeds, particularly in soybeans and potatoes.

[0009] It has been observed that in the preparation of stable compositions, especially liquid compositions of sulfentrazone and triazone herbicides (e.g., metribuzin), the physical incompatibility of the two actives can lead to unstable compositions. Such unstable compositions are unacceptable both from the formulation and application parts. During the formulation process, such liquid compositions may fail to pass quality inspections due to uneven dispersion. Moreover, during the application process, such liquid compositions may not provide uniform concentrations of actives on site and may cause clogging of the nozzles of the applicators.

[0010] Therefore, there is a need to develop a stable system in which sulfentrazone can be formulated with other triazone herbicides as binary mixtures. In addition, there is a need to develop a stable system in which sulfentrazone and triazone herbicides do not show crystal growth when formulated together and remain stable during formulation and on storage.

[0011] Purpose of the Invention

[0012] One object of the present invention is to provide a co-crystal of sulfentrazone and a triazone herbicide.

[0013] Another object of the present invention is to provide an agricultural chemical composition of sulfentrazone and a triazone herbicide.

[0014] An object of the present invention is to provide an agricultural chemical composition of sulfentrazone and a triazone herbicide having long-term storage stability.

[0015] Another object of the present invention is to provide an agricultural chemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide.

[0016] Another object of the present invention is to provide an agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin.

[0017] Another object of the present invention is to provide a method for preparing an agrochemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide. Summary of the invention

[0018] In one aspect of the present invention, a co-crystal of sulfentrazone and a triazone herbicide is provided.

[0019] In another aspect, the present invention provides a method for preparing a co-crystal of sulfentrazone and a triazone herbicide.

[0020] In another aspect, the present invention provides an agricultural chemical composition consisting of a co-crystal of sulfentrazone and a triazone herbicide.

[0021] In another aspect, the present invention provides a method for preparing an agrochemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide.

[0022] In another aspect of the present invention, a method for preparing an agricultural chemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide, the method comprising:

[0023] Pretreatment of sulfentrazone and triazone herbicides to form cocrystals;

[0024] mixing the co-crystal of step (a) with an agrochemical excipient as required to obtain a mixture; and

[0025] The resulting mixture of step (b) is further processed to obtain said composition.

[0026] In one aspect of the present invention, a method for preparing a liquid agricultural chemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide, the method comprising:

[0027] Pretreatment of sulfentrazone and triazone herbicides to form cocrystals;

[0028] mixing the co-crystal of step (a) with an agrochemical excipient in an aqueous condition as required to obtain a mixture; and

[0029] The resulting mixture of step (b) is further processed to obtain the combination

[0030] In still another aspect of the present invention, the agricultural chemical composition comprises a co-crystal of sulfentrazone and metribuzin.

[0031] In another aspect of the present invention, an agrochemical composition comprising a co-crystal of sulfentrazone and metribuzin, wherein the composition comprises 10-90% by weight of sulfentrazone and 90-10% by weight of metribuzin.

[0032] In another aspect of the present invention, an agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin, wherein the co-crystal exhibits at least one characteristic XRD reflection at 2θ values ​​(±0.2) of 7.8°, 11.8°, 14.1°, 17.8°, 22.1°, 23.4° and 24.4°.

[0033] In one aspect of the present invention, a co-crystal of sulfentrazone and metribuzin is provided.

[0034] In another aspect of the present invention, a method for preparing a co-crystal of sulfentrazone and metribuzin by using any of the following methods:

[0035] Solution crystallization,

[0036] Dry grinding,

[0037] Solvent drop grinding technology,

[0038] Melt crystallization, or

[0039] Mix sulfentrazone with triazone herbicide under aqueous conditions and then provide energy.

[0040] In yet another aspect of the present invention, a method for preparing an agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin, the method comprising:

[0041] Sulfentrazone and metribuzin were pretreated to form cocrystals;

[0042] mixing the co-crystal of step (a) with an agrochemical excipient as required to obtain a mixture; and

[0043] The resulting mixture of step (b) is further processed to obtain the combination

[0044] In another aspect of the present invention, a method for preparing a liquid agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin, the method comprising:

[0045] Sulfentrazone and metribuzin were pretreated to form cocrystals;

[0046] The co-crystal of step (a) is mixed with an agrochemical excipient in aqueous conditions to obtain the composition

[0047] In another aspect of the present invention, a method for controlling weeds comprises applying a herbicidally effective amount of a composition comprising a co-crystal of sulfentrazone and a triazone herbicide to a plant or its habitat, a plant seed or soil.

[0048] In another aspect of the present invention, a method for controlling weeds comprises applying a herbicidally effective amount of a composition comprising a co-crystal of sulfentrazone and metribuzin to a plant or its habitat, a plant seed or soil.

[0049] Another object of the present invention is to provide use of a liquid agricultural chemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] The present invention may be understood by reference to the following drawings:

[0051] Figure 1 : High performance liquid chromatography (HPLC) chromatogram of the co-crystal of sulfentrazone and metribuzin.

[0052] Figure 2 : Fourier transform infrared (FTIR) spectrum of the cocrystal of sulfentrazone and metribuzin.

[0053] Figure 3 : Powder X-ray diffraction (P-XRD) diffraction pattern of the co-crystal of sulfentrazone and metribuzin.

[0054] Figure 4 : Differential scanning calorimetry (DSC) thermogram of the co-crystal of sulfentrazone and metribuzin.

[0055] Figure 5 : FTIR spectrum of co-crystal of sulfentrazone and metribuzin in suspension concentrate.

[0056] Figure 6 : P-XRD diffraction pattern of the co-crystal of sulfentrazone and metribuzin in the suspension concentrate.

[0057] Figure 7 : Single crystal structure of the cocrystal of sulfentrazone and metribuzin (in the ball-and-stick model). DETAILED DESCRIPTION

[0058] Unexpectedly, the inventors of the present invention have discovered that an agrochemical composition of sulfentrazone and metribuzin can be formed when the two actives are allowed to undergo a pretreatment, including the interaction of the two actives and further formulation using surfactants and other agrochemical excipients. This pretreatment promotes intermolecular interactions between the actives and results in the formation of cocrystals of the two actives. And, this preformed cocrystal can then be formulated into a desired product using surfactants and other agrochemical excipients. In addition, the inventors of the present invention have observed that when the agrochemical composition is formulated into a liquid composition comprising a cocrystal of sulfentrazone and a triazone herbicide, it does not suffer from the particle growth problems associated with liquid compositions, and further noted that the composition remains fairly stable during long-term storage.

[0059] In the context of the present invention, the term "eutectic" is defined as "a solid of a crystalline material composed of two or more molecules in the same crystal lattice". A eutectic is also defined as a crystalline material composed of two or more different molecules, with a definite stoichiometric ratio in the same crystal lattice, associated by non-ionic and non-covalent bonds.

[0060] Therefore, in an embodiment, the present invention provides an agricultural chemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide.

[0061] In an embodiment of the present invention, an agricultural chemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide is provided, wherein the composition comprises 10-90% by weight of sulfentrazone and 90-10% by weight of the triazone herbicide.

[0062] In an embodiment of the present invention, the triazone herbicide of the agrochemical composition is selected from the group consisting of terzinone, terfenadone, ethidiumbion, hexazinone, buthiclothion, metamitron, metribuzin and trifluoxetine.

[0063] In an embodiment of the present invention, the triazone herbicide is metamitron.

[0064] In an embodiment of the present invention, the triazone herbicide is terbazone.

[0065] In a preferred embodiment of the present invention, the triazone herbicide is metribuzin.

[0066] In an embodiment of the present invention, the sulfentrazone of the agricultural chemical composition comprising the co-crystal of sulfentrazone and a triazone herbicide is about 10% w / w to about 90% w / w of sulfentrazone based on the total weight of the agricultural chemical composition.

[0067] In an embodiment of the present invention, the sulfentrazone of the agricultural chemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide is about 20% w / w to about 80% w / w of sulfentrazone, and preferably about 40% w / w to about 60% w / w of sulfentrazone, based on the total weight of the agricultural chemical composition.

[0068] In an embodiment of the present invention, the triazone herbicide of the agricultural chemical composition comprising the co-crystal of sulfentrazone and a triazone herbicide is about 10% w / w to about 90% w / w of the triazone herbicide based on the total weight of the agricultural chemical composition.

[0069] In an embodiment of the present invention, the triazone herbicide of the agricultural chemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide is about 20% w / w to about 80% w / w of the triazone herbicide, and preferably about 40% w / w to about 60% w / w of the triazone herbicide, based on the total weight of the agricultural chemical composition.

[0070] In an embodiment of the present invention, there is provided a method for preparing an agricultural chemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide, the method comprising the following steps:

[0071] Pretreatment of sulfentrazone and triazone herbicides to form cocrystals;

[0072] mixing the co-crystal of step (a) with an agrochemical excipient as required to obtain a mixture; and

[0073] The resulting mixture of step (b) is further processed to obtain the combination

[0074] As used hereinafter, the term "pretreatment" refers to a process of allowing sulfentrazone and a triazone herbicide to form a co-crystal before they are incorporated into an agrochemical composition.

[0075] In embodiments of the present invention, pretreatment includes milling, grinding or providing a suitable form of energy sufficient to allow the formation of co-crystals of sulfentrazone and triazone herbicide.

[0076] In an embodiment of the present invention, the pretreatment comprises heating a mixture of sulfentrazone and a triazone herbicide and allowing a co-crystal of sulfentrazone and a triazone herbicide to form.

[0077] In an embodiment of the present invention, the pretreatment includes subjecting the mixture of sulfentrazone and triazone herbicide to amorphization by grinding, melting, pulverizing or other suitable means, and allowing the formation of eutectics of sulfentrazone and triazone herbicide.

[0078] In an embodiment of the present invention, sulfentrazone and triazone herbicide are provided with a pre-treatment for a sufficient period of time to form a co-crystal.

[0079] According to another embodiment of the present invention, in the method for preparing an agrochemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide, the mixing order of the co-crystal and the agrochemical excipient is not fixed and can be varied according to the preference of the formulator.

[0080] According to another embodiment of the present invention, in the method for preparing an agrochemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide, the mixture obtained in step (b) is subjected to a particle size reduction by applying shear to the mixture of the co-crystal and the agrochemical excipient. Apparatus suitable for this purpose is an apparatus providing a milling operation, such as a high shear mixer, such as ROSS HSM, Ultra-Turrax apparatus and dissolvers, a static mixer, such as a system with a mixing nozzle, a bead mill, a vibrating mill, an agitated bead mill, a colloid mill, a cone mill, a circulation mill (agitated ball mill with a pin mill system), a disc mill, an annular chamber mill, a double cone mill, a sprocket disperser or homogenizer, and other homogenizers.

[0081] According to another embodiment of the present invention, in the method for preparing the agrochemical composition comprising the co-crystal of sulfentrazone and a triazone herbicide, the further treatment of step (c) may be performed under ambient temperature conditions.

[0082] According to another embodiment of the present invention, in the method for preparing an agrochemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide, the further treatment of step (c) may be carried out under elevated temperature conditions of ≥40°C, preferably ≥60°C.

[0083] According to another embodiment of the present invention, in the method for preparing an agricultural chemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide, the further treatment of step (c) can be performed at a low temperature of ≤40°C, preferably ≤20°C.

[0084] According to another embodiment of the present invention, the agricultural chemical composition of the present invention can be formulated into granules and liquid compositions.

[0085] In an embodiment, a method of preparing a granular composition comprising a co-crystal of sulfentrazone and a triazone herbicide is provided.

[0086] In an embodiment of the present invention, a granular composition comprising a co-crystal of sulfentrazone and a triazone herbicide is prepared by a method comprising:

[0087] a) pre-treating sulfentrazone and a triazone herbicide to form a co-crystal;

[0088] b) mixing the co-crystal of step (a) with an agrochemical excipient into a mixture as required;

[0089] c) optionally grinding and pulverizing; and further granulating the mixture to obtain a granular composition.

[0090] The step of granulating the mixture is not particularly limited. Suitable granulation methods are conventional methods described in granulation technology, such as spray drying, fluidized bed granulation, agglomeration, pan granulation and extrusion granulation.

[0091] In an embodiment of the present invention, the agricultural chemical composition comprises from about 10% to about 40% w / w of a co-crystal of sulfentrazone and metribuzin, from about 1% to about 20% of a solvent, from about 0.1% to about 20% of a nonionic and anionic dispersant, from about 0.1% to about 10% of a wetting agent, from about 0.1% to about 10% of a defoaming agent, and from about 0.1% to about 30% of a thickener, based on the total weight of the agricultural chemical composition.

[0092] In an embodiment of the present invention, the agricultural chemical composition comprises from about 10% to about 40% w / w co-crystal of sulfentrazone and metribuzin, from about 1% to about 20% glycol, from about 0.1% to about 20% acrylic acid polymer, from about 0.1% to about 20% alkali swellable polyacrylate, from about 0.1% to about 10% polyalkylene glycol ether, from about 0.1% to about 10% silicone defoamer, and from about 0.1% to about 30% thickener, based on the total weight of the agricultural chemical composition.

[0093] The present invention relates to a method for preparing a liquid agricultural chemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide, the method comprising:

[0094] providing a pre-treatment of sulfentrazone and triazone herbicides to form co-crystals;

[0095] mixing the co-crystal of step (a) with an agrochemical excipient in an aqueous condition as required to obtain a mixture; and

[0096] The resulting mixture of step (b) is further processed to obtain the combination

[0097] In embodiments of the present invention, pretreatment includes milling, grinding or providing a suitable form of energy sufficient to allow the formation of co-crystals of sulfentrazone and triazone herbicide.

[0098] In an embodiment of the present invention, the pretreatment comprises heating a mixture of sulfentrazone and a triazone herbicide in aqueous conditions and allowing a co-crystal of sulfentrazone and a triazone herbicide to form.

[0099] In an embodiment of the present invention, the pretreatment includes subjecting the mixture of sulfentrazone and triazone herbicide in aqueous conditions to amorphization by grinding, melting, milling or other suitable means, and allowing the formation of eutectics of sulfentrazone and triazone herbicide.

[0100] In an embodiment of the present invention, the mixing of step b) is performed under aqueous conditions.

[0101] In an embodiment of the present invention, the treatment of step c) is carried out in aqueous conditions to obtain the desired product.

[0102] Preferred methods for carrying out step b) and step c) are as described above.

[0103] In an embodiment of the present invention, the agricultural chemical composition comprises a co-crystal of sulfentrazone and metribuzin.

[0104] In an embodiment of the present invention, an agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin, wherein the composition comprises 10-90% by weight of sulfentrazone and 90-10% by weight of metribuzin.

[0105] In an embodiment of the present invention, the sulfentrazone in the agricultural chemical composition comprising the co-crystal of sulfentrazone and metribuzin is about 20% w / w to about 80% w / w of sulfentrazone, and preferably about 40% w / w to about 60% w / w of sulfentrazone, based on the total weight of the agricultural chemical composition.

[0106] In an embodiment of the present invention, the amount of metribuzin in the agricultural chemical composition comprising the co-crystal of sulfentrazone and metribuzin is about 20% w / w to about 80% w / w of metribuzin, and preferably about 40% w / w to about 60% w / w of metribuzin, based on the total weight of the agricultural chemical composition.

[0107] In an embodiment of the present invention, an agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin, wherein the co-crystal exhibits at least one characteristic XRD reflection at 2θ values ​​(±0.2) of 7.8°, 11.8°, 14.1°, 17.8°, 22.1°, 23.4° and 24.4°.

[0108] In an embodiment of the present invention, the agricultural chemical composition comprises from about 10% to about 40% w / w of a co-crystal of sulfentrazone and metribuzin, from about 1% to about 20% of a solvent, from about 0.1% to about 20% of a nonionic and anionic dispersant, from about 01.% to about 10% of a wetting agent, from about 0.1% to about 10% of a defoaming agent, and from about 0.1% to about 30% of a thickener, based on the total weight of the agricultural chemical composition, wherein the agricultural chemical composition is formulated as a suspension concentrate.

[0109] In an embodiment of the present invention, the agricultural chemical composition comprises from about 10% to about 40% w / w co-crystal of sulfentrazone and metribuzin, from about 1% to about 20% glycol, from about 0.1% to about 20% acrylic acid polymer, from about 0.1% to about 20% alkali swellable polyacrylate, from about 01.% to about 10% polyalkylene glycol ether, from about 0.1% to about 10% silicone defoamer, from about 0.1% to about 30% xanthan gum, based on the total weight of the agricultural chemical composition, wherein the agricultural chemical composition is formulated as a suspension concentrate.

[0110] In an embodiment of the present invention, an agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin, wherein the co-crystal exhibits at least one characteristic XRD reflection at 2θ values ​​(±0.2) of 7.8°, 11.8°, 14.1°, 17.8°, 22.1°, 23.4° and 24.4°.

[0111] In an embodiment of the present invention, an agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin, wherein the molar ratio of sulfentrazone to metribuzin is 1:9 to 9:1.

[0112] In an embodiment of the present invention, an agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin, wherein the molar ratio of sulfentrazone to metribuzin is 1:5 to 5:1.

[0113] In an embodiment of the present invention, an agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin, the molar ratio of sulfentrazone to metribuzin is generally in the range of 2:1 to 1:2, preferably from 1.5:1 to 1:1.5, and particularly 1:1.

[0114] In an embodiment of the present invention, an agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin, wherein the molar ratio of sulfentrazone to metribuzin is 1:9 to 9:1.

[0115] In an embodiment of the present invention, an agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin, the molar ratio of sulfentrazone to metribuzin is generally in the range of 2:1 to 1:2, preferably from 1.5:1 to 1:1.5, and particularly 1:1.

[0116] In one aspect of the present invention there is provided a co-crystal comprising sulfentrazone and at least one triazone herbicide.

[0117] In an embodiment of the present invention, a co-crystal of sulfentrazone and metribuzin is provided.

[0118] In an embodiment, sulfentrazone and metribuzin are present in the co-crystal in a molar ratio of from 2:1 to 1:2.

[0119] In an embodiment of the present invention, a co-crystal of sulfentrazone and metribuzin, wherein the co-crystal exhibits at least one characteristic XRD reflection at 2θ values ​​(±0.2) of 7.8°, 11.8°, 14.1°, 17.8°, 22.1°, 23.4° and 24.4°.

[0120] In an embodiment, the eutectic is characterized by at least one of the following

[0121] a powder X-ray diffraction pattern comprising at least one peak at diffraction angles of 2θ values ​​of 7.8°, 11.8°, 14.1°, 17.8°, 22.1°, 23.4° and 24.4° (±0.2), or

[0122] The DSC thermogram includes an endothermic peak starting at 107.3°C and peaking at 110.5°C, or

[0123] Single crystal X-ray diffraction with lattice parameters: α=90°, β=93.5058°(7) and γ=90°.

[0124] In an embodiment of the present invention, a method for preparing a co-crystal of sulfentrazone and metribuzin is provided by using any of the following methods:

[0125] Mix sulfentrazone with triazone herbicide under aqueous conditions and then provide energy;

[0126] Solution crystallization

[0127] Dry grinding

[0128] Solvent drop grinding technology

[0129] Melt crystallization

[0130] In the embodiments of the present invention, the co-crystal of sulfentrazone and metribuzin herbicide can be obtained by any conventional method known to those skilled in the art for preparing such a co-crystal.

[0131] The present invention further provides a method for preparing a co-crystal of sulfentrazone and a triazone herbicide.

[0132] In an embodiment, a method for preparing a co-crystal of sulfentrazone and a triazone herbicide, wherein the co-crystal is obtained by solution crystallization or grinding or heating or solvent drop grinding or melt crystallization or mixing sulfentrazone and a triazone herbicide under aqueous conditions.

[0133] In an embodiment of the present invention, a method of preparing a co-crystal of sulfentrazone and metribuzin by mixing sulfentrazone and metribuzin involves suspending sulfentrazone and metribuzin in water and then providing energy sufficient to promote intermolecular interaction between sulfentrazone and metribuzin.

[0134] In an embodiment of the present invention, a method for preparing a co-crystal of sulfentrazone and metribuzin comprises mixing sulfentrazone and metribuzin in an aqueous condition, and then providing energy.

[0135] In an embodiment of the present invention, a method for preparing a co-crystal of sulfentrazone and metribuzin comprises preparing a solution of sulfentrazone and a triazone herbicide using an organic solvent, water or a mixture of water and an organic solvent, and triturating or precipitating with an anti-solvent to obtain the co-crystal of sulfentrazone and a triazone herbicide.

[0136] The solvent is selected from aliphatic alcohols, ketones, esters, ethers, polar protic solvents, polar aprotic solvents, halogenated solvents, aliphatic hydrocarbons or aromatic hydrocarbons, and the anti-solvent is selected from aliphatic hydrocarbon solvents or aromatic hydrocarbon solvents.

[0137] In an embodiment, the method for preparing the co-crystal of sulfentrazone and metribuzin comprises heating a mixture of sulfentrazone and a triazone herbicide to melt to obtain the co-crystal of sulfentrazone and a triazone herbicide.

[0138] In an embodiment of the present invention, the method for preparing the co-crystal of sulfentrazone and metribuzin by solution crystallization involves dissolving sulfentrazone and metribuzin in a suitable solvent, and further co-crystallization is induced by cooling or evaporation or precipitation.

[0139] In an embodiment, the solvent may be selected from aliphatic alcohols, ketones, esters, ethers, polar protic solvents, polar aprotic solvents, halogenated solvents, aliphatic hydrocarbons, and aromatic hydrocarbons.

[0140] In an embodiment, the solvent may be selected from methanol, ethanol, isopropanol, acetone, dichloromethane, dichloroethane, dichloropropane, trichloroethane, chloroform, and ethyl acetate.

[0141] In an embodiment of the present invention, the co-crystallization induced by cooling comprises separately preparing saturated solutions of sulfentrazone and metribuzin at elevated temperature. Thereafter, the two solutions are combined at the same temperature and cooled to 0°C to 20°C, preferably to 3°C to 8°C (e.g., 5°C). The co-crystals thus formed can be separated from the resulting suspension by conventional techniques (e.g., filtration).

[0142] In embodiments of the present invention, co-crystallization induced by evaporation involves partial or complete removal of the solvent by using common evaporation techniques such as heating or reduced pressure.

[0143] In an embodiment of the present invention, the co-crystallization induced by precipitation involves the complete dissolution of sulfentrazone and metribuzin in a suitable solvent. Crystallization is induced by reducing the solubility of the solute by adding a solvent, wherein the solubility of sulfentrazone and the solubility of metribuzin at room temperature are preferably less than 10 g / l, in particular less than 2 g / l (hereinafter referred to as "anti-solvent"). Conveniently suitable anti-solvents are non-polar solvents, such as n-hexane, n-heptane, ether, petroleum ether, 1,4-dioxane, cyclohexanone, toluene or xylene.

[0144] In an embodiment of the present invention, a method for preparing a co-crystal of sulfentrazone and metribuzin by dry milling comprises combining sulfentrazone and metribuzin and then applying a shear force.

[0145] In an embodiment of the present invention, the dry grinding method for preparing the co-crystal of sulfentrazone and metribuzin by applying shear force is preferably carried out at a temperature of at least 15°C, often at a temperature of at least 20°C, preferably at a temperature of at least 30°C, in particular at least 35°C, for example, from 15°C to 80°C.

[0146] In an embodiment of the present invention, a method for preparing a co-crystal of sulfentrazone and metribuzin is provided by a solvent drop grinding technique.

[0147] In an embodiment of the present invention, the method for preparing the co-crystal of sulfentrazone and metribuzin by solvent drop grinding technique involves an organic solvent, or a mixture of water and an organic solvent, wherein the solubility of sulfentrazone and metribuzin is comparable.

[0148] More preferred are organic solvents from group 1, and their mixtures with water. In the mixture with water, the relative amounts of organic solvent and water may vary from 200:1 to 1:200 (v / v), in particular from 1:5 to 1:100 (v / v).

[0149] Suitable solvents are polar solvents as defined above.

[0150] Particularly suitable organic solvents, used alone or in a mixture with water, are the alcohols mentioned above (C1-C4-alkanols, for example methanol, ethanol, n-propanol or isopropanol).

[0151] The solvent drop milling process can be performed simply by pouring the solvent in a dropwise manner onto the mixture of sulfentrazone and metribuzin and applying shear force (eg, using a rotor-stator mill).

[0152] The solvent drop grinding process is usually carried out at a temperature of at least 5°C, preferably at least 10°C, especially at least 20°C, such as 5 to 80°C, preferably 10 to 55°C, especially 20 to 40°C.

[0153] The time required for the formation of the cocrystal by solvent drop grinding depends on the temperature and type of solvent and is usually 1 hour. In any case, complete conversion is achieved after one week; however, complete conversion usually takes no longer than 24 hours.

[0154] In an embodiment of the present invention, a method for preparing a co-crystal of sulfentrazone and metribuzin by melt crystallization comprises heating a mixture of sulfentrazone and metribuzin in a porcelain dish maintained on a paraffin oil bath at 200° C. In addition, the molten material is incubated at 90° C. using a water bath in a container filled with 25 ml of water. The co-crystal thus obtained is dried overnight at room temperature and further analyzed for its characterization.

[0155] In an embodiment of the present invention, a method for preparing a co-crystal of sulfentrazone and metribuzin by mixing sulfentrazone and metribuzin under aqueous conditions and then providing energy involves grinding a mixture of sulfentrazone and metribuzin under aqueous conditions (optionally in the presence of other agrochemical excipients) and forming a co-crystal through interaction under aqueous conditions.

[0156] In an embodiment of the present invention, a method for preparing an agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin is provided, the method comprising:

[0157] Sulfentrazone and metribuzin were pretreated to form a cocrystal;

[0158] mixing the co-crystal of step (a) with an agrochemical excipient as required to obtain a mixture; and

[0159] The resulting mixture of step (b) is further processed to obtain the combination

[0160] In an embodiment of the present invention, pretreatment includes grinding, milling or providing energy in a suitable form sufficient to allow the formation of a co-crystal of sulfentrazone and metribuzin herbicide.

[0161] In an embodiment of the present invention, the pretreatment comprises heating a mixture of sulfentrazone and metribuzin herbicides and allowing a co-crystal of sulfentrazone and triazone herbicide to form.

[0162] In an embodiment of the present invention, the pretreatment includes subjecting the mixture of sulfentrazone and metribuzin herbicides to amorphization by grinding, melting, pulverizing or other suitable means, and allowing the formation of eutectics of sulfentrazone and triazone herbicides.

[0163] In an embodiment of the present invention, the co-crystal so formed in step (b) is then mixed with a suitable agrochemical excipient to obtain a mixture and further processed to obtain an agrochemical composition in a suitable form.

[0164] Preferred methods for carrying out step b) and step c) are as described above.

[0165] In an embodiment, a method for preparing an agricultural chemical composition of a co-crystal of sulfentrazone and a triazone herbicide is provided, the method comprising:

[0166] Pretreatment of sulfentrazone and triazone herbicides to form cocrystals;

[0167] The co-crystal of step (a) is mixed with an agrochemically acceptable excipient to obtain the composition.

[0168] According to another embodiment of the present invention, a method for preparing an agricultural chemical composition comprises:

[0169] pretreating sulfentrazone and metribuzin to obtain cocrystals by heating and then cooling the mixture to room temperature;

[0170] The co-crystal of step (a) is mixed with an agrochemical excipient in the presence of water to obtain a homogeneous agrochemical composition.

[0171] Typically, the process for preparing an agrochemical composition comprises:

[0172] pre-treating sulfentrazone and metribuzin to obtain a co-crystal by heating in the range of about 70-80° C. for about 1 hour followed by cooling the mixture to room temperature;

[0173] The co-crystal of step (a) is mixed with an agrochemical excipient in the presence of water and high shear and one or more dispersants and / or wetting agents are added to obtain a slurry.

[0174] Optionally, the slurry is ground by maintaining the mill temperature at ≤ 25°C to achieve a preferred d according to the specification. 10 ≤1,d 50 ≤4,d 90 ≤10 and d 100 Particle size ≤35μm.

[0175] The slurry was mixed for about 1 hour to obtain a homogeneous agrochemical composition.

[0176] According to an embodiment of the present invention, a method for preparing an agricultural chemical composition comprises:

[0177] preparing an aqueous mixture of an agrochemically suitable excipient to obtain a homogeneous solution;

[0178] adding metribuzin and sulfentrazone to the homogeneous solution of step (a) to obtain a slurry;

[0179] The slurry is optionally milled.

[0180] The slurry from step (b) or (c) is heated and cooled to room temperature.

[0181] Other agrochemical excipients are optionally added to the slurry of step (d) and mixed to obtain a homogeneous agrochemical composition.

[0182] According to an embodiment of the present invention, a method for preparing an agricultural chemical composition comprises:

[0183] An aqueous solution of agrochemically suitable excipients (preferably anionic and nonionic dispersants) is prepared and passed through a mixer under high shear to obtain a homogeneous solution.

[0184] adding metribuzin and sulfentrazone to the homogeneous solution of step (a) to obtain a slurry;

[0185] The slurry is optionally ground to achieve a powder according to the specification d 10 ≤1,d 50 ≤4,d 90 ≤10 and d 100The particle size was ≤35 μm and the mill temperature was maintained at ≤25 °C.

[0186] The slurry of step (b) or (c) is heated at a temperature in the range of 70 to 80° C., mixed for about 1 hour and cooled to room temperature;

[0187] Other agrochemical excipients such as thickener gel are added to the slurry of step (b) or step (d) and mixed to obtain a homogeneous agrochemical composition.

[0188] The method comprises optionally following step (c) after step (d) to achieve the particle size specification of step (c);

[0189] Step (e) involves preparing a thickener (2% solution) gel by adding Proxel GXL and Rhodopol 23 to a container, mixing for 30 minutes and adding water and continuing mixing for 1 hour.

[0190] In an embodiment of the present invention, the steps in the method for preparing an agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin may not be fixed and may be in any order to achieve the agricultural chemical composition according to the present invention.

[0191] In embodiments of the present invention, the agricultural chemical composition of the present invention may be in a solid or liquid form.

[0192] According to a preferred embodiment, the agricultural chemical composition of the present invention is a liquid formulation.

[0193] According to an embodiment of the present invention, the liquid agrochemical composition may be formulated into a suspension concentrate (SC), an emulsion (EW), an oil-based suspension concentrate (OD) and / or a suspoemulsion (SE).

[0194] According to a preferred embodiment of the present invention, the liquid agrochemical composition is formulated as a suspension concentrate (SC).

[0195] The present invention relates to a method for preparing a liquid agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin, the method comprising:

[0196] Sulfentrazone and metribuzin were pretreated to form cocrystals;

[0197] mixing the co-crystal of step (a) with an agrochemical excipient in an aqueous condition as required to obtain a mixture; and

[0198] The resulting mixture of step (b) is further processed to obtain the combination

[0199] In an embodiment of the present invention, the steps in the method for preparing a liquid agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin may not be fixed and may be in any order to achieve the liquid agricultural chemical composition according to the present invention.

[0200] In the embodiment of the present invention, the co-crystal of the liquid agricultural chemical composition is obtained by "pre-treatment", which refers to a process of allowing sulfentrazone and triazone herbicide to form a co-crystal before being incorporated into the liquid agricultural chemical composition.

[0201] In an embodiment of the present invention, pre-treatment of sulfentrazone and metribuzin involves bringing them together and grinding, milling or heating or providing energy in a suitable form sufficient to allow the formation of a co-crystal of sulfentrazone and metribuzin.

[0202] In one embodiment, a slurry of agrochemical excipients is first prepared and milled, and then sulfentrazone and metribuzin are added at elevated temperature (54°C-60°C) and milled with the slurry of agrochemical excipients. Then, further processing is performed by adding a thickener to prepare a suspension concentrate.

[0203] In another embodiment, a slurry of agrochemical excipients is first prepared, and then sulfentrazone and metribuzin are added at elevated temperature (54°C-60°C) and then milled with the slurry of agrochemical excipients. Further processing is performed by adding a thickener to prepare a suspension concentrate.

[0204] In another embodiment, sulfentrazone and metribuzin are mixed and ground, and then allowed to melt (125°C-140°C) by providing heat to obtain a eutectic. The eutectic is then cooled and broken up under grinding conditions. A separately prepared slurry of an agrochemical excipient is then added to the mixture and ground again. Finally, further processing is performed by adding a thickener to prepare a suspension.

[0205] In another embodiment, sulfentrazone and metribuzin are mixed and ground to obtain a mixture. The mixture is dynamically heated (54°C-70°C), and then a separately prepared slurry of the agrochemical excipient is added to the mixture and ground again. Finally, further processing is performed by adding a thickener to prepare a suspension.

[0206] The present invention provides a liquid agricultural chemical composition comprising;

[0207] Cocrystals of sulfentrazone and triazone herbicides;

[0208] Acrylate polymers; and

[0209] glycerin.

[0210] According to an embodiment of the present invention, the liquid agricultural chemical composition includes an acrylate polymer.

[0211] According to an embodiment of the present invention, the acrylate polymer is selected from the group consisting of methyl acrylate, methacrylate, ethyl acrylate, 2-chloroethyl vinyl ether, 2-ethylhexyl acrylate, hydroxyethyl methacrylate, butyl acrylate, butyl methacrylate and trimethylolpropane triacrylate (TMPTA). Acrylic polymers include but are not limited to modified styrene / maleic anhydride copolymer (Envi-Pol 871), PAPI 27 polymer MDI, polymethyl methacrylate, polyacrylate, polyacrylate such as sodium polyacrylate, poly(vinyl acetate) (PVAc) and polyacrylamide.

[0212] In an embodiment of the present invention, the liquid agricultural chemical composition may further contain urea.

[0213] According to an embodiment of the present invention, the liquid agricultural chemical composition comprises from about 0.1% w / w to about 40% w / w, preferably from about 0.1% w / w to about 30% w / w of the acrylate polymer based on the total weight of the liquid agricultural chemical composition.

[0214] According to a preferred embodiment of the present invention, the liquid agrochemical composition comprises from about 1% w / w to about 30% w / w, preferably from about 0.1% w / w to about 30% w / w glycerin based on the total weight of the liquid agrochemical composition.

[0215] According to an embodiment of the present invention, the liquid agrochemical composition comprises water.

[0216] According to an embodiment of the present invention, the liquid agrochemical composition comprises from about 0.1% to about 99% w / w, preferably from about 10% to about 70% w / w of water based on the total weight of the liquid agrochemical composition.

[0217] In an embodiment of the present invention, the liquid agrochemical composition may further comprise a liquid agrochemical excipient selected from one or more anionic and nonionic surfactants, antifreeze agents, wetting agents, fillers, surfactants, anti-caking agents, pH regulators, preservatives, bactericides, antifoaming agents, colorants and other formulation adjuvants.

[0218] Suitable anionic surfactants include polyacrylates, alkylbenzene sulfonates (example: TERWET 1004) such as dodecylbenzene sulfonates, for example calcium dodecylbenzene sulfonate, ethoxylated and / or propoxylated di- or tri-styrylphenol phosphates, ethoxylated and / or propoxylated di- or tri-styrylphenol sulfates, phenyl sulfonates, alkylnaphthalene sulfonates, ethoxylated and / or propoxylated alcohol phosphates, ethoxylated and / or propoxylated alkylaryl phosphates, taurates, sulfosuccinates and polycarboxylates, sodium alkylnaphthalene sulfonate formalin condensates or modified styrene-maleic anhydride copolymers). Examples of commercially available sodium alkylnaphthalene sulfonate formalin condensates include Morwet D425, TERSPERSE 2020, Agrosurf WG-2300, etc. An example of a commercially available modified styrene-maleic anhydride copolymer is TERSPERSE 2612.

[0219] Suitable nonionic surfactants include alkoxylated surfactants and block copolymer surfactants. Examples of alkoxylated surfactants useful in the present invention include castor oil ethoxylate, tridecanol ethoxylate, nonylphenol ethoxylate, octylphenol ethoxylate, tristyrylphenol ethoxylate, phosphate ethoxylate, tallow amine ethoxylate, cocoamine ethoxylate and oleylamine ethoxylate.

[0220] Suitable antifreeze agents that may be added to the liquid agrochemical compositions are liquid polyols, such as ethylene glycol and propylene glycol.

[0221] Suitable pH adjusters may be citric acid or phosphoric acid.

[0222] Wetting agents that can be added to the liquid agricultural chemical composition of the present invention include, but are not limited to: polyaryl alkoxylated phosphates and potassium salts thereof (e.g., FLK, Stepfac TSP PE-K). Other suitable wetting agents include dioctyl sodium sulfosuccinate (e.g., SDS, OT) and ethoxylated alcohols (e.g., Trideth-6; BC 610; 4894).

[0223] Optionally, about 0.1 wt % to about 5.0 wt % of an anti-foaming agent or defoaming agent is used to prevent any unwanted foaming generated when making the suspension concentrate composition of the present application. Preferred anti-foaming agents are selected from the group consisting of silicone-based compounds, alcohols, glycol ethers, mineral spirits, acetylene glycols, polysiloxanes, organosiloxanes, siloxane diols, reaction products of silicon dioxide and organosiloxane polymers, polydimethylsiloxanes or polyalkylene glycols, alone or in combination. Suitable defoamers include AGNIQUE DFM 111S; SAG-10; SAG-1000AP; SAG-1529; SAG-1538; SAG-1571; SAG-1572; SAG-1575; SAG-20 01; SAG-220; SAG-290; SAG-30; SAG-30E; SAG-330; SAG-47; SAG-5440; SAG-7133 and SAG-770.

[0224] Examples of thickeners based on anionic heteropolysaccharides from the xanthan group are in particular Rhodopol 23 , Rhodopol G 、Rhodopol 50MD 、Rhodicare T Kelzan , Kelzan S and Satiaxane CX91 .

[0225] The preservatives used can be benzisothiazolinone (Proxel GXL) or phenols, 2-bromo-2-nitropropane-1,3-diol, also known as bronopol (Bioban BP 30), 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one (Kathon CG / ICP), glutaraldehyde (Ucarcide 50), chloromethylisothiazolinone (CMIT) / methylisothiazolinone (MIT) (Isocil Ultra 1.5), 2.2-dibromo-3-nitrilopropionamide (Reputain 20), natamycin and nisin, Bropol / CMIT / MIT (Mergal 721K3).

[0226] Suitable colorants (eg red, blue and green) are preferably pigments and water-soluble dyes which are sparingly soluble in water. Examples are inorganic colorants (eg iron oxide, titanium oxide and ferric ferrocyanide) and organic colorants (eg alizarin, azo and phthalocyanine colorants).

[0227] According to an embodiment of the present invention, the composition of the present invention comprises a co-crystal of sulfentrazone and metribuzin and one or more pesticides other than the two components of the co-crystal.

[0228] The pesticide may be selected from the group consisting of herbicides, fungicides, insecticides, nematicides, miticides, plant growth regulators and safeners.

[0229] Preferably, the pesticide is a herbicide selected from the following: isoxazolidinone herbicides, urea herbicides, triazine herbicides, hydroxybenzonitrile herbicides, thiocarbamate herbicides, pyridazine herbicides, chloroacetanilide herbicides; benzothiazole herbicides; phenylcarbamate herbicides, cyclohexene oxime herbicides; pyridine carboxylic acid herbicides; pyridine herbicides; quinolinecarboxylic acid herbicides; chlorotriazine herbicides, aryloxyphenoxypropionic acid herbicides, oxadiazolone herbicides, phenylurea herbicides, sulfonamide herbicides, triazolopyrimidine herbicides, amide herbicides, pyridazine herbicides, dinitroaniline herbicides or combinations thereof.

[0230] Preferably, the pesticide is a fungicide selected from the group consisting of amide fungicides, acylamino acid fungicides, aniline fungicides, benzamide fungicides, sulfonamide fungicides, strobilurin fungicides, aromatic fungicides, benzimidazole fungicides, carbamate fungicides, phenylcarbamate fungicides, conazole fungicides (imidazoletriazoles), copper fungicides, dithiocarbamate fungicides, imidazole fungicides, organophosphorus fungicides, oxazole fungicides, pyrazole fungicides, pyridine fungicides or combinations thereof.

[0231] Preferably, the insecticide is selected from arsenic insecticides, botanical insecticides, carbamate insecticides, benzofuranylmethylcarbamate insecticides, dimethylcarbamate insecticides, insecticides, dinitrophenol insecticides, fluorine insecticides, formamidine insecticides, fumigant insecticides, inorganic insecticides, insect growth regulators, benzoylphenylurea chitin synthesis inhibitors, macrolide insecticides, neonicotinoid insecticides, nereis toxin analog insecticides, organochlorine insecticides, organophosphorus insecticides, organothiophosphate insecticides, heterocyclic organothiophosphates. Insecticides, phenyl organothioate phosphorothioate insecticides, phosphonate insecticides, thiophosphonate insecticides, aminophosphorate insecticides, thiophosphoramidate insecticides, phosphorodiamidates insecticides, oxadiazine insecticides, oxadiazolone insecticides, phthalimide insecticides, physical insecticides, pyrazole insecticides, pyrethroid insecticides, pyrethroid insecticides, pyrimidine amine insecticides, pyrrole insecticides, quaternary ammonium insecticides, sulfoximine insecticides, cypermethrin insecticides, superacid insecticides, thiazole insecticides, thiazolidine insecticides and thiourea insecticides.

[0232] Preferably, the acaricide is selected from the group consisting of avermectin, carvacrol, benomyl, carbofuran, carbosulfan, dimethoate, benomyl, aldicarb, aldicarb, oxamyl, carbamidophos, carbon disulfide, cyanide, 1,2-dichloropropane, 1,3-dichloropropylene, dimethyl disulfide, methyl bromide, methyl iodide, sodium tetrathiocarbonate, chlorpyrifos, chlorpyrifos, chlorpyrifos, dimethoate, ethoxyproline, fenthiophos, thiothioate, thiothioate, thiothioate, thiothioate, chlorpyrifos ...

[0233] Preferably, the safener is selected from the group consisting of fenthiocarb, BPCMS, clofonet-mexyl, cyfluthrin, cyproconazole, dicyclonon, pyraclostrobin, fenthiocarb, fenthiocarb, fluazifop, oxadiazine, isoxadiazole, fenthiocarb, fenthiocarb, mefenpyr, mephenate, metcamifen, naphthalene dicarboxylic anhydride and fenthiocarb.

[0234] In an embodiment of the present invention, the liquid agricultural chemical composition comprises from about 10% to about 40% w / w of a co-crystal of sulfentrazone and metribuzin, about 1% to about 20% of an acrylic acid polymer, and about 1% to about 20% of glycerol, based on the total weight of the liquid agricultural chemical composition.

[0235] In an embodiment of the present invention, the liquid agricultural chemical composition comprises from about 10% to about 40% w / w of a co-crystal of sulfentrazone and metribuzin, about 1% to about 20% of an acrylic acid polymer, and about 1% to about 20% of glycerol, based on the total weight of the liquid agricultural chemical composition, wherein the agricultural chemical composition is formulated as a suspension concentrate.

[0236] In an embodiment of the present invention, the liquid agricultural chemical composition comprises from about 10% to about 40% w / w of a co-crystal of sulfentrazone and metribuzin, about 1% to about 20% of an alkali-swellable polyacrylate, about 0.1% to about 30% of glycerol, and about 10% to about 30% of water, based on the total weight of the liquid agricultural chemical composition, wherein the liquid agricultural chemical composition is formulated as a suspension concentrate.

[0237] The compositions according to the invention can also be prepared by tank mixing the active ingredients with auxiliaries suitable for the formulation of these active ingredients, or alternatively can be sold as a kit of parts containing the active ingredients and other ingredients which can be mixed before spraying.

[0238] According to an embodiment of the present invention, a method for controlling weeds is provided, wherein the method comprises applying an effective amount of a composition comprising a co-crystal of sulfentrazone and a triazone herbicide to a plant or its habitat, a plant seed or soil.

[0239] According to an embodiment of the present invention, a method for controlling weeds is provided, wherein the method comprises applying an effective amount of a composition comprising a co-crystal of sulfentrazone and metribuzin to a plant or its habitat, a plant seed or soil.

[0240] The herbicide composition of the present invention can be used to target weeds in crops, such as corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybean, peanut, buckwheat, beet, rapeseed, sunflower, sugarcane, tobacco, etc.; vegetables: nightshade vegetables, such as eggplant, tomato, sweet pepper, pepper, potato, etc., melon vegetables such as cucumber, pumpkin, zucchini, watermelon, melon, pumpkin, etc., cruciferous vegetables such as radish, white radish, horseradish, kohlrabi, cabbage, kale, mustard, broccoli, cauliflower, etc., Asteraceae vegetables such as burdock, sedge, artichoke, lettuce, etc., Liliaceae vegetables such as green onion, onion, garlic and asparagus, Amieceae vegetables such as carrot, parsley, celery, parsnip, etc., Chenopodiaceae vegetables such as spinach, Swiss chard, etc., Lamiaceae vegetables such as perilla, mint, Le, etc., strawberry, sweet potato, yam, taro, etc., flowers, foliage plants, lawn grass, fruits: pome fruits such as apples, pears, quinces, etc., stone fruits such as peaches, plums, nectarines, plums, cherries, apricots, prunes, etc., citrus fruits such as oranges, lemons, rime, grapefruit, etc., nuts such as chestnuts, walnuts, hazelnuts, almonds, pistachios, cashews, macadamia nuts, etc., berries such as blueberries, cranberries, blackberries, raspberries, etc., grapevines, persimmons, olives, plums, bananas, oil palm, coffee, dates, coconuts, etc.; trees other than fruit trees: tea trees, mulberry trees, flowering plants, trees such as ash trees, birch trees, dogwood trees, eucalyptus trees, ginkgo trees, lilac trees, maple trees, oak trees, poplar trees, Judas trees, southern European bauhinias, sweetgum trees, plane trees, beech trees, Japanese cypress trees, fir trees, hemlock trees, pine trees, spruce trees and northeastern yew trees, etc.

[0241] Thus, in another aspect, the present invention provides a method of controlling weeds at a locus, the method comprising applying to the locus a co-crystal of sulfentrazone and metribuzin.

[0242] The target weeds may be selected from Urticaceae weeds: Urtica dioica, Polygonaceae weeds: Polygonum convolvulus, Polygonum lapathifolium, Polygonum pensylvanicum, Polygonum persicaria, Polygonum longisetum, Polygonum aviculare, Polygonum arenastrum, Polygonum cuspidatum, Rumex japonicus, Rumex crispus, Rumex obtusifolius, Rumex acetosa; Portulacaceae weeds: Portulaca oleracea; Caryophyllaceae weeds: Stellaria media, Cerastium holosteoides), Cerastium glomeratum, Spergula arvensis, Silene gallica

[0243] Weeds in the Fabaceae family: Mollugo verticillata; Weeds in the Chenopodium family: Chenopodium album, Chenopodium ambrosioides, Kochia scoparia, Salsola kali, Atriplex spp.; Weeds in the Amaranthaceae family: Amaranthus retroflexus, Amaranthus viridis, Amaranthus lividus, Amaranthus spinosus, Amaranthus hybridus, Amaranthus palmeri, Amaranthus rudis, Amaranthus patulus, Amaranthus stuberculatos, Amaranthus blitoides), Amaranthus deflexus, Amaranthus quitensis, Alternanthera philoxeroides, Alternanthera sessilis, Alternanthera tenella; Poppy family weeds: Papaver rhoeas, Argemone Mexicana; Cruciferous weeds: Raphanus raphanistrum, Raphanus sativus, Sinapis arvensis, Capsella bursa-pastoris, Brassica juncea, Brassica campestris, Descurainia pinnata, Rorippa islandica, Rorippa sylvestris, Thlaspi arvense, Myagrum rugosum, Lepidiumvirginicum, Coronopus didymus;Dinebra weeds: Dinebra Americana, Dinebra aquatic, Dinebra aristidoides, Dinebra bromoides, Dinebra calycina, Dinebra caudata, Dinebra chinensis, Dinebra chloride, Dinebra chondrosioides, Dinebra coerulescens, Dinebra cristata, Dinebra curtipendula, Dinebra decipiens, Dinebra divaricate, Dinebra divaricatissima, Dinebra dura, Dinebra guineensis, Dinebra hirsute, Dinebra hirta, Dinebra juncifolia, Dinebra ligulata, Dinebra lima, Dinebra melicoides, Dinebra nealleyi, Dinebra neesii, Dinebra panicea, Dinebra panicoides, Dinebra pubescens, Dinebra repens, Dinebra scabra, Dinebra secunda, Dinebra simoniana, Dinebra southwoodii, Dinebra squarrosa, Dinebra srilankensis, Dinebra tuaensis, Dinebra verticillate, Dinebra retroflexa..Dinebra haareri, Dinebra marquisensis, Dinebra perrieri, Dinebra polycarpha, Dinebra somalensis; Cleome weeds of the family Crataegaceae: Cleome affinis;Weeds in the Fabaceae family: Aeschynomene indica, Aeschynomenerudis, Sesbania exaltata, Cassia obtusifolia, Cassiaoccidentalis, Desmodium tortuosum, Desmodium adscendens, Trifolium repens, Pueraria lobata, Vicia angustifolia, Indigofera hirsute, Indigofera truxillensis, Vigna sinensis; Weeds in the Oxalidaceae family: Oxalis corniculata, Oxalis strica, Oxalis oxyptera; Weeds in the Geranium family: Geranium carolinense, Erodium cicutarium; Euphorbia weeds: Euphorbia helioscopia, Euphorbia maculata, Euphorbia humistrata, Euphorbia esula, Euphorbia heterophylla, Euphorbia brasiliensis, Acalypha australis, Croton glandulosus, Crotonlobatus, Phyllanthus corcovadensis, Ricinus communis; Malvaceae weeds: Abutilon theophrasti, Sida rhombiforia, Sida cordifolia, Sida spinosa, Sida glaziovii, Sida santaremnensis, Hibiscus trionum, Anoda cristata, Malvastrum coromandelianum);

[0244] Weeds in the Sterculiaceae family: Waltheria indica; Weeds in the Violaceae family: Viola arvensis, Viola tricolor; Weeds in the Cucurbitaceae family: Sicyos angulatus, Echinocystis lobata, Momordica charantia; Weeds in the Leptothrix family: Lythrum salicaria; Weeds in the Apiaceae family: Hydrocotyle sibthorpioides; Weeds in the Sapindaceae family: Cardiospermum halicacabum; Weeds in the Primulaceae family: Anagallis arvensis; Weeds in the Asclepiaceae family: Asclepias syriaca, Ampelamus albidus; Weeds in the Rubiaceae family: Galium umaparine, Galium spurium var.echinospermon, Spermacoce latifolia, Richardia brasiliensis, Borreria alata; Convolvulaceae weeds: morning glory (Ipomoeanil), Ipomoea hederacea, round-leaved morning glory (Ipomoea purpurea), Ipomoea hederaceavar.integriuscula, tuberous sweet potato (Ipomoea lacunosa), three-lobed sweet potato (Ipomoea triloba), color-changing morning glory (Ipomoea acuminata), ivy-leaved morning glory (Ipomoea hederifolia), orange-red morning glory (Ipomoea coccinea), feather-leaved morning glory (Ipomoea quamoclit), Ipomoea grandifolia, Ipomoea aristolochiafolia, five-clawed golden dragon (Ipomoea cairica), field bindweed (Convolvulus arvensis), Calystegia hederacea, Calystegia japonica, Merremia hedeacea, Merremia aegyptia, Merremia cissoides, Jacquemontia tamnifolia; Boraginaceae weeds: Myosotisarvensis; Lamiaceae weeds: Lamiumpurpureum, Lamium amplexicaule, Leonotis nepetaefolia, Hyptissuaveolens, Hyptis lophanta, Leonurus sibiricus, Stachysarvensis; Solanaceae weeds: Datura stramonium, Solanum nigrum, Solanum americanum, Solanum ptycanthum, Solanum sarrachoides, Solanum rostratum, Solanum aculeatissimum, Solanum sisymbriifolium, Solanum carolinense, Physalis angulata, Physalis subglabrata, Nicandra physaloides; Scrophulariaceae weeds: Veronica hederaefolia, Veronica persica, Veronica arvensis; Plantaginaceae weeds: Plantago asiatica; Asteraceae weeds: Xanthium pensylvanicum, Xanthium occidentale, Helianthus annuus, Matricaria chamomilla, Matricaria perforata, Chrysanthemum segetum, Matricaria matricarioides, Arteraisia ​​princeps, Artemisia vulgaris, Artemisia verlotorum, Solidago altissima, Taraxacum officinale, Galinsoga ciliata), Galinsoga parviflora, Senecio vulgaris, Seneciobrasiliensis, Seneciogrisebachii, Conyza bonariensis, Conyza canadensis, Ambrosiaartemisiaefolia, Ambrosia trifida, Bidens pilosa, Bidens frondosa, Bidens subalternans, Cirsium arvense, Cirsium vulgare, Silybum marianum, Carduus nutans, Lactuca serriola, Sonchus oleraceus, Sonchus asper, Wedelia glauca, Melampodium perfoliatum, Emilia sonchifolia, Tagetes minuta, Blainvillea latifolia), Tridax procumbens, Porophyllum ruderale, Acanthospermum australe, Acanthospermum hispidum, Cardiospermum halicacabum, Ageratum conyzoides, Eupatorium perfoliatum, Eclipta alba, Erechtites hieracifolia, Gamochaeta spicata, Gnaphalium spicatum, Jaegeria hirta, Parthenium hysterophorus, Siegesbeckia orientalis, Soliva sessilis; Liliaceae weeds: Allium canadense, Allium vineale); Cornaceae weeds: Commelina communis, Commelina bengharensis, Commelina erecta; Gramineae weeds: Echinochloacrus-galli), Setaria viridis, Setaria faberi, Setaria glauca, Setaria geniculata, Digitaria ciliaris, Digitaria sanguinalis, Digitaria horizontalis, Digitaria insularis, Eleusine indica, Poa annua, Alospecurus aequalis, Alopecurus myosuroides, Avena fatua, Sorghum halepense, Sorghum vulgare, Agropyron repens, Lolium multiflorum, Lolium perenne, Lolium rigidum, Bromus secalinus, Bromus tectorum), Hordeum jubatum, Aegilops cylindrica, 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, Cenchrus echinatus, Cenchrus pauciflorus, Eriochloa villosa, Pennisetum setosum), African tiger tail grass (Chloris gayana), teff grass (Eragrostis pilosa), Rhynchelitrumrepens, Dactylocteniumaegyptium, Ischaemum rugosum, Oryza sativa, Paspalum notatum, Paspalum maritimum, Pennisetum clandestinum, Pennisetum setosum, Rottboellia cochinchinensis; Cyperaceae weeds: Cyperus microiria, Cyperus iria, Cyperus odoratus, Cyperus rotundus, Cyperus esculentus, Kyllingagracillima; Oleaceae weeds: Equisetum arvense, Equisetum palustre, red flower weed, etc.

[0245] In a preferred embodiment, the composition of the present invention is applied to soybean crops and is effective against several broadleaf weeds and grass weeds, namely, velvet leaf, redroot pigweed, common lambsquarters, tumbleweed, and giant foxtail.

[0246] In embodiments, the composition may be applied as a tank mix or as a premix composition.

[0247] In an embodiment, the composition of the present invention can be applied before or after emergence. In a preferred embodiment, the composition of the present invention can be used before emergence and before planting. The advantages of this composition are unexpectedly good residual effects and rapid burning of weeds when applied before planting or before emergence.

[0248] According to an embodiment of the present invention, the method of applying the agrochemical composition and mixture according to the present invention is not particularly limited. It can be a premix or tank mix of the active ingredient and the adjuvant suitable for the formulation, or it can be applied one by one in sequence.

[0249] According to an embodiment of the present invention, use of an agricultural chemical composition comprising a co-crystal of sulfentrazone and a triazone herbicide.

[0250] According to an embodiment of the present invention, use of an agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin.

[0251] According to an embodiment of the present invention, use of a liquid agricultural chemical composition comprising a co-crystal of sulfentrazone and metribuzin.

[0252] According to an embodiment of the present invention, a kit is provided, wherein the kit comprises a co-crystal of sulfentrazone and a triazone herbicide and other agricultural chemical excipients.

[0253] According to an embodiment of the present invention, a kit is provided, wherein the kit comprises a co-crystal of sulfentrazone and a triazone herbicide.

[0254] According to an embodiment of the present invention, a kit comprises a co-crystal of sulfentrazone and metribuzin.

[0255] The present invention will now be described with reference to the following specific examples. It should be noted that the examples attached below illustrate rather than limit the present invention, and that those skilled in the art will be able to design many alternative examples without departing from the scope of the present invention.

[0256] Examples

[0257] Example 1: Preparation of cocrystals of sulfentrazone and metribuzin

[0258] For the 1:1 cocrystal of sulfentrazone and metribuzin, 193.5 g of sulfentrazone and 107 g of metribuzin were added to a round bottom flask. To the mixture was added 150 ml of dichloroethane. The solution was stirred at 30°C overnight, 1000 ml of hexane was added and stirred to obtain a solid, which was filtered and dried under vacuum to obtain 268 g of crystals. HPLC analysis: metribuzin-33.48% (w / w) and sulfentrazone-65.31% (w / w), which corresponds to about 1:1 metribuzin:sulfentrazone (mole:mole). ( Figure 1 ).

[0259] Spectral analysis of eutectic

[0260] The cocrystal prepared according to Example-1 was further characterized by FT-IR ( Figure 2 ). It was found that the FT-IR spectrum of the cocrystal of sulfentrazone and metribuzin exhibited at least 3 characteristic values, in particular at least 5 characteristic values, or all values ​​selected from the following items: (±4 cm -1 )3314, 3264, 2970, 1736, 1685, 1630, 1521, 1494, 1467, 1420, 1392, 1367, 1348, 1332, 1303, 1262, 1193, 1163, 1116, 1098, 1072, 976, 942, 893, 877, 824, 796, 764, 740, 670, 661, 645, 602, 570, 458, especially (±4cm -1)3314, 3264, 1736, 1685, 1630, 1521, 1494, 1467, 1420, 1392, 1367, 1348, 1332, 1163, 1116, 1098, 1072, 976 and 824.

[0261] Crystallographic analysis of cocrystals

[0262] The co-crystal prepared according to Example-1 was characterized by PXRD. Figure 3 ) The co-crystal of sulfentrazone and metribuzin shows an X-ray powder diffraction pattern at 25°C. (PXRD conditions: instrument: 2nd generation D2 Phaser powder X-ray diffractometer manufactured by Bruker; operating parameters: 30.0 kV, 10 mA; radiation: Cu-Kα; wavelength: 1.54060°A, scanning range: 2–40 2θ, step length: 0.02°). The co-crystal of sulfentrazone and metribuzin shows at least 3, particularly at least 4 and more preferably all of the following reflection angles, which are given as 2θ values ​​in the following Table 1:

[0263] Table 1

[0264]

[0265] Single crystal X-ray diffraction

[0266] Single crystal X-ray analysis determined the atomic and molecular structure of the cocrystal, including the molar relationship between the two compounds forming the cocrystal. Single crystal X-ray diffraction data of the cocrystal of sulfentrazone and metribuzin were collected on a Bruker D8 QUEST PHOTON-100 detector. The structure was solved using direct methods and refined and extended by Fourier techniques using the SHELXTL-PLUS software package. Figure 7 Single crystal X-ray diffraction is given in , showing the hydrogen bonding interactions that form the cocrystal of sulfentrazone and metribuzin.

[0267] The single crystal X-ray diffraction data and refinement of the co-crystal of sulfentrazone and metribuzin are given in Table 2 below:

[0268] Table 2

[0269]

[0270] Thermal Analysis of Eutectic

[0271] DSC measurements of the cocrystals were performed on a Mettler-Toledo DSC 3STARe system and STARe software was used to analyze the DSC data. The measurements were performed using a closed aluminum pan with a capacity of 40 microliters and under nitrogen flow at a heating rate of 10°C / min and a sample weight of 5 to 10 mg.

[0272] The DSC of the cocrystal showed an endothermic peak starting at 107.3°C and peaking at 110.5°C. Figure 4 ) and the specific heat of melting (normalized) were between -69 J g^-1 and -81 J g^-1. The endothermic peaks seen in DSC did not match the respective melting points of sulfentrazone and metribuzin. Therefore, analysis using DSC indicated co-crystallization.

[0273] Example 2: Suspension concentrate (SC) of co-crystal of sulfentrazone and metribuzin

[0274]

[0275]

[0276] 5 g of propylene glycol, 1 g of polyalkylene glycol ether, 5 g of alkali swollen polyacrylate, 2 g of acrylic polymer were stirred with 42.60 g of water for at least 1 hour. 0.2 g of silicone defoamer was added to the above mixture and stirred. 13.867 g of eutectic of sulfentrazone and metribuzin and 22.43 g of metribuzin were added and homogenized for at least 1 hour and then ground. 7.5 g of 2% xanthan gum gel was added and the mixture was homogenized for at least 1 hour. The homogenized mixture was then set to uniform gelation. The analytical technique, FT-IR ( Figure 5 ) and P-XRD( Figure 6 ) to characterize the obtained composition.

[0277] Example 3: 26.77% sulfentrazone and 8.93% metribuzin SC

[0278] Element Amount (w / w%) Sulfonamide (98% purity) 9.1 Metribuzin 27.6 glycerin 5 Polyalkylene glycol ether 1 Alkali swellable polyacrylate 4.7 Acrylic polymer 2.3 Silicone defoamer 0.2 Clay 0.3 Xanthan gum 0.15 water QS total 100

[0279] 27.85g metribuzin and 9.30g sulfentrazone technology are mixed to prepare a homogeneous powder. The powder is then kept in a 54°C incubator for 14 days to promote eutectic formation. Separately, 5.0g glycerol, 1.0g polyalkylene glycol ether, 2.3g acrylic acid polymer, 4.70g alkali swollen polyacrylate are added to the slurry preparation and stirred for 30 minutes to make the solution uniform, thereby preparing a slurry in water. Further, 0.2g of silicone defoamer and 0.3g of clay are added successively under constant stirring. Then, in the slurry obtained in the above steps, a homogeneous powder of metribuzin sulfentrazone for pretreatment is added under continuous stirring. The slurry is stirred for 30 minutes to break up the agglomeration and keep cooling to less than 15°C and used for bead milling. After the slurry reaches the desired particle size (D90<10 microns), it is used for gelation. A 2% hydrogel is obtained by adding 8g xanthan gum and 0.2g bronopol.

[0280] Example 4: 26.77% sulfentrazone and 8.93% metribuzin SC

[0281] Element Amount(%w / w) Metribuzin Tech @97% 27.85 Sulfentrazone Tech@98% 9.30 Alkali swellable polyacrylate 4.70 Polyalkylene glycol ether 1.00 Acrylic polymer 2.30 1,2-Benzisothiazoline-3-one 0.20 Silicone defoamer 0.20 Clay 0.30 glycerin 5.00 Xanthan gum 8.00 water QS total 100

[0282] The above amounts of metribuzin and sulfentrazone are mixed to prepare a uniform powder. The powder thus obtained is melted on an oil bath at 105-110°C. It is then cooled at room temperature to obtain flakes. The flakes are then ground to obtain a powder. Separately, a slurry is prepared in water by adding glycerol, polyalkylene glycol ether, acrylic polymer, alkali-swollen polyacrylate to a slurry formulation and stirring for 30 minutes to make the solution uniform. Further, a silane defoamer, clay, and 1,2-benzisothiazolin-3-one are added in sequence under constant stirring. Then, the powder of metribuzin sulfentrazone obtained from the pretreatment is added to the slurry obtained in the above steps under continuous stirring. The slurry is stirred for 30 minutes to break up the agglomerates and kept to cool to less than 15°C and used for bead milling. After the slurry reaches the desired particle size (D90<10 microns), it is used for gelation. A 2% hydrogel is obtained by adding 8g of xanthan gum and 1,2-benzisothiazolin-3-one.

[0283] Example 5: SC Composition of Sulfonamide and Metribuzin

[0284]

[0285]

[0286] 5 g of propylene glycol, 1 g of polyalkylene glycol ether, 5 g of alkali-swollen polyacrylate and 2 g of acrylic polymer were stirred with 42.60 g of water for at least 1 hour. 0.2 g of silicone defoamer was added to the above mixture and stirred. 8.98 g of sulfentrazone and 27.22 g of metribuzin were added and homogenized for at least 1 hour and then ground. 7.5 g of 2% xanthan gum gel was added and the mixture was homogenized for at least 1 hour. The homogenized mixture was then set to uniform gelation.

[0287] Example 6: Sulfonamide and metribuzin SC

[0288] Element Amount(%w / w) Metribuzin Tech @97% 27.85 Sulfentrazone Tech@98% 9.3 Alkali swellable polyacrylate 4.7 Polyalkylene glycol ether 1 Acrylic polymer 2.3 1,2-Benzisothiazoline-3-one 0.2 Silicone defoamer 0.2 Clay 0.3 glycerin 5 Xanthan gum 8 water QS total 100

[0289] Add part of the water to a temperature regulating container equipped with a high-speed mixer and stir. Add alkali-swollen polyacrylate, acrylic polymer, polyalkylene glycol ether, silicone defoamer, part of the amount of glycerol and clay to obtain a solution. Then cool the solution to ≤25°C. Under high shear, metribuzin and sulfentrazone are added to the solution to obtain a mixture. The mixture is then ground at a grinding temperature of ≤25°C (particle size specifications d10≤1, d50≤4, d90≤10 and d100≤35μm) to obtain a ground matrix. The ground matrix is ​​returned to a mixing container heated to 54°C and mixed for about 1 hour. In addition, a thickener is prepared by adding glycerol, 1,2-benzisothiazolin-3-one, xanthan gum and water to a container and mixing for 30 minutes. The thickener is added to the ground matrix. The final composition is adjusted with water and released for quality inspection and packaging.

[0290] Example 7: Sulfonamide and metribuzin SC

[0291] Element Amount(%w / w) Sulfonamide (98% purity) 12.1 Metribuzin 24.6 glycerin 5 Polyalkylene glycol ether 1 Alkali swellable polyacrylate 6 Acrylic polymer 3 Xanthan Gum (2% Gel) 7.5 Clay 0.15 water QS total 100

[0292] The above amounts of metribuzin, sulfentrazone, glycerin, polyalkylene glycol ether, alkali-swellable polyacrylate, acrylic acid polymer, xanthan gum, clay and water were mixed and treated as given in Example-6 to obtain a suspension concentrate composition comprising a co-crystal of sulfentrazone and metribuzin.

[0293] Example 8: Sulfonamide and metribuzin SC

[0294]

[0295]

[0296] The above amounts of metribuzin, sulfentrazone, glycerin, polyalkylene glycol ether, alkali-swellable polyacrylate, acrylic polymer, silicone defoamer, xanthan gum, clay and water were mixed and treated as given in Example-6 to obtain a suspension concentrate composition comprising a co-crystal of sulfentrazone and metribuzin.

[0297] Example 9: Sulfonamide and metribuzin SC

[0298]

[0299] Processing: Add part of water to a temperature-regulated container equipped with a high-speed mixer and stir. Add alkali-swollen polyacrylate, acrylic acid polymer, polyalkylene glycol ether, silicone defoamer, part of glycerin and viscosity to obtain a solution. Then cool the solution to ≤25°C. Add metribuzin and sulfentrazone to the solution under high shear to obtain a mixture. Grind the material to the required particle size and measure the wet screen retention rate at a temperature of 25°C or below during the grinding process according to the process specification. Add a thickener to the grinding base. The final composition is adjusted with water and released for quality inspection and packaging.

[0300] Example 10

[0301] Stability study of suspension concentrate compositions

[0302] The stability characteristics associated with the compositions developed according to the present invention were studied. The compositions described in Example-3 and Example-4 were further used to evaluate the physicochemical parameters. It was found that the compositions of Example-3 and Example-4 remained stable when tested under ambient conditions, i.e., room temperature and pressure. The composition also passed the accelerated thermal stability (AHS) test for 14 days and 28 days and remained a flowable suspension with an off-white appearance. The amount of active content was also evaluated at all three stages (ambient, 14-day AHS, and 28-day AHS). It was found that the active ingredient remained almost unchanged without any obvious deterioration or loss. The composition also passed the wet sieve test because no crystals were observed to remain on the wet sieve. The particle size of the composition was analyzed and found to be almost constant, indicating that there was little / negligible particle size growth or crystal formation. (Table 3)

[0303] Table 3

[0304]

[0305] Example 11

[0306] Biological efficacy data

[0307] Pre-emergence studies were conducted on soybean crops to test the efficacy of the agrochemical compositions developed according to the present invention on several broadleaf and grass weeds, namely velvet leaf, redroot pigweed, common lambsfoot, tumbling pigweed and giant foxtail. The composition of Example-7 with a 1:2 ratio of sulfentrazone and metribuzin was tested in a soybean field at a rate of 630 g ai. It was found that the composition was effective for velvet leaf, redroot pigweed, common lambsfoot, tumbling pigweed and giant foxtail at all time intervals from 14 DAA (14 days after application) to 35 DAA (35 days after application). By the agrochemical composition of the present invention, the control rate of velvet leaf was observed to be more than 60%; the control rate of redroot pigweed was observed to be 100%. Similarly, the control rate for common lambsfoot and tumbling pigweed was observed to be more than 90%. Good control of 50-83% of giant foxtail was also observed in the 35 DAA-21 DAA observations, as shown in the following table.

[0308] Table 4

[0309]

[0310] Thus, the inventors of the present invention have discovered that an agrochemical composition made from a cocrystal of sulfentrazone and a triazone herbicide produces a stable composition. Forming a cocrystal of sulfentrazone and a triazone herbicide (particularly metribuzin) prior to incorporation into an agrochemical composition imparts physical stability to the system. The acrylate polymer and glycerol in the agrochemical composition of the cocrystal provide good performance, low or no sedimentation, and little particle size degradation over time. It should be understood that the present invention is not limited to the details of the above-described embodiments, which are described by way of example only.

Claims

1. A co-crystal comprising sulfentrazone and metribuzin, wherein the co-crystal is characterized by a powder X-ray diffraction pattern comprising peaks at diffraction angles of 2θ values ​​of 7.8°, 11.8°, 14.1°, 17.8°, 22.1°, 23.4° and 24.4° (±0.2), and wherein sulfentrazone and metribuzin are present in a molar ratio of 1:

1.

2. The co-crystal according to claim 1, wherein the co-crystal is characterized by at least one of the following: A DSC thermogram comprising an endothermic peak with an onset at 107.3°C and a peak at 110.5°C; or Single crystal X-ray diffraction with lattice parameters: α=90°, β=93.5058°(7) and γ=90°.

3. A method for preparing the co-crystal according to claim 1 or 2, wherein the co-crystal is obtained by solution crystallization using ethylene dichloride and hexane as solvents.

4. A suspension concentrate comprising the co-crystal according to claim 1 or 2.

5. The suspension concentrate according to claim 4, wherein the co-crystal comprises 10-90% sulfentrazone and 90-10% metribuzin by weight of the co-crystal.

6. A method for preparing a composition comprising the co-crystal according to claim 1 or 2, the method comprising: a) preparing an aqueous mixture of an agrochemically suitable excipient to obtain a homogeneous solution; b) adding metribuzin and sulfentrazone to the homogeneous solution of step (a) to obtain a slurry; c) optionally grinding the slurry; d) heating the slurry of step (b) or (c) and cooling to room temperature; e) optionally adding other agrochemical excipients to the slurry of step (d) and mixing to obtain a homogeneous agrochemical composition.

7. A method for controlling weeds, comprising applying a herbicidally effective amount of a composition to a plant or its habitat, a plant seed or soil, wherein the composition comprises the co-crystal according to claim 1 or 2.

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