Stable liquid herbicide formulations with high loading of pyrazosulfuron

Abstract

The present invention relates to a stable and efficient liquid herbicide formulation system comprising at least 125 g / L, based on the total volume, of pyrazosulfuron; an organic amine compound and an organic solvent system; and to a method for controlling undesired plant species. The present invention also relates to novel solid solvates of pyrazosulfuron.

Description

[0001] Related Applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 346,920, filed on May 30, 2022; the entire contents of that provisional application are hereby incorporated by reference herein.

[0003] Throughout this application, various publications are cited. The disclosures of the documents and publications cited herein are hereby incorporated into this application by reference in their entirety. Technical Field

[0004] The present invention relates to a stable and highly effective liquid herbicide formulation system comprising at least 125 g / L of pyrasulfonyl sulfone based on total volume; an organic amine compound and an organic solvent system; and to a method for controlling undesirable plant species. The present invention also relates to a new solid solvate of pyrasulfonyl sulfone, which is found to be formed with dimethyl sulfoxide in the absence of an organic amine in the formulation. Background Art

[0005] Many herbicidal active ingredients are known to be inhibitors of the enzyme p-hydroxyphenylpyruvate dioxygenase (HPPD). As is the case with many other herbicidal active ingredients, these HPPD inhibitors are not always tolerated well enough (i.e. not sufficiently selective) by certain important crop plants such as corn, rice or cereals, and their use is therefore very limited. Therefore, they cannot be used in certain crops, or can only be used at low application rates, so that the desired broad herbicidal activity against harmful plants cannot be ensured.

[0006] Pyrazole is one such HPPD inhibitor that is effective against a wide range of broadleaf weeds found in fields of several types of crops. It is an albino herbicide and inhibits the HPPD enzyme that affects the formation of carotenoid pigments in plants and causes chlorophyll degradation.

[0007] Like most herbicides, liquid formulations of pyrasulfotole, such as emulsifiable concentrates (EC), are common formulation forms because they can have low production costs and involve simple technology. The liquid formulation can be tank mixed or otherwise combined with water and possibly other additives to form a field formulation. The field formulation can then be applied to the crop by boom spraying or the like to deliver the herbicide to the field or crop.

[0008] Sulfonylpyrazone was first disclosed in the publication WO 01 / 74785 of Bayer. There are many types of commercially available liquid formulations of sulfonylpyrazone, which are suitable for selectively controlling weeds in crops. The effectiveness of herbicides like sulfonylpyrazone generally depends on the concentration of active sulfonylpyrazone in the formulation system, and also on its stability during storage and field application.

[0009] Formulating commercially acceptable pyrasulfone-containing herbicides is fraught with many challenges. Pyrasulfone is highly soluble in water, but not in organic solvents. Physical and biological incompatibilities naturally arise when formulating compositions containing multiple chemicals, including active compounds. Selecting the right blend of materials to incorporate high concentrations of pyrasulfone in liquid formulations remains a major challenge in the art.

[0010] Many efforts have been made in the related art to prepare effective liquid formulations with high concentrations of pyrasulfonyl sulfone. Various surfactant systems and solvent systems have been tried. However, the prior art has not addressed the problem of formulations with solvate deposition of pyrasulfonyl sulfone in highly soluble solvents and solved the problem to obtain very high concentration liquid formulations of pyrasulfonyl sulfone.

[0011] In view of the above, the present invention is directed to a novel stable and highly effective liquid high-concentration herbicide formulation system of pyrasulfone, which overcomes the solvate deposition and thus improves the overall efficiency of the formulation. Summary of the invention

[0012] We have rationally solved the challenges described above in whole or in part by obtaining novel stable herbicide formulation systems (as defined below) comprising suitable co-formulations and the solvent-surfactant system of the present invention.

[0013] The present invention relates to a liquid herbicide formulation system comprising (a) at least 125 g / L of pyrasulfone based on the total volume of the formulation; (b) an effective amount of an organic amine compound; and (c) an effective amount of an organic solvent.

[0014] The present invention relates to a liquid herbicide formulation system, which comprises (a) at least 125 g / L of pyrasulfone based on the total volume of the formulation; (b) an effective amount of an organic amine compound; and (c) an effective amount of an organic solvent, which includes dimethyl sulfoxide, cyclohexanone, propylene carbonate, aromatic solvents, vegetable oils and solvent systems thereof.

[0015] The present invention relates to a liquid herbicide formulation system, which comprises (a) at least 180 g / L of pyrasulfone based on the total volume of the formulation; (b) an effective amount of an organic amine compound; and (c) an effective amount of an organic solvent, which includes dimethyl sulfoxide, cyclohexanone, propylene carbonate, aromatic solvents, vegetable oils and solvent systems thereof.

[0016] The present invention relates to a liquid herbicide formulation system, which comprises (a) at least 250 g / L of pyrasulfone based on the total volume of the formulation; (b) an effective amount of an organic amine compound; and (c) an effective amount of an organic solvent, which includes dimethyl sulfoxide, cyclohexanone, propylene carbonate, aromatic solvents, vegetable oils and solvent systems thereof.

[0017] The present invention relates to a liquid herbicide formulation system, which comprises (a) at least 350 g / L of pyrasulfone based on the total volume of the formulation; (b) an effective amount of an organic amine compound; and (c) an effective amount of an organic solvent, which includes dimethyl sulfoxide, cyclohexanone, propylene carbonate, aromatic solvents, vegetable oils and solvent systems thereof.

[0018] The present invention also relates to a liquid herbicide formulation system, which further comprises an effective amount of a safener and an effective amount of an agriculturally acceptable carrier, wherein the safener is selected from the group consisting of mefenpyr, clofomycet-mexyl and isoxadifen-ethyl.

[0019] More specifically, the present invention relates to a liquid herbicide formulation system comprising (a) at least 125 g / L of pyrasulfone based on the total volume of the formulation; (b) an effective amount of an organic amine compound selected from the group consisting of organic amine alkoxylates and alkanolamines; and (c) an effective amount of an organic solvent, which is dimethyl sulfoxide.

[0020] More specifically, the present invention relates to a liquid herbicide formulation system comprising (a) at least 125 g / L of pyrasulfone based on the total volume of the formulation; (b) an effective amount of an organic amine compound, which is an organic amine alkoxylate; and (c) an effective amount of an organic solvent, which is propylene carbonate.

[0021] More specifically, the present invention relates to a liquid herbicide formulation system comprising (a) at least 125 g / L of pyrasulfone based on the total volume of the formulation; (b) an effective amount of an organic amine compound, which is an alkyl alcohol amine; and (c) an effective amount of an organic solvent, which is propylene carbonate.

[0022] More specifically, the present invention relates to a liquid herbicide formulation system comprising (a) at least 125 g / L of pyrasulfone based on the total volume of the formulation; (b) an effective amount of an organic amine compound, which is an organic amine alkoxylate; and (c) an effective amount of an organic solvent, which is an aromatic solvent.

[0023] More specifically, the present invention relates to a liquid herbicide formulation system comprising (a) at least 125 g / L of pyrasulfone based on the total volume of the formulation; (b) an effective amount of an organic amine compound, which is an alkyl alcohol amine; and (c) an effective amount of an organic solvent, which is an aromatic solvent.

[0024] The present invention also provides a method of treating plants against undesirable vegetation, which method comprises applying the herbicide formulation system disclosed herein, after dilution with water, to target parts of the plants so as to treat the plants against undesirable vegetation.

[0025] The present invention also provides a process for preparing the herbicide formulation system disclosed herein from the individual component parts.

[0026] The present invention further provides a method for controlling undesirable vegetation, the method comprising applying the herbicide formulation system disclosed herein to a locus. The present invention also provides a method for controlling grass weeds and broadleaf weeds, the method comprising diluting the herbicide formulation system disclosed herein with water, and applying the aqueous formulation to a locus where the plants are located.

[0027] The present invention provides a method for controlling undesirable vegetation, the method comprising applying to a locus a liquid herbicide formulation system comprising: (a) at least 125 g / L of pyrasulfotole based on the total volume of the formulation; (b) an effective amount of an organic amine compound; and (c) an effective amount of an organic solvent.

[0028] The present disclosure also includes a solid state form of pyrasulfone dimethyl sulfoxide solvate, which is referred to as Form B and may be characterized by an XRPD pattern having peaks at 6.1, 11.2, 11.6, 13.4, and 22.5 degrees 2θ ± 0.2 degrees 2θ. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 Shown is the X-ray powder diffraction pattern (XRPD) of Form B of the dimethyl sulfoxide (DMSO) solvate of pyrasulfone.

[0030] Figure 2 The X-ray powder diffraction pattern (XRPD) of Form A of anhydrous pyrasulfone obtained according to the method disclosed in the US2002065200 publication is shown. DETAILED DESCRIPTION

[0031] definition

[0032] Before describing the subject matter of the present invention in detail, it may be helpful to provide definitions of certain terms used herein. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the subject matter belongs.

[0033] Certain exemplary embodiments are described to provide an overall understanding of the principles of the invention disclosed herein. It is assumed that those skilled in the art will understand that the inventive features and methods specifically described herein and illustrated in the experimental section are non-limiting exemplary embodiments and that the scope of the invention is defined solely by the claims. Features illustrated or described in one exemplary embodiment may be combined with features of other embodiments. Such modifications and variations are intended to be included within the scope of the invention.

[0034] Reference will now be made in detail to the embodiments described in the subsequent paragraphs, wherein reference numerals refer to similar elements throughout. In this regard, embodiments of the present invention may have different forms and should not be construed as being limited to the descriptions set forth herein. Therefore, only embodiments are described below to explain aspects of the present disclosure.

[0035] As used herein, the term "pesticide" generally refers to an agent that can be used to control and / or kill harmful organisms. The term is understood to include, but is not limited to, fungicides, insecticides, nematicides, herbicides, miticides, parasiticides or other control agents. For chemical classes and applications and the specific compounds of each class, see "The Pesticide Manual Thirteenth Edition" (British Crop Protection Council, Hampshire, England, 2003) and "The e-Pesticide Manual, Version 3" (British Crop Protection Council, Hampshire, England, 2003-04), the contents of each of which are incorporated herein by reference in their entirety.

[0036] As used herein, the term "system" means, but is not limited to, a collection of active ingredients and / or acceptable co-formulations for administration by simultaneous, contemporaneous and / or sequential administration. It also means a combination of individual components at any administration time (e.g., sequential), and / or in any physical form (e.g., blends, solutions, suspensions, dispersions, emulsions, alloys, etc.). "System" may also refer to combining and administering active ingredients and acceptable co-formulations as a composition and / or formulating each active ingredient in a mixture or combination as a separate composition and administering simultaneously or at the same time or at different times in separate administrations.

[0037] The mixture or the individual components may be in any physical form, such as a blend, solution, suspension, dispersion, emulsion, admixture, and the like.

[0038] As used herein, the term "effective amount" refers to the amount of an active ingredient commercially recommended for controlling weeds. The commercially recommended amount of each active ingredient (usually specified as the application rate for commercial formulations) can be found on the label accompanying the commercial formulation. The commercially recommended application rate of a commercial formulation may vary depending on factors such as the plant species and the weeds to be controlled.

[0039] As used herein, the term "more effective" includes, but is not limited to, increasing the efficacy of weed control, prolonging protection and reducing the amount of time required to achieve a given level of weed control, prolonging the duration of protection against weeds after application and prolonging the period of protection against weeds and / or reducing the amount of time required to achieve a level of weed control compared to a herbicide formulation which does not contain a suitable co-formulation therein.

[0040] As used herein, when used with any mixture or formulation system, the term "effective" may include, but is not limited to, increasing control of weeds, reducing the time to effectively control weeds, reducing the amount of one or more herbicides required to effectively control weeds, extending the control effect of individual herbicide actives in a mixture on crop and weed types, extending the time of control of the formulation. In particular, the term "effective" may refer to increasing the efficacy of weed control in untreated plant areas, reducing the amount of time required to achieve a given level of weed control, extending the protection period against weeds, and / or reducing the amount of time required to achieve a level of weed control.

[0041] As used herein, the term "effective amount" refers to the amount of a single component in an agrochemical formulation system or a mixture that is essential to make an effective formulation and control weeds harmful to crop plants without causing any significant damage to the treated crop plants.

[0042] As used herein, the term "agriculturally acceptable carrier" means a carrier known and accepted in the art for forming compositions for agricultural or horticultural use.

[0043] As used herein, the term "co-formulation" is defined as any substance that is not an active ingredient itself but is added to a composition or formulation, such as additives, thickeners, stickers, wetting agents, surfactants, antioxidants, defoamers and thickeners.

[0044] As used herein, the term "plant" or "crop" includes reference to agricultural crops, including field crops (soybean, corn, wheat, rice, etc.), vegetable crops (potato, cabbage, etc.), fruit trees (peach trees, etc.), semi-perennial crops (sugar cane), and perennial crops (coffee and guava).

[0045] As used herein, the term "plant" or "crop" includes reference to whole plants, plant organs (e.g., leaves, stems, twigs, roots, trunks, branches, shoots, fruits, etc.), plant cells, seedlings or plant seeds. This term also includes plant crops such as fruits.

[0046] The term "plant" may also include its propagation material, which may include all reproductive parts of the plant (such as seeds) and vegetative plant material (such as cuttings and tubers) that can be used to propagate the plant. The term may also include spores, corms, bulbs, rhizomes, sprouts, basal branches, runners, and buds and other parts of the plant, including seedlings and young plants, which will be transplanted after germination, rooting or after emergence from soil or any other type of substrate (artificial or natural).

[0047] As used herein, the term "locus" includes not only areas that may already display weeds, but also areas that do not yet display undesirable vegetation and also areas under cultivation. The locus includes, but is not limited to, soil and other plant growth media.

[0048] As used herein, the terms "control," "controlling," or "treatment" refer to, but are not limited to, preventing weeds, protecting plants from weeds, delaying the emergence of undesirable vegetation, and combating weeds.

[0049] As used herein, the term "applying" or "application" refers to, but is not limited to, applying the compounds and compositions of the present invention to plants, locations of weeds, potential locations of weeds (locations that may need protection from undesirable vegetation), or the environment surrounding the habitat or potential habitat of weeds. The application can be carried out by the methods described in the present invention, such as by spraying, dipping, etc.

[0050] Throughout the application, the description of various embodiments uses the term "comprising"; however, those skilled in the art will appreciate that in some specific cases, the language "consisting essentially of" or "consisting of" may alternatively be used to describe the embodiments. Unless otherwise specifically stated, the terms "a / an" as used herein include the singular and the plural. Therefore, the terms "a / an", "one or more", or "at least one" may be used interchangeably in this application.

[0051] Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0052] In this regard, the use of the term "about" herein specifically includes ±10% of the indicated value within the range. Additionally, the endpoints of all ranges herein directed to the same component or property are inclusive of the endpoints, are independently combinable, and include all intermediate points and ranges.

[0053] As used herein, the term "and / or" includes any and all combinations of one or more of the listed associated items. When a statement such as "at least one of..." precedes a list of elements, it modifies the entire list of elements and does not modify the individual elements in the list.

[0054] The crystal form characteristics mentioned herein can be in the graphical data as shown in the figure. Such data include, for example, powder X-ray diffraction patterns and solid-state NMR spectra. As is well known in the art, graphical data potentially provide additional technical information to further define the corresponding solid form, which does not have to be described by reference to a separate numerical value or peak position. In any case, the technician will understand that due to factors well known to the technician such as changes in instrument response and changes in sample concentration and purity, the graphical representation of these data may have small changes, such as changes in peak relative intensity and peak position. Nevertheless, the technician will be able to easily compare the graphical data in the figure with the graphical data generated by the unknown crystal form, and confirm whether the two sets of graphical data are the same crystal form or the characteristics of two different crystal forms. Therefore, the crystal form of pyrazole sulfonyl mentioned herein characterized by the graphical data "as shown in the figure" will be understood to include any crystal form of pyrazole sulfonyl, which is characterized in that its graphical data has such a small change compared to the figure, which is well known to those skilled in the art.

[0055] Pure solid-state form (or polymorph) can be referred to herein as polymorphically pure or substantially free of any other solid-state (or polymorph) form. As used herein, in this context, the statement "substantially free of any other form" will be understood to mean that the solid-state form contains about 20% or less, about 10% or less, about 5% or less, about 2% or less, about 1% or less or 0% of any other form of the subject compound, as measured, for example, by XRPD. Therefore, the solid-state form described herein as being substantially free of any other solid-state form of pyrazole should be understood to contain greater than about 80% (w / w), greater than about 90% (w / w), greater than about 95% (w / w), greater than about 98% (w / w), greater than about 99% (w / w) or 100% of the subject solid-state form of pyrazole. Thus, in some embodiments of the present disclosure, the solid state forms of pyrasulfone described may contain about 1% to about 20% (w / w), about 5% to about 20%, or about 5% to about 10% (w / w) of one or more other solid state forms of the same pyrasulfone.

[0056] In one aspect, the present disclosure contemplates that a certain solid form of pyrasulfonyl sulfone can exist in the presence of any other solid form or mixture thereof. Thus, in one embodiment, the present disclosure provides Form B, for example, wherein Form B exists in a solid form that contains less than 95%, less than 90%, less than 80%, less than 70%, less than 60%, less than 50%, less than 40%, less than 30%, less than 20%, less than 10%, less than 5%, less than 3% or less than 1% of any other physical form of pyrasulfonyl sulfone by weight. The solid form of pyrasulfonyl sulfone as characterized herein can also be present in an agrochemical composition or formulation in trace amounts.

[0057] As used herein, unless otherwise indicated, XRPD peaks reported herein are optionally obtained using CuKα radiation. Measurement.

[0058] As used herein, the term "isolated" with respect to the solid state form of pyrasulfonazole of the present disclosure corresponds to the solid state form of pyrasulfonazole being physically separated from the reaction mixture in which the pyrasulfonazole was formed.

[0059] A substance, such as a reaction mixture, may be described herein as being at or allowed to reach "room temperature" (often abbreviated as "RT"). This means that the temperature of the substance is close to or the same as the temperature of the space (e.g., a room or fume hood) in which the substance is located. Typically, room temperature is from about 20°C to about 30°C, about 22°C to about 27°C, or about 25°C.

[0060] A process or step may be referred to herein as being performed "overnight". This refers to a time interval, e.g., for a process or step, that spans the time during the night when the process or step may not be actively observed. The time interval is from about 8 to about 20 hours, about 10 to about 18 hours, or about 16 hours.

[0061] The amount of solvent used in a chemical process (such as a reaction or crystallization) may be referred to herein as the number of "volumes" or "vol" or "V". For example, a material may be referred to as being suspended in 10 volumes (or 10 vol or 10 V) of solvent. In this context, the expression will be understood to mean the milliliters of solvent per gram of suspended material, so suspending 5 grams of material in 10 volumes of solvent means that the amount of solvent used per gram of suspended material is 10 milliliters, or 50 mL of solvent in this example. In another context, the term "v / v" may be used to indicate the volume of solvent added to the mixture based on the volume of the liquid mixture. For example, adding methyl tert-butyl ether (MTBE) (1.5 v / v) to a 100 ml reaction mixture will indicate that 150 mL of MTBE has been added.

[0062] As used herein, the term "reduced pressure" refers to a pressure of about 10 mbar to about 50 mbar.

[0063] For a better understanding of the present teachings and in no way for the purpose of limiting the scope of the present teachings, each numerical parameter should be interpreted in light of the number of reported significant figures and by applying ordinary rounding techniques. In addition, the endpoints of all ranges involving the same component or property herein include the endpoints, are independently combinable, and include all intermediate points and ranges.

[0064] Herbicide formulations

[0065] It has been a challenge to prepare liquid herbicide formulation systems containing pyrasulfotole at high concentrations for increasing the desired effect on target surfaces of plants, thereby improving the overall efficiency of the formulation.

[0066] In this effort, the inventors tried several options to prepare a stable and efficient liquid formulation system by judiciously selecting aggregates of co-formulations that made it possible to produce high concentrations of pyrasulfone formulations without any precipitation of solid by-products. Several combinations of co-formulations, solvents and organic amines were tried and the desired results were finally achieved.

[0067] Several small experiments were conducted to determine the solubility of pyrasulfonyl sulfone in different solvents, and it has been unexpectedly found that organic amines, such as Genamin C-50 (a product of Clariant), play a key role in increasing the solubility of pyrasulfonyl sulfone in the corresponding solvents and adjuvants. Some of the results are listed in the following table:

[0068] Experiment 1:

[0069] The solubility of pyrasulfone in dimethyl sulfoxide (DMSO) and in a mixture of pyrasulfone with DMSO and an amine was tested at room temperature (24°C).

[0070] Solvents ratio Solubility (%) DMSO 100 26.98 DMSO / GENAMIN C-50 66 / 34 39.24

[0071] The solubility of pyrasulfotole increased by about 26%.

[0072] Experiment 2:

[0073] The solubility of pyrasulfone in cyclohexanone and in a mixture of pyrasulfone with cyclohexanone and an amine was tested at room temperature (24°C).

[0074] Solvents ratio Solubility (%) Cyclohexanone 100 8.24 Cyclohexanone / Genamin C-50 66 / 34 32.99

[0075] The solubility of pyrasulfotole increased by approximately 400%.

[0076] Experiment 3:

[0077] The solubility of pyrasulfonyl sulfonazole in propylene carbonate and in a mixture of pyrasulfonyl sulfonazole with propylene carbonate and an amine was tested at room temperature (24°C).

[0078] Solvents ratio Solubility (%) Propylene carbonate 100 4.59 Propylene carbonate / Genamin C-50 70 / 30 28.57

[0079] The solubility of pyrasulfotole increased by about 620%.

[0080] In an embodiment, the present invention is directed to a liquid herbicide formulation system comprising (a) at least 125 g / L of pyrasulfone based on the total volume of the formulation; (b) an effective amount of an organic amine compound; and (c) an effective amount of an organic solvent.

[0081] In an embodiment, the present invention relates to a liquid herbicide formulation system comprising (a) at least 180 g / L pyrasulfotole based on the total volume of the formulation.

[0082] In an embodiment, the present invention relates to a liquid herbicide formulation system comprising (a) at least 250 g / L of pyrasulfotole based on the total volume of the formulation.

[0083] In a specific embodiment, the present invention relates to a liquid herbicide formulation system comprising (a) at least 350 g / L of pyrasulfotole based on the total volume of the formulation.

[0084] In an embodiment, the present invention further relates to a liquid herbicide formulation system comprising an effective amount of a safener selected from the group consisting of mefenpyr-butyl, clofonet-mexyl and isoxadifen-ethyl; and an effective amount of an agriculturally acceptable carrier.

[0085] In an embodiment, the present invention relates to a liquid herbicide formulation system comprising an effective amount of an organic amine compound selected from the group consisting of organic amine alkoxylates and alkanolamines.

[0086] In a specific embodiment, the present invention is directed to a liquid herbicide formulation system comprising an effective amount of an organic amine compound which is a fatty amine ethoxylate.

[0087] In a more specific embodiment, the present invention relates to a liquid herbicide formulation system comprising an effective amount of an organic amine compound, wherein the organic amine compound is Genamin C 50.

[0088] In a specific embodiment, the present invention is directed to a liquid herbicide formulation system comprising an effective amount of an organic amine compound, which is an alkylolamine.

[0089] In a more specific embodiment, the present invention relates to a liquid herbicide formulation system comprising an effective amount of an organic amine compound, which is ethanolamine.

[0090] In a more specific embodiment, the present invention relates to a liquid herbicide formulation system comprising an effective amount of an organic amine compound, wherein the organic amine compound is triisopropanolamine.

[0091] In an embodiment, the present invention relates to a liquid herbicide formulation system comprising an effective amount of an organic solvent selected from the group consisting of dimethyl sulfoxide (DMSO), cyclohexanone, propylene carbonate, aromatic solvents, vegetable oils and solvent systems thereof.

[0092] In a specific embodiment, the present invention relates to a liquid herbicide formulation system comprising an effective amount of an organic solvent, wherein the organic solvent is dimethyl sulfoxide.

[0093] In another specific embodiment, the present invention is directed to a liquid herbicide formulation system comprising an effective amount of an organic solvent, wherein the organic solvent is propylene carbonate.

[0094] In another embodiment, the present invention relates to a liquid herbicide formulation system comprising agriculturally acceptable carriers including, but not limited to, adjuvants and defoamers.

[0095] In an embodiment, the invention provides a method of treating plants against undesirable weeds, the method comprising applying, after dilution with water, a herbicide formulation system as discussed herein to a target part of the plant so as to treat the plant against the undesirable weeds.

[0096] In an embodiment, the present invention provides a method of treating plants against undesirable weeds, wherein the undesirable weeds are selected from the group consisting of grass weeds and broadleaf weeds.

[0097] In an embodiment, the invention provides the use of a herbicide formulation system as discussed herein for controlling grass weeds and broadleaf weeds.

[0098] In an embodiment, the invention provides the use of a herbicide formulation system as discussed herein, wherein the grassy and broadleaf weeds are selected from the group comprising Echinochloa colonum, Alternentherasessilis, Commelina communis, Eclipta alba., Ludvigia species.

[0099] In one aspect of the embodiments, the present invention also relates to a solid state form of pyrasulfone dimethyl sulfoxide (DMSO) solvate formed during the development of a formulation involving DMSO.

[0100] In another aspect of the embodiments, the present invention also relates to a solid state form of pyrasulfone dimethyl sulfoxide (DMSO) solvate, which is referred to as Form B and can be characterized by an XRPD pattern having peaks at 6.1, 11.2, 11.6, 13.4 and 22.5 degrees 2θ ± 0.2 degrees 2θ, such as Figure 1 The XRPD patterns depicted in and combinations of these data.

[0101] In an embodiment, the crystalline form B of the DMSO solvate of pyrasulfone may be characterized by: Figure 1 Any combination of at least four peaks in the XRPD pattern depicted in .

[0102] The following examples illustrate the practice of the present invention in some embodiments thereof but should not be construed as limiting the scope of the present invention. By considering the description and examples, other embodiments will be apparent to those skilled in the art. It is contemplated that the description (including examples) is considered to be exemplary only, and does not limit the scope and spirit of the present invention.

[0103] Preparation Example:

[0104] Various methods were tried to prepare a liquid formulation of pyrasulfone at a high concentration. The inventors finally locked in dimethyl sulfoxide (DMSO) as a solvent. The following results were observed regarding the dissolution pattern of pyrasulfone in DMSO:

[0105]

[0106]

[0107] It can be clearly seen that the solution prepared by adding the organic amine is clear, while the solution prepared unexpectedly without the amine is turbid, forming insoluble crystals. This turbidity problem caused by these insoluble crystals is solved by adding an effective amount of organic amine (e.g. Genamin C-50, ethanolamine, triisopropanolamine, Genamin O-50).

[0108] The insoluble crystals were identified as pyrasulfonyl sulfoxide solvate. To determine the physical properties of the pyrasulfonyl sulfoxide solvate, a sample was prepared separately and XRPD data was generated.

[0109] Analytical methods

[0110] X-ray powder diffraction method:

[0111] Powder X-ray diffraction was performed on an X-ray powder diffractometer

[0112] PanAlytical X'pert Pro; CuKα radiation Zero background sample holder.

[0113] Measurement parameters:

[0114] Scanning range: 4-40 degrees 2θ

[0115] Scanning speed 3° / min (for Form C, Form D); and 1.2° / min (for Form F)

[0116] Sample holder: zero background silicon plate

[0117] Before analysis, grind the sample gently using a mortar and pestle to obtain a fine powder. Optionally, an appropriate amount of silicon powder can be added as an internal standard to calibrate the position of the diffraction. Adjust the ground sample into the chamber of the sample holder and use the cover to smooth the surface of the sample.

[0118] Examples

[0119] The solid form of pyrasulfone-dimethyl sulfoxide solvate was prepared according to the following procedure:

[0120] The technical grade of pyrasulfone was prepared according to the publication US2002065200.

[0121] In a flask, 32 g of pyrasulfone technical grade was added to 68 g of dimethyl sulfoxide (DMSO). The flask was stirred until the compound was completely dissolved. Stirring was continued until precipitated solids were observed in the solution. The solids were filtered and dried in vacuo. The solids were then gently ground with a spatula and analyzed by XRD. XRPD data were generated and are available at Figure 1 Displayed in.

[0122] Preparation:

[0123] The following table shows exemplary embodiments of the formulations of the present invention:

[0124] Table 1: Sulfonylpyraclostrobin 350SLa.

[0125] g / 1L Sulfonylpyrazone 350 Dimethyl sulfoxide (DMSO) 810

[0126] The formulation was unstable due to precipitation of pyrasulfone solvate.

[0127] b.

[0128] g / 1L Sulfonylpyrazone 350 Dimethyl sulfoxide (DMSO) 636 Genamin C-50 174

[0129] The above formulation was found to contain no traces of solid pyrasulfone DMSO solvate crystals.

[0130] Table 2: Formulations of pyrasulfone 180SLc. unstable at room temperature

[0131] g / 1L Sulfonylpyrazone 180 Propylene carbonate 1020

[0132] d. Room temperature Stable composition

[0133] g / 1L Sulfonylpyrazone 180 Propylene carbonate 840 Genamin C-50 180

[0134] The following table discloses specific compositions embodying the present invention:

[0135] Table 3: Emulsifiable Concentrate (EC) Formulation:

[0136]

[0137]

[0138] The preparation process of the formulation is summarized as follows:

[0139] Agnique ME 18RD-F, propylene glycol monomethyl ether and dimethyl sulfoxide (DMSO) were charged into a container. After that, BYK-024, Emulsogen EL 360, Genamin C 050 and Nansa_EVM70 / 2E were added under stirring. The container was placed under continuous stirring, and then pyrasulfone technical grade and pyraclostrobin were added. All materials were mixed thoroughly until uniform.

[0140] Although the disclosure of the present invention can be susceptible to various modifications and alternative changes, specific embodiments have been described in detail herein by way of example. However, it should be understood that this disclosure is not intended to be limited to the specific form disclosed. On the contrary, this disclosure will cover all modifications, equivalents, and alternatives that fall within the scope of this disclosure as defined by the following claims and their legal equivalents.

Claims

1. A liquid herbicide formulation system comprising: (a) at least 125 g / L pyrasulfotole based on the total volume of the formulation; (b) an effective amount of an organic amine compound; (c) an effective amount of an organic solvent.

2. The liquid herbicide formulation system according to claim 1, wherein: The organic amine compound is selected from the group consisting of organic amine alkoxylates and alkanolamines.

3. The liquid herbicide formulation system according to any one of claims 1 or 2, wherein: The organic amine alkoxylate compound is fatty amine ethoxylate, and the fatty amine ethoxylate is Genamin C 50.

4. The liquid herbicide formulation system according to any one of claims 1 to 2, wherein: The alkylolamine compound is selected from the group consisting of ethanolamine and triisopropanolamine.

5. The liquid herbicide formulation system according to any one of claims 1 to 4, wherein The organic solvent is selected from the group consisting of dimethyl sulfoxide (DMSO), cyclohexanone, propylene carbonate, aromatic solvents, vegetable oils and solvent systems thereof.

6. The liquid herbicide formulation system according to any one of claims 1 to 5, wherein: The organic solvent is DMSO or a solvent system thereof.

7. The liquid herbicide formulation system according to claim 5, wherein: The organic solvent is an aromatic solvent.

8. The liquid herbicide formulation system according to claim 5, wherein: The organic solvent is propylene carbonate.

9. The liquid herbicide formulation system according to claim 5, wherein: The vegetable oil is selected from the group comprising rapeseed oil.

10. The liquid herbicide formulation system according to any one of claims 1 to 6, wherein The formulation system does not contain a solid form of pyrasulfotole DMSO solvate.

11. The liquid herbicide formulation system according to any one of claims 1 to 10, wherein: The herbicide formulation system comprises (a) at least 180 g / L pyrasulfotole based on the total volume of the formulation.

12. The liquid herbicide formulation system according to any one of claims 1 to 10, wherein: The herbicide formulation system comprises (a) at least 250 g / L pyrasulfotole based on the total volume of the formulation.

13. The liquid herbicide formulation system according to any one of claims 1 to 10, wherein: The herbicide formulation system comprises (a) at least 350 g / L pyrasulfotole based on the total volume of the formulation.

14. The liquid herbicide formulation system according to any one of claims 1 to 13, wherein The herbicide formulation system further comprises an effective amount of a safener and an effective amount of an agriculturally acceptable carrier.

15. The liquid herbicide formulation system according to claim 14, wherein: The safener is selected from the group consisting of mefenpyr-butyl, clofometyl-mexyl and isoxadiazine.

16. A method for treating plants against undesirable weeds, said method comprising applying, after dilution with water, a herbicide formulation system according to any one of claims 1 to 15 to target parts of said plants so as to treat said plants against undesirable weeds.

17. The method of claim 16, wherein: The undesirable weeds are selected from the group comprising grass weeds and broadleaf weeds.

18. Use of the herbicide formulation system according to any one of claims 1 to 15 for controlling grass weeds and broadleaf weeds.

19. Use of the herbicide formulation system according to claim 18, wherein: The grass weeds and broadleaf weeds are selected from the group comprising Echinochloa baldii, Alternanthera, Commelina, Eclipta prostrata, Polygonum spp.

20. A solid state form of pyrasulfone dimethyl sulfoxide (DMSO) solvate.

21. A crystalline form B of the DMSO solvate of pyrasulfone as claimed in claim 20, characterized in that Data selected from one or more of the following: i. an XRPD pattern having peaks at 6.1, 11.2, 11.6, 13.4 and 22.5 degrees 2θ ± 0.2 degrees 2θ; ii. XRPD pattern as depicted in Figure 1.

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