BR102019017785A2 - FORM OF SULFOMETURON-METHYLIC, PROCESS FOR ITS PREPARATION AND USE OF THE SAME - Google Patents

Abstract

"Form of sulfometuron-methyl, process for its preparation and use" is a new crystalline form of sulfometuron-methyl of formula (i), of the process of crystal preparation, of crystal analysis through various analytical methods and the use of crystal to prepare a stable agrochemical formulation. the invention also describes the use of various solvents with respect to the conditions of preparation in crystalline form. the innovative crystal form is particularly suitable for use in herbicidal compositions and to control unwanted plant growth.

Description

FORM OF SULFOMETURON-METHYLIC, PROCESS FOR ITS PREPARATION AND USE OF THE SAME FIELD OF THE TECHNIQUE OF THE INVENTION

[0001] The present disclosure describes a crystalline form of methyl 2 - [(4,6-dimethylpyrimidin-2-yl) carbamoylsulfamoyl] benzoate (sulfometuron-methyl), for its preparation processes and for its use in agrochemical preparations.

BACKGROUND OF THE INVENTION

[0002] 2 - [(4, 6-dimethylpyrimidin-2-yl) carbamoyl sulfamoyl] methyl benzoate (sulfomethuron-methyl) is a member of the sulfonylurea chemical class. Sulfometuron-methyl is a broad spectrum herbicide that can be used for annual, biennial and permanent grass control and large leaf weeds. It also has agroforestry applications in which it is used to control woody tree species. Pre-emergence treatments suppress weeds through root absorption and post-emergence treatments control through root and leaf absorption. Sulfometuron-methyl is rapidly absorbed by foliage and roots, and moves quickly throughout the plant with initial effects normally seen in 2 to 3 weeks after application and final effects seen after 4 to 6 weeks after application. Its mode of action is to prevent cell division in regions of active growth of the tips, roots and shoots of the plant by disrupting the activity of acetolactate synthase (ALS), which is an enzyme to catalyze the first stage in biosynthesis of the amino acids valine , leucine and isoleucine for the plant.

[0003] Sulfometuron-methyl has a molecular formula of C15H16N4O5S. Its chemical structure is

[0004] Patent documents No. EP 0007687, EP 0030138, US 4,238,621, EP 0034431, US 4,394,506, EP 0046626, US 4,546,179, US 5,153,324, CN 103483270 and CN 103497162 reported the process for the preparation sulfometuron-methyl and its intermediates together with the derivatives. Commercially available methyl sulfometuron, which is normally manufactured by the process described in document No. EP 0030138 and is present in an amorphous state, is incorporated into this document as a reference for all purposes. It has been found that sulfometuron-methyl in amorphous state is not suitable to be prepared as compositions or formulations that have the property of cleaning spray equipment. Sulfometuron-methyl residues remain in the spray equipment after spraying. Proper cleaning prior to reusing spray equipment will typically require a rinsing procedure that is not only time consuming, but also results in the problem of eliminating waste water. Furthermore, it has been found that amorphous sulfometuron-methyl is not suitable to be prepared as compositions or formulations due to the residues formed after diluting the formulated products, which can block the spray filters easily. Additionally, amorphous sulfometuron-methyl has been found to have relatively low biological efficacy. Therefore, there is a need to provide an innovative form of sulfometuron-methyl with reduced viscosity, reduced aggregates / residues and with high efficiency.

BRIEF SUMMARY OF THE INVENTION

[0005] In an attempt to solve some or all of the problems with the existing amorphous form of sulfometuron-methyl, a new and stable crystalline form of sulfometuron-methyl was prepared.

[0006] In a first aspect, the invention provides an innovative crystalline form of methyl 2 - [(4,6-dimethylpyrimidin-2-yl) carbamoylsulfamoyl] benzoate (sulfometuron-methyl), called "crystalline modification I", which exhibits at least 3 of the following reflections, in any combination, as 2θ ± 0.2 degree in an X-ray powder diffractogram (X-RPD) recorded using Cu-Kα radiation at 25 ° C:
2θ = 6.9 ± 0.2 (1)
2θ = 11.6 ± 0.2 (2)
2θ = 13.8 ± 0.2 (3)
2θ = 16.3 ± 0.2 (4)
2θ = 19.8 ± 0.2 (5)
2θ = 21.9 ± 0.2 (6)
2θ = 22.9 ± 0.2 (7)
2θ = 23.4 ± 0.2 (8)
2θ = 27.3 ± 0.2 (9)
2θ = 28.7 ± 0.2 (10).

[0007] In one embodiment, the crystalline modification, according to the first aspect of the invention, exhibits at least 3, 4 or all reflections, in any combination among the following:
2θ = 13.8 ± 0.2 (3)
2θ = 16.3 ± 0.2 (4)
2θ = 21.9 ± 0.2 (6)
2θ = 23.4 ± 0.2 (8)
2θ = 27.3 ± 0.2 (9).

[0008] In a second aspect, the present invention provides a crystalline modification I of sulfometuron-methyl, optionally according to the first aspect of the invention, which exhibits an infrared (IR) spectrum with characteristic functional group vibration peaks in numbers of waves (cm-1, ± 0.2%) of one or more out of 3,221, 3,115, 3,006, 1,730, 1,694, 1,602, 1,549, 1,297, 1,122, 1,010, 954, 829, 783 and 756 cm-1 as shown in Figure 2.

[0009] In a third aspect, the present invention provides a crystalline modification I of sulfometuron-methyl, optionally according to the first or the second aspect of the invention, which exhibits a melting point of about 197 to 202 ° C.

[0010] In a fourth aspect, the present invention provides a crystalline modification I of sulfometuron-methyl, optionally according to any of the first to third aspects of the invention, which exhibits a differential calorimetry scanning profile (DSC) that has a endothermic melting peak starting at 197.4 ° C, maximum peak at 200.5 ° C, and displacement at 201.7 ° C, in addition, optionally with a melting enthalpy of 118 J / g.

[0011] In a fifth aspect, the present invention provides a crystalline modification I of sulfometuron-methyl, optionally according to any one of the first to fourth aspects of the invention, characterized by the X-ray powder diffraction model, as substantially shown in Figure 1, and / or by an IR spectrum. as substantially shown in Figure 2, and / or by a DSC thermogram, as substantially shown in Figure 3.

[0012] In a sixth aspect, the present invention provides a crystalline modification I of sulfometuron-methyl, optionally according to any one of the first to fifth aspects of the invention, obtainable by the process, as substantially described in Example 2 or 3.

[0013] In a seventh aspect, the present invention provides a crystalline modification I of sulfometuron-methyl, optionally according to any one of the first to sixth aspects of the invention, obtainable by the process of the eighth aspect of the invention.

[0014] It has been found that the crystalline modification I of sulfometuron-methyl has a significant improvement in its cleaning property of spray equipment. In addition, it has been found that the crystalline modification I of sulfometuron-methyl is easier to filter, fragment or grind compared to amorphous sulfometuron-methyl prepared in accordance with disclosure No. EP 0030138 and that formulations prepared using this crystalline modification I are stable after prolonged storage. This allows the preparation of commercial formulations, such as water-dispersible granules (WG) and oil dispersions (OD). For these reasons, crystalline modification I is more suitable for preparing commercial formulations. It is possible to prepare any crystalline modification I sulfometuron-methyl formulations, which will be disclosed hereinafter.

• i) dissolver sulfometuron-metílico em um solvente, ou mistura de solventes;
• ii) precipitar o composto dissolvido em modificação cristalina I de sulfometuron-metílico; e
• iii) isolar a modificação cristalina I precipitada.

[0015] In an eighth aspect, the present invention provides a process for preparing a crystalline modification I of sulfometuron-methyl which comprises the steps of:

• i) dissolve sulfometuron-methyl in a solvent, or mixture of solvents;
• ii) precipitating the dissolved compound in crystalline modification I of sulfometuron-methyl; and
• iii) isolating the precipitated crystalline modification I.

[0016] In an embodiment of the eighth aspect of the invention, sulfometuron-methyl in step i) is amorphous sulfometuron-methyl.

[0017] Methods for preparing amorphous methyl sulfometuron are known in the art. Amorphous methyl sulfometuron is manufactured and is available on a commercial scale. A particularly suitable method for preparing amorphous methyl sulfometuron is described in EP No. 0030138.

[0018] In an embodiment of the eighth aspect of the invention, the solvent is selected from the group consisting of halogenated hydrocarbons (for example, chlorobenzene, bromobenzene, dichlorobenzene, trifluoro-methyl-benzene, trichlorobenzene and chlorotoluene), ethers (for example, ethylpropyl-ether, n-butyl-ether, anisol, phenethol, cyclohexyl-methyl-ether, dimethyl-ether, dimethylglycol, diphenyl-ether, dipropyl-ether, di-isopropyl-ether, di-n-butyl-ether, diisobutyl-ether, diisoamyl-ether, ethylene glycol-dimethyl-ether, isopropyl-ethyl-ether, methyl-tert-butyl-ether, tetrahydrofuran, methyl-tetrahydrofuran, dioxane, dichlorodiethyl-ether, methyl-tetra- hydrofuran, polyethers of ethylene oxide and / or propylene oxide), nitrated hydrocarbons (for example, nitromethane, nitroethane, nitropropane, nitrobenzene, chloronitrobenzene and ethyl benzene), aliphatic, cycloaliphatic or aromatic hydrocarbons (for example, pentane, n- hexane, n-heptane, n-octane, nonane), cymene, oil fractions that have a butyl-is acetic acid ester (n-butyl acetate), methyl acetate, ethyl acetate, isobutyl acetate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and ethylene carbonate), and aliphatic alcohols (for example, methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-amyl alcohol), mesitylene, diethyl ketone, methyl ethyl ketone, acetonitrile and mixtures thereof.

[0019] In an embodiment of the eighth aspect of the invention, the solvent is selected from the group consisting of xylene, benzene, chlorobenzene, dichlorobenzene, dichloromethane, ethyl-benzene, trifluoro-methyl-benzene, mesitylene, nitrobenzene, diethyl-ketone, methyl ethyl ketone, methanol, ethanol, isopropanol, acetonitrile or mixture of THF-hexane, ethyl-acetate-hexane, dichloromethane-hexane, dichloromethane-methanol, THF-water and methanol-water. Solvent mixtures of more than 2, 3 or 4 components are also provided by embodiments of the invention.

[0020] In an embodiment of the eighth aspect of the present invention, the solvent is selected from the group consisting of acetone, dichloromethane or a mixture thereof.

[0021] In accordance with an embodiment of the eighth aspect of the present invention, crystalline modification I of sulfometuron-methyl is prepared by dissolving amorphous sulfometuron-methyl in a solvent or a mixture of solvent as a concentrated solution by heating to the temperature of environment to a temperature at or below the reflux temperature of the solvent or solvent mixture. Optionally, the concentrated solutions can be prepared at the reflux temperature of the solvents. The concentration of the solution depends on the solubility of sulfometuron-methyl in the corresponding solvent or solvent mixture.

[0022] In an embodiment of the eighth aspect of the invention, the concentrated homogeneous solution thus prepared as in step (i) is then cooled to room temperature or to a temperature of about 0 ° C to 20 ° C to crystallize the crystalline form of the solvent. The crystalline modification I of sulfometuron-methyl can also be crystallized by concentrating the homogeneous solution by removing the solvent or solvent mixture to a certain volume with or without applying a vacuum and cooling to below the reflux temperature of the solvent or of the solvent mixture.

[0023] In an embodiment of the eighth aspect of the invention, the crystalline modification I of sulfometuron-methyl can also be carried out by adding initial crystals of the desired crystalline form during crystallization in a solution prepared in step (i), which can promote or accelerate crystallization.

[0024] The amount of initial crystal added to the concentrated solution is typically in the range of 0.001% to 10% by weight, optionally 0.01% to 2.5% by weight, in addition, optionally 0.005 to 0 , 5% by weight based on the weight of sulfometuron-methyl used for the preparation of the concentrated solution in step (i). Optionally, the initial crystals are added to the concentrated solution at a temperature below the boiling point of the corresponding solvent or solvent mixture.

[0025] In an embodiment of the eighth aspect of the invention, the precipitated crystalline modification I of sulfometuron-methyl obtained from step (ii) is isolated by the normal solid component separation techniques from the solutions, such as filtration, centrifugation or decanting. Then, the isolated solid is washed with solvent one or more times. Optionally, the solvent used in the washing stage consists of one or more components of the solvent or solvent mixture used for the preparation of the concentrated solution in step (i), as previously described in this document. Washing is normally conducted with the use of the corresponding solvent or solvent mixture between room temperature and 0 ° C, depending on the solubility of the crystal, in order to minimize or avoid the loss of crystalline material in the corresponding washing solvent as much as possible. In an embodiment of the eighth aspect of the invention, the crystalline modification I of sulfometuron-methyl is dissolved and recrystallized. The washes and / or the crystallization solvent in either method can be concentrated to obtain solid methyl sulfometuron which can be recycled.

[0026] In a ninth aspect, the present invention provides a crystalline material which comprises a crystalline modification I of sulfometuron-methyl obtained according to the eighth aspect of the invention, which has a content of a crystalline modification I of sulfometuron-methyl of at least minus 98% by weight.

[0027] In a tenth aspect, the present invention provides a composition comprising crystalline modification I of sulfometuron-methyl, according to any one of the first to seventh and ninth aspects of the invention, and at least one auxiliary.

[0028] In an eleventh aspect, the present invention provides a use of crystalline modification I of sulfometuron-methyl according to any one of the first to seventh and ninth aspects of the invention, or a composition, according to the eleventh aspect of the invention , for weed control.

[0029] In an embodiment of the tenth aspect of the invention, the amount of crystalline modification I of sulfometuron-methyl is less than 90% by weight of the composition, optionally less than 75% by weight of the composition, moreover, optionally less than 60% in weight of the composition, even more optionally about 50% by weight of the composition.

[0030] The use of amorphous methyl sulfometuron as an herbicide is known in the art and is used on a commercial scale. It has been found that the crystalline modification I of sulfometuron-methyl is also active in the control of undesirable plants, such as weeds. As a result, the techniques of formulation and application of sulfometuron-methyl known in the art with respect to amorphous sulfometuron-methyl, for example, as disclosed in the prior art documents described earlier in the present document, can also be applied in an analogous manner to sulfometuron -methyl in the crystalline modification I of the invention.

[0031] Accordingly, the invention provides a herbicidal composition comprising sulfometuron-methyl in crystalline modification I, as defined earlier in this document.

[0032] The invention additionally provides processes for preparing compositions to control undesirable plants, such as weeds, with the use of crystalline modification I of sulfometuron-methyl.

[0033] The invention also provides a method for controlling unwanted plant growth which comprises applying to the plant, plant part or surroundings of the plant, an herbicide effective amount of the crystalline modification I of sulfometuron-methyl, according to any of the first to the seventh and ninth aspects of the invention, or a composition, according to the tenth aspect of the invention. Consequently, this provides control of unwanted plants in plants, plant parts, and / or their surroundings, which comprises applying to the foliage or fruit of the plant, plant parts or plant surroundings, an herbicide effective amount of the sulfometuron crystalline modification I -methyl.

[0034] In an embodiment of the tenth aspect of the invention, the composition is in the form of a suspension concentrate (SC), oil dispersion (OD), water soluble granule (SG), dispersible concentrate (DC), emulsifiable concentrate ( EC), seed treatment by emulsion, seed treatment by suspension, a granule (GR), a microgranule (MG), suspoemulsion (SE) or a water dispersible granule (WG). The crystalline modification I of sulfometuron-methyl can be included in these traditional formulations in a known manner with the use of suitable and similar auxiliaries, carriers and solvents, in a manner analogous to that known for amorphous sulfometuron-methyl.

[0035] In an embodiment of the tenth aspect of the invention, the composition is in the form of a water-dispersible granule (WG).

[0036] In an embodiment of the tenth aspect of the invention, the composition is in the form of an oil dispersion (OD).

[0037] In an embodiment of the tenth aspect of the invention, the crystalline modification I of sulfometuron-methyl may be present in a concentration sufficient to obtain the necessary dosage when applied to plants or in the locations thereof, desirably at a concentration of about 1 about 85% by weight of the total mixture. The formulations are prepared, for example, by extending the crystalline modification I of sulfometuron-methyl with water, solvents and carriers, using, if appropriate, emulsifiers and / or dispersants, and / or other auxiliaries.

[0038] These formulations are prepared by mixing crystalline modification I of sulfometuron-methyl with at least one auxiliary as an herbicide, for example surfactants, liquid diluents, solid diluents, wetting agents, dispersants, thickening agents, antifoaming agents, agents antifreeze, preservatives, antioxidants, solid adherents, inert fillers and other formulation ingredients.

[0039] Surfactants can be an emulsifier, dispersant or wetting agent of ionic or nonionic type. Examples that can be used include, but are not limited to, salts of polyacrylic acids, salts of lignosulfonic acid, salts of phenylsulfonic or naphthalenesulfonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols, especially alkylphenols, sulfosuccinic ester salts, taurine derivatives, especially alkyltaurates or phosphoric esters of phenols or polyethoxylated alcohols.

[0040] Liquid diluents include, but are not limited to, water, N, N-dimethylamide, dimethylsulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, propylene carbonate, dibasic esters, paraffins, alkyl benzene, alkylnaphthalene, glycerin, triacetin oils, triacetin , castor, linseed, sesame, corn, peanut, cottonseed, soy, rapeseed and coconut, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates , such as hexyl acetate, heptyl acetate and octyl acetate, and alcohols, such as methanol, cyclohexanol, decanol, benzyl and tetrahydrofurfuryl alcohol, and mixtures thereof.

[0041] Solid thinners can be water-soluble or water-insoluble. Solid water-soluble diluents include, without limitation, salts, such as alkali metal phosphates (eg sodium dihydrogen phosphate), alkaline earth phosphates, sodium, potassium, magnesium and zinc, sodium and potassium chloride , sodium acetate, sodium carbonate and sodium benzoate, and sugars and sugar derivatives, such as sorbitol, lactose, sucrose and mannitol. Examples of solid water-insoluble diluents include, but are not limited to, clays, synthetic silica and diatoms, calcium and magnesium silicates, titanium dioxide, aluminum, calcium and zinc oxide, and mixtures thereof.

[0042] Wetting agents include, but are not limited to, alkyl sulfosuccinates, laureates, alkyl sulfates, phosphate esters, acetylenic diols, ethoxy fluorinated alcohols, ethoxylated silicones, alkylphenol ethoxylates, benzene sulfonates, benzene sulfonates, benzene sulfonates alkyl-α-olefin sulfonates, naphthalene sulfonates, substituted alkyl naphthalene sulfonates, condensates of naphthalene sulfonates and alkyl naphthalene sulfonates substituted with formaldehyde, and alcohol ethoxylates, and mixtures thereof. Sodium salts of alkyl naphthalene sulfonates are particularly useful for the composition of the invention.

[0043] Dispersants include, without limitation, sodium, calcium and ammonium salts of ligninsulfonates (optionally, polyethoxylates); sodium and ammonium salts of maleic anhydride copolymers; sodium salts of condensed phenolsulfonic acid; and condensates of naphthalene sulfonate-formaldehyde. Ligninsulfonates, such as sodium ligninsulfonates are particularly useful for the composition of the invention. Naphthalene sulfonate-formaldehyde condensates, such as naphthalenesulfonic acid, polymers with formaldehyde, and sodium salts are particularly useful for the composition of the invention.

[0044] Thickeners, however, include, without limitation, guar gum, pectin, casein, carrageenan, xanthan gum, alginates, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and carboxymethylcellulose, and mixtures thereof. Synthetic thickening agents include derivatives of the previous categories, as well as polyvinyl alcohols, polyacrylamides, polyvinylpyrrolidones, various polyethers, their copolymers, as well as polyacrylic acids and their salts, and mixtures thereof. Alkylpolyvinylpyrrolidones are particularly useful for the composition of the invention.

[0045] Defoaming agents include all substances that can normally be used for this purpose in agrochemical compositions. Suitable antifoam agents are known in the art and are commercially available. Particularly preferred antifoam agents are mixtures of polydimethylsiloxanes and perfluroalkylphosphonic acids, such as silicone antifoam agents available from GE or Compton.

[0046] Preservatives include all substances that can normally be used for this purpose in such agrochemical compositions and are again well known in the art. Suitable examples that can be mentioned include PREVENTOL® (from Bayer AG) and PROXEL® (from Bayer AG).

[0047] Antioxidants include all substances that can normally be used for this purpose in agrochemical compositions, as known in the art. Preference is given to butylated hydroxytoluene.

[0048] Solid adhesives include organic adhesives, which include taquifiers, such as celluloses or substituted celluloses, natural and synthetic polymers in the form of powders, granules or latex, and inorganic adhesives such as plaster, silica or cement.

[0049] Inert fillers include, without limitation, natural ground minerals, such as kaolin, aluminas, talc, chalk, quartz, atapulgite, montmorillonite and diatomaceous earth, or synthetic ground minerals, such as highly dispersed silicic acid, aluminum oxide , calcium silicates and phosphates, and calcium hydrogen phosphates. Inert fillers suitable for granules include, for example, crushed and fractionated natural minerals, such as calcite, marble, pumice, sepiolite and dolomite, or synthetic granules of inorganic and organic ground materials, as well as granules of organic materials, such as sawdust. , coconut shells, corn cobs and tobacco stalks.

[0050] Other formulation ingredients can also be used in the present invention, such as dyes, drying agents and the like. These ingredients are known to a person skilled in the art.

[0051] In an embodiment of the tenth aspect of the invention, the crystalline modification I of sulfometuron-methyl may be present in the formulations and in other forms that are prepared from these formulations, and as a mixture with other active compounds (such as attractants, sterilizing agents, bactericides, acaricides, nematicides, fungicides, growth regulating substances, herbicides, protective agents, fertilizers, semi-chemicals and other insecticides) or with agents to improve plant properties.

[0052] All plants, plant parts and their surroundings can be treated with the crystalline modification I of sulfometuron-methyl, in accordance with any aspect or modality of the invention. In the present context, plants should be understood to mean all plants and plant populations, such as wild plants or desired and unwanted crop plants (which include naturally occurring crop plants). Crop plants can be plants that can be obtained through conventional breeding and optimization methods, through biotechnological and genetic engineering methods, or through combinations of these methods, which include transgenic plants and plant cultivars that may or may not be protected for the protection of plant varieties.

[0053] Treatment of plants, plant parts, and / or their surroundings, with the compositions or formulations of the invention can be conducted directly or by allowing the compositions or formulations to act in their surroundings, habitat or storage space through the methods traditional treatment methods. Examples of such traditional treatment methods include dipping, spraying, vaporizing, fogging, diffusing, painting, in the case of propagating material, and applying one or more coatings particularly in the case of seed.

[0054] The benefits of the invention are best seen when the herbicidal composition is applied to eliminate weeds in useful plant growth crops: legumes (such as soybeans), oil plants (such as sunflower), maize (corn) which includes field corn, popcorn and sweet corn, cotton, cereal, barley, wheat, rice, oats, potatoes, beets, plantation crops (such as bananas, fruit trees, rubber trees, nurseries), vines, citrus fruits, olive trees, amenities, vegetables (such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, paprika, garlic and leeks), blueberries (such as blackberries), blackberries, cranberries, flax, sorghum, okra, mint , rhubarb, peanut mint, grass, grapevine and sugar cane.

[0055] Throughout the description and claims of this specification, the words "understand" and variations of the words, for example "that understands" and "understands", mean "that includes, but is not limited to", and does not exclude other chemical portions, additives, components, whole numbers or steps. In addition, the singular encompasses the plural unless the context requires otherwise: in particular, where the indefinite article is used, the specification should be understood as contemplating the plurality as well as the singularity, unless the context requires it. contrary.

[0056] Preferred features of each aspect of the invention can be as described in combination with any other aspects. Other features of the invention will become apparent from the following examples. In general, the invention extends to any innovative feature, or any innovative combination of features revealed in this specification (which includes any claims and attached drawings). Thus, resources, integers, characteristics, compounds, chemical compounds or groups described together with a specific aspect, modality or example of the invention must be understood as applicable to any other aspect, modality or example described in this document, except when incompatible with the same. In addition, unless otherwise stated, any resource disclosed in this document may be replaced by an alternative resource that serves the same or a similar purpose.

[0057] Where upper and lower limits are quoted for a property, then a range of values defined by a combination of any of the upper limits with any of the lower limits can also be implied.

[0058] In this specification, references to properties are - unless stated otherwise - for properties measured under ambient conditions, that is, at atmospheric pressure and at a temperature of around 20 ° C.

[0059] As used herein, the term "about" or "approximately" when used in combination with a quantity or numerical range, means slightly more or slightly less than the stated quantity or numerical range and, for example, for a deviation of ± 10% from the quantity or end point of the stated numerical range.

[0060] "Plants" as used in this document, refers to complete plants, which include the roots, leaves and stem.

[0061] "Plant parts" as used in this document, refers to all plant parts and organs above and below ground, such as bud, leaves, needles, bases, stems, flowers, fruit bodies, fruits, seeds, heads, grains, roots, tubers and rhizomes. Harvested materials, and materials of vegetative and generative propagation, for example, cut, tubers, meristem tissue, rhizomes, displacements, seeds, single and multiple plant cells and any other plant tissues, are also included.

[0062] "Surroundings" as used in this document, refers to the place where the plants grow, the place where the plant propagation materials of the plants are planted or the place where the plant propagation materials of the plants will be planted.

[0063] "Precipitation" as used in this document, refers to the sedimentation of a solid material (a precipitate), which includes the sedimentation of a crystalline material, of a liquid solution in which the solid material is present in greater quantities than its solubility in the amount of liquid solution.

[0064] The term "herbicide effective amount" as used herein, refers to the amount of such a compound or combination of such compounds that is capable of producing a controlling effect on plant growth. The control effects include any deviation from the natural development of the targeted plants, for example death, delay in one or more aspects of the development and growth of the plant, leaf burning, albinism, dwarfism and the like.

[0065] All percentages are given in% of weight unless otherwise indicated.

BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Various features and aspects of the modalities of the invention disclosed in this document can be more clearly understood by reference to the drawings, which are intended to exemplify and illustrate, but not limit, the scope of the invention, and in which:
Figure 1 is an X-ray powder diffractogram (X-RPD) of sulfometuron-methyl crystalline modification I;
Figure 2 is an infrared (IR) spectrum of crystalline modification I of sulfometuron-methyl; and
Figure 3 is a differential calorimetry scanning thermogram (DSC) of crystalline modification I of sulfometuron-methyl.

DETAILED DESCRIPTION OF THE INVENTION

[0067] The present invention will now be described by the following examples, in which the following measurement techniques have been employed, and that the examples are provided for illustrative purposes only and are not intended to limit the scope of the disclosure.

[0068] All X-ray powder diffractograms were determined using a powder diffractometer in reflection geometry at 25 ° C, using the following acquisition parameters:

[0069] The IR spectrum was measured with the resolution of 4 cm-1 and with the number of scans of 16 for the crystallized samples. The crystalline modification I of sulfometuron-methyl can be identified by its characteristic functional group vibration peaks in wave numbers (cm-1, ± 0.2%) of one or more among 3,221, 3,115, 3,006, 1,730, 1,694, 1,602, 1,549, 1,297, 1,122, 1,010, 954, 829, 783 and 756 cm-1 as shown in Figure 2.

[0070] All IR spectra were obtained using the following acquisition parameters:

[0071] All DSC thermograms were obtained using the following acquisition parameters:

Examples Example 1: Preparation of amorphous sulfometuron-methyl according to the disclosure of document No. EP 0030138 (Example 1 and Example 3 with slight change)

[0072] A stirred mixture containing 157 g of methyl 2-sulfamoylbenzoate, 73 g of butyl isocyanate, 0.3 g of 1,4-diazabicyclo [2,2,2] octane and 1,0 l of xylene heated to reflux in one and a half hours. Phosgene gas was then passed into the system under a reflux condenser of dry ice that allows the reaction temperature to drop by 120 ° C. This addition was continued until the reflux temperature remained at 120 ° C without adding additional phosgene. The temperature of the reaction mixture was then raised to 136 ° C (by removing the dry ice reflux condenser) after which it was cooled to room temperature and filtered. Evaporation of the filtrate yielded the desired crude methyl 2- (isocyanatesulfonyl) benzoate which could be purified by distillation at 132 to 138 ° C under pressure.

[0073] Methyl 2- (isocyanatesulfonyl) benzoate (14.1 g) and 5.7 g of 2-amino-4,6-dimethylpyrimidine were stirred in 80 ml of acetonitrile at room temperature for 16 hours at room temperature environment. 400 ml of water was added and the pH of this mixture was adjusted to pH 8 by the addition of 10% aqueous sodium hydroxide. The aqueous phase was separated and acidified to pH 1 with hydrochloric acid to precipitate a thick white gum. Sufficient 50% aqueous sodium hydroxide was added to obtain pH 12 and the mixture was heated on a steam bath until a clear solution resulted. The solution was again acidified with hydrochloric acid to pH 3 and the resulting cloudy solution was extracted with dichloromethane. The organic phase was dried and the solvent was removed to generate 3.7 g of methyl sulfometuron.

Example 2: Preparation of crystalline modification I of sulfometuron-methyl from acetone

[0074] Sulfometuron-methyl sample (3 g) was obtained in a three-necked round-bottom flask together with acetone (100 ml) and the resulting slurry was heated to 56 to 58 ° C to generate a homogeneous solution. The homogeneous solution was stirred at 56 to 58 ° C for 2 hours and the insoluble particles, if any, were filtered. The resulting solution was slowly cooled to room temperature. After cooling, fine crystals were formed and the resulting heterogeneous mixture was stirred at 10 to 20 ° C for 2 hours. Then, the slurry was filtered and washed with cooled acetone (10 ml). The filtered crystals were dried under vacuum at 40 ° C in order to remove traces of acetone from the crystalline product. The crystalline product thus obtained had a purity of about 98% and the product recovered as a crystal had about 85% yield.

[0075] The obtained crystals were analyzed by X-RPD, IR and DSC spectrometry, and it was shown to be crystalline modification I of sulfometuron-methyl as shown in Figure 1, Figure 2 and Figure 3, respectively.

[0076] The IR spectrum of sulfometuron-methyl exhibited the vibration peaks characteristic of functional group in wave numbers within one or more of about 3,220.49, 3,115.38, 3,006.03, 1,729.93, 1,694.47, 1,602,10, 1,548.64, 1,296,58, 1,122,13, 1,010,10, 954,06, 828,53, 782,85 and 755,86 cm-1 shown in Figure 2.

[0077] The DSC thermogram of sulfometuron-methyl exhibited an endothermic melting peak starting at 197.4 ° C and maximum peak at 200, 5 ° C, in addition optionally with a melting enthalpy of 118.3 J / g as shown in Figure 3.

[0078] The powder X-ray powder diffractogram showed the reflections in Figure 1 and the values are summarized in Table 1.
Table 1 - Diffractogram reflections of X-ray powder of crystalline modification of sulfometuron-methyl

Example 3: Preparation of crystalline modification I of sulfometuron-methyl from dichloromethane

[0079] Sulfometuron-methyl sample (6 g) was obtained in a 3-neck round-bottom flask together with dichloromethane (100 ml) and the resulting slurry was heated to 35 to 37 ° C to generate a homogeneous solution. The resulting hot solution was stirred at 35 to 37 ° C for 2 hours and filtered to remove insoluble material (if any) and the solution was slowly cooled to room temperature. The desired crystalline product was precipitated as a fine crystal during cooling and the mixture was stirred at 10 to 20 ° C for 2 hours. Then, the slurry was filtered, washed with cooled dichloromethane (10 ml) and dried under vacuum at 40 ° C in order to remove traces of dichloromethane from the crystal. The crystal thus obtained had a purity of about 98% and the yield found was about 86%. Crystalline I modification of sulfometuron-methyl was obtained.

[0080] The DSC thermogram of sulfometuron-methyl exhibited an endothermic melting peak starting at 197.1 ° C and maximum peak at 200.9 ° C, in addition optionally with a melting enthalpy of 119.1 J / g.

Example 4: Preparation of water-dispersible granules (WG) of amorphous sulfometuron-methyl

[0081] All components listed in Table 2 below have been mixed, mixed and ground in a high speed rotary mill. Sufficient water was added to obtain an extrudable paste. The paste was extruded through a die or sieve to form an extrudate. The wet extrudate was dried at 70 ° C in a vacuum oven and then sieved through 0.71 mm to 2 mm sieves to obtain the product granules.

Example 5: Preparation of water-dispersible granules (WG) from crystalline modification I of sulfometuron-methyl

[0082] All components listed in Table 3 below were mixed, mixed and ground in a high speed rotary mill. Sufficient water was added to obtain an extrudable paste. The paste was extruded through a die or sieve to form an extrudate. The wet extrudate was dried at 70 ° C in a vacuum oven and then sieved through 0.71 mm to 2 mm sieves to obtain the product granules.

Example 6: Preparation of amorphous methyl sulfometuron-methyl oil dispersion (OD)

[0083] All components listed in Table 4 below were mixed uniformly and the resulting mixture was ground with a Dyno-Mill (manufactured by Willy A. Bachofen AG) to obtain an oil dispersion.

Example 7: Preparation of oil dispersion (OD) of crystalline modification I of sulfometuron-methyl

[0084] All components listed in Table 5 below were mixed uniformly and the resulting mixture was ground with a Dyno-Mill (manufactured by Willy A. Bachofen AG) to obtain an oil dispersion.

Example 8: Cleaning test

[0085] The test was conducted by dispersing a sample in water to produce a concentration that is normally used when applying the herbicide: 20% sulfometuron-methyl. The sample was added under running water (300 ml) in a 400 ml beaker and magnetically stirred for 2 minutes. The mixture was then stirred for 2 minutes, in which the resulting dispersion was distributed in three 100 ml aliquots in 118 ml (4-oz) polyethylene bottles. The bottles were capped, inverted twice and left standing overnight.

[0086] After being stopped overnight, each individual bottle was inverted twice and the liquid content was then poured. Running water (10 ml) was added and the bottle was inverted until all the sediment was resuspended, in which the contents were poured. Running water (100 ml) was added and the bottle was inverted twice and then left standing undisturbed for 10 minutes. The bottle was inverted twice more and the contents were poured. Acetonitrile (10 ml) was added to the bottle to extract all the remaining material. The acetonitrile solution was analyzed by reverse phase liquid chromatography with UV detection. The cleanliness rating (the concentration of sulfometuron-methyl herbicide in the acetonitrile solution) is reported in% in Table 6 below. Lower cleaning ratings indicate more effective cleaning compared to higher cleaning ratings.

[0087] The results are summarized in Table 6 below.

[0088] The results in Table 6 demonstrate that the crystalline modification I of sulfometuron-methyl exhibited cleaning properties markedly superior to those of the known amorphous sulfometuron-methyl product.

Example 9: Wet Sieve Test

[0089] Examples 4 and 5 were diluted with water with a dilution factor of 50 and their residues were compared by passing through a 325 mesh wet sieve (44 μm openings). The amount of material retained in the sieve is determined by drying and weighting. The results are tabulated in Table 7.

[0090] It was surprisingly found that the crystalline modification I of sulfometuron-methyl is extremely stable after dilution. It has a reduced tendency to produce aggregates and waste after dilution compared to the amorphous form. The residue retained in the test for crystalline modification I of sulfometuron-methyl was 0.3%. In comparison, the corresponding retained residues when amorphous sulfometuron-methyl was used were 7%. For these reasons, the crystalline modification I of sulfometuron-methyl is highly suitable for preparing commercial formulations since such aggregates / residues can block the spray filters, which results in a loss of productivity.

Example 10: Effectiveness Test

[0091] Different types of weed and their relative densities in a field have been recorded and are listed in Table 8 below. Examples 4 and 5 were applied in the field. 4 weeks after application, the field was examined to determine the efficiency of the treatments. The results are shown below in Table 9 below.

[0092] The results in Table 9 demonstrate that the crystalline modification I of sulfometuron-methyl surprisingly exhibited superior herbicidal properties against Vulpia myuros, Vulpia bromoides and Cirsium vulgare than those of the known amorphous methyl sulfometuron product.

Claims (22)

Crystalline modification I of 2 - [(4, 6-dimethylpyrimidin-2-yl) carbamoylsulfamoyl] methyl benzoate (sulfometuron-methyl) characterized by exhibiting at least 3 of the following reflections, in any combination, such as 2θ ± 0.2 degree in X-ray powder diffractogram (X-RPD) recorded using Cu-Kα radiation at 25 ° C:
2θ = 13.8 ± 0.2 (3)
2θ = 16.3 ± 0.2 (4)
2θ = 21.9 ± 0.2 (6)
2θ = 23.4 ± 0.2 (8)
2θ = 27.3 ± 0.2 (9). Crystalline I modification of sulfometuron-methyl according to claim 1, characterized by exhibiting an IR spectrum with characteristic functional group vibration peaks in wave numbers (cm-1, ± 0.2%) of one or more out of 3,221 , 3,115, 3,006, 1,730, 1,694, 1,602, 1,549, 1,297, 1,122, 1,010, 954, 829, 783 and 756 cm-1. Crystalline modification I of sulfometuron-methyl according to either of claims 1 or 2, characterized in that it has a melting point of about 197 to 202 ° C. Crystalline modification I of sulfometuron-methyl according to any one of claims 1, 2 or 3, characterized by exhibiting a differential calorimetry scanning profile (DSC) that has an endothermic melting peak starting at 197.4 ° C, maximum peak at 200.5 ° C and displacement at 201.7 ° C, in addition, optionally with a melting enthalpy of 118 J / g. Crystalline modification I of sulfometuron-methyl, according to any one of claims 1, 2, 3 or 4, characterized by the X-ray powder diffraction model, as substantially shown in Figure 1, and / or by an IR spectrum, as substantially shown in Figure 2, and / or by a DSC thermogram, as substantially shown in Figure 3. Crystalline modification I of sulfometuron-methyl according to any one of claims 1, 2, 3, 4 or 5, characterized by being obtainable by the process, as substantially described in Example 2 or 3. Crystalline modification I of sulfometuron-methyl, optionally according to any one of claims 1, 2, 3, 4, 5 or 6, characterized by being obtainable by the process, according to any one of claims 8 to 13. Process for preparing the crystalline modification I of sulfometuron-methyl according to any one of claims 1, 2, 3 or 4, characterized by comprising:

• i) dissolve sulfometuron-methyl in a solvent, or mixture of solvents;
• ii) precipitating the dissolved compound in crystalline modification I of sulfometuron-methyl; and
• iii) isolating the precipitated crystalline modification I.

Process according to claim 8, characterized in that the sulfometuron-methyl in step i) is amorphous sulfometuron-methyl. Process according to claim 8 or 9, characterized by the fact that the solvent is selected from the group consisting of xylene, benzene, chlorobenzene, dichlorobenzene, dichloromethane, ethyl-benzene, trifluoro-methyl-benzene, mesitylene, nitrobenzene, acetone, diethyl ketone, methyl ethyl ketone, methanol, ethanol, isopropanol, acetonitrile or THF-hexane mixture, ethyl acetate-hexane, dichloromethane-hexane, dichloromethane-methanol, THF-water and methanol-water, and mixtures of the same. Process according to any one of claims 8, 9 or 10, characterized in that the solvent comprises acetone, dichloromethane or mixtures thereof. Process according to any one of claims 8, 9, 10 or 11, characterized by the fact that step ii) comprises concentrating the solution and / or cooling and / or by adding a solubility-reducing solvent and / or by adding an initial crystal of the sulfometuron-methyl crystalline modification I. Process according to claim 12, characterized by the fact that step ii) is carried out by cooling to about 0 to 20 ° C. Crystalline material characterized in that it comprises a crystalline modification I of sulfometuron-methyl obtained according to any one of claims 8, 9, 10, 11, 12 or 13 and which has a content of crystalline modification I of sulfometuron-methyl of at least 98% in weight. Composition characterized by comprising the crystalline modification I of sulfometuron-methyl according to claim 1, 2, 3, 4, 5, 6 or 7 and 14, and at least one auxiliary. Composition, according to claim 15, characterized by the fact that the auxiliary is selected from the group consisting of a surfactant, a diluent, a wetting agent, a dispersant, a thickening agent, an antifoaming agent, an antifreeze agent, a preservative, an antioxidant, a solid adherent, an inert filler and mixtures thereof. Composition according to claim 16, characterized in that the other formulation ingredients can be dyes and drying agents. Composition according to any one of claims 15, 16 or 17, characterized in that it is in the form of a suspension concentrate (SC), an oil dispersion (OD), a water soluble granule (SG), a dispersible concentrate ( DC), an emulsifiable concentrate (EC), an emulsion seed treatment, a suspension seed treatment, a granule (GR), a microgranule (MG), a suspoemulsion (SE) or a water dispersible granule (WG) . Composition according to claim 18, characterized in that it is in the form of a water-dispersible granule (WG) or oil dispersion (OD). Method for controlling unwanted plant growth characterized in that it comprises applying to the plant, part of the plant or surroundings of the plant, an herbicide effective amount of the crystalline modification I of sulfometuron-methyl according to any one of claims 1, 2, 3, 4 , 5, 6 or 7 and 14, or a composition according to any one of claims 15, 16, 17, 18 or 19. Use of the crystalline modification I of sulfometuron-methyl according to any one of claims 1, 2, 3, 4, 5, 6 or 7 and 14, or a composition according to any one of claims 15, 16, 17, 18 or 19, characterized for being for weed control. Crystalline modification I of sulfometuron-methyl according to any one of claims 1, 2, 3, 4, 5, 6 or 7, characterized in that it is substantially as previously described in the present document with reference to any of the examples, figures or the description.

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