UA113540U - COMPRESSING DEVICE FOR BONE FILLING - Google Patents

Abstract

The compression device for fixing bone fragments consists of a plate that has round threaded holes and a shortened half-length. The plate has a notch. The openings are obliquely oval in shape, including a shortened half-length secured from above to the plate by means of a groove and fixed by a screw with a conical head through the threaded hole. The plate is provided with locking screws to secure the bone fragment.

Description

The present invention relates to solid forms of antidotes, which are -M- acylsulfamoylphenylurea, to methods of their preparation, compositions containing solid forms, and to methods of their use as antidotes.

Herbicide antidotes selectively protect crops from herbicide damage without reducing activity against target weed species. They are used on an industrial scale to improve the selectivity of herbicides between crop and weed species, and can be used, for example, in the form of a mixture with a herbicide or as a seed treatment in relation to the seeds of agricultural crops before sowing. US Patent 5,215,570 discloses that certain M-acylsulfamoylphenylurea derivatives can act as antidotes. In particular, the compound of the formula (I), M-(2-methoxybenzoyl) /-4-((methylaminocarbonyl) amino|benzenesulfonamide: (c, (c,

AND! What" c) o) -hi- / o 0)

This antidote is suitable for protecting cultivated plants from phytotoxic effects, for example, acylcyclohexanedione herbicides, sulfonylurea herbicides, chloroacetanilide herbicides, and aryloxyphenoxypropionic acid herbicides.

To date, new solid forms of this compound, their compositions and methods of their preparation and application have been discovered.

Accordingly, the present invention relates to new crystalline forms of the antidote of formula (1).

In one aspect of the present invention, a crystalline polymorph of a compound of the formula is provided

And, said form 1, which is characterized by a powder X-ray pattern expressed in angles 28, wherein the X-ray powder pattern includes at least three, at least four, at least five, at least six, at least 7, or all values of the angle 28 (in degrees) selected from the group, which includes 7.4x20.2, 9.3x0.2, 11.7-0.2, 12.030.2, 14.3x20.2, 15.1-0.2, 17.4530.2 and 19.020.2. These values of the angle 29 are obtained from the powder X-ray pattern of the form 1 polymorph obtained using the method of example 1a. The values were obtained using a wavelength of 1.540564A with a step size of 29 0.022.

In another aspect, a crystalline polymorph of a compound of formula I, designated Form 1, has a melting point of 198"Cg57"Fsb. This melting point is obtained using differential

From scanning calorimetry (0550) with a heating rate of 10"C/minute.

In the next aspect of this invention, a crystalline polymorph of the compound of formula I, called form 2, is presented, which is characterized by the unit cell parameters of its single crystal, as shown in Table 1. This polymorph was obtained using the method of example 14.

Table 1 a - 19.38(5)

Cell lengths (A) b - 7.34(5) s - 22.95(5 o - 90.00

The corners of the cell (2) r.- 90.00 - 90.00 v

In table a, b, c - the length of the edges of the elementary cell; c, p, y - corners of the elementary cell; and 2 - the number of molecules per cell.

Thus, in one aspect of the present invention, the crystalline polymorph of the present invention, designated form 2, has the following lattice parameters: a-19.38(5), b-7.34(5), c-22.95(5), w - 90.00, r - 90.00, y - 90.00 and volume - 3264.8(5) AZ.

In another aspect of the present invention, the crystalline polymorph of the present invention, called form 2, is characterized by a powder X-ray pattern expressed in angles 28, where the powder X-ray pattern includes (a) at least one value of the angle 28, which is 9.0:50.2; and (p) one value of angle 28, which is 21.750.2; and (c) at least three, at least four, at least five, at least six, or all values of angle 20 selected from the group consisting of 7.750.2, 11.9:0.2, 13.4x0.2, 15.050.2 , 15.6:0.2, 16.120.2 and 18.0:0.2.

In one embodiment, the crystalline polymorph of the present invention, called form 2, is characterized by a powder X-ray pattern expressed in angles 298, where the powder X-ray pattern includes (a) at least one value of the angle 28, which is 9.0:50.2; and (p) one value of angle 28, which is 21.750.2; and (c) at least three values of angle 28 selected from the group consisting of 7.7-0.2, 11.9:20.2, 13.420.2, 15.030.2, 15.6:5-0.2, 16,120.2 and 18,050.2.

In another embodiment, the crystalline polymorph of the present invention, called form 2, is characterized by a powder X-ray pattern expressed in angles 298, where the powder X-ray pattern includes (a) at least one value of the angle 28, which is 9.0:50.2; and (p) one value of angle 28, which is 21.750.2; and (c) at least four values of angle 28 selected from the group consisting of 7.750.2, 11.9:-0.2, 13.420.2, 15.030.2, 15.6:5-0.2, 16.120.2 and 18,050.2.

In another embodiment, the crystalline polymorph of the present invention, called form 2, is characterized by a powder X-ray pattern expressed in angles 28, where the powder X-ray pattern includes (a) at least one value of the angle 28, which is 9.0:50.2; and (p) one value of angle 28, which is 21.750.2; and (c) at least five values of angle 28 selected from the group consisting of 7.750.2, 11.9:0.2, 13.420.2, 15.050.2, 15.6:50.2, 16.1- 0.2 and 18.0:50.2.

In another embodiment, the crystalline polymorph of the present invention, called form 2, is characterized by a powder X-ray pattern expressed in angles 298, where the powder X-ray pattern includes (a) at least one value of the angle 29, which is 9.0:50.2; and (p) one value of angle 28, which is 21.750.2; and (c) at least six values of angle 29 selected from the group consisting of 7.750.2, 11.9:0.2, 13.420.2, 15.030.2, 15.6:5-0.2, 16.120.2, and 18,050.2.

In another embodiment, the crystalline polymorph of the present invention, called form 2, is characterized by a powder X-ray pattern expressed in angles 28, where the powder X-ray pattern includes (a) at least one value of the angle 28, which is 9.0:50.2; and (p) one value of angle 28, which is 21.750.2; and (c) all values of angle 28 selected from the group consisting of 7.7520.2, 11.90.2, 13.420.2, 15.050.2, 15.6:0.2, 16.120.2, and 18.05 -0.2.

These values of the angle 28 are obtained from the powder X-ray pattern of polymorph form 2 obtained using the method of example 14. The values are obtained using the wavelength 1.540564A with a step size 29 of 0.022.

In a further aspect, the crystalline polymorph of the present invention, designated Form 2, has a melting point of 216°C.5°C. This melting point is obtained using differential scanning calorimetry (О5С) with a heating rate of 10"С/minute.

In another aspect of this invention, a crystalline polymorph of the compound of formula I, called form 3, is presented, which is characterized by the unit cell parameters of its single crystal, as shown in Table 2. This polymorph was obtained using the method of example 16.

Table 2 a - 7.96(5)

Cell lengths (A) b - 23.56(5) s-9.11(5 o - 90.00

The corners of the cell (2) r - 92.58 (5) - 90.00

In table a, b, c - the length of the edges of the elementary cell; c, p, y - corners of the elementary cell; and 2 - the number of molecules per cell.

Thus, in one aspect of the present invention, the crystalline polymorph of the present invention, designated Form 3, has the following lattice parameters: a-/.96(5), B-23.56(5), c-9.11(5), c - 90.00, D - 92.58(5), y - 90.00 and volume - 1708.2(5) Az.

In another aspect of the present invention, the crystalline polymorph of the present invention, called form 3, is characterized by a powder X-ray pattern expressed in angles 29, where the powder X-ray pattern includes (a) one value of the angle 28, which is 16.9:0.2; and (p) one value of angle 28, which is 18.9:0.2; and (c) at least three, at least four, at least five, at least six, at least seven, at least eight, at least nine, at least ten, or all values of angle 20 selected from the group consisting of 7.5:20.2 , 12.3x0.2, 13.40.2, 14.420.2, 14.9:50.2, 15.68:20.2, 18.3:20.2, 20.950.2, 21.9:0 ,2, 22.6:50.2 and 23.8:-0.2.

In one embodiment, the crystalline polymorph of the present invention, named form

C is characterized by a powder X-ray pattern expressed in angles 28, where the powder X-ray pattern includes (a) one value of the angle 28, which is 16.9:0.2; and (p) one value of angle 28, which is 18.9:20.2; and (c) at least three values of angle 28 selected from the group consisting of 7.5520.2, 12.350.2, 13.420.2, 144502, 14.950.2, 15.68:0.2, 18.3:20, 2, 20.950.2, 21.9:0.2, 22.6:50.2 and 23.6:0.2.

In another embodiment, the crystalline polymorph of the present invention is named form

C, is characterized by a powder X-ray pattern expressed in angles 29, where the powder X-ray pattern includes (a) one value of the angle 28, which is 16.9:0.2; and (p) one value of angle 28, which is 18.9:0.2; and (c) at least six angle 20 values selected from the group consisting of 7.5:50.2, 12.350.2,

From 13.450.2, 14.450.2, 14.950.2, 15.8:-0.2, 18.3:20.2, 20.950.2, 21.950.2, 22.650.2 and 23.8:50 2.

In another embodiment, the crystalline polymorph of the present invention is named form

C is characterized by a powder X-ray pattern expressed in angles of 2989, where the powder X-ray pattern includes (a) one value of the angle 28, which is 16.9:0.2; and (p) one value of angle 28, which is 18.9:0.2; and (c) at least nine values of angle 26 selected from the group consisting of 7.5:0.2, 12.350.2, 13.420.2, 144502, 14.950.2, 15.68:0.2, 18, 3:20.2, 20.950.2, 21.9:0.2, 22.6:50.2 and 23.6:0.2.

In another embodiment, the crystalline polymorph of the present invention is named form

C, is characterized by a powder X-ray pattern expressed in angles 289, where the powder X-ray pattern includes (a) one value of the angle 28, which is 16.9:0.2; and (p) one value of angle 28, which is 18.9:0.2; and (c) all values of angle 28 selected from the group consisting of 7.5:20.2, 12.350.2, 13.450.2, 14.450.2, 14.9:20.2, 15.8:.0, 2, 18.3:50.2, 20.9:0.2, 21.9520.2, 22.6:50.2 and 23.6:0.2.

These values of the angle 29 are obtained from the powder X-ray pattern of polymorph form 3 obtained using the method of example Te. The values were obtained using a wavelength of 1.540564A with a step size of 29 0.022.

In another aspect, the crystalline polymorph of the present invention, designated Form 3, has a melting point of 202"Sbzh5"Sb. This melting point is obtained using differential scanning calorimetry (0550) with a heating rate of 10°C/minute.

In the context of this invention, a polymorph is a specific crystalline form of a chemical compound that can exist in more than one crystalline form in the solid state. The crystalline form of a compound contains the molecules that make it up, which form ordered repeating structures that extend in all three spatial dimensions (and vice versa, in an amorphous solid form there is no long-range order in the arrangement of molecules). Different polymorphs of the compound have different arrangements of atoms and or molecules in their crystal structure. If the compound is a biologically active compound, such as an antidote, differences in crystal structures may result in different polymorphs having different chemical, physical and biological properties.

Properties that may vary include crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspending ability, dissolution rate, and bioavailability. In this regard, a particular polymorph may have properties that make it more advantageous in a particular application compared to another polymorph of the same compound: in particular, the physical, chemical and biological properties listed above may have a significant impact on the development of production methods, and the compositions, quality, and effectiveness of plant treatments such as antidotes. It is noted that it is impossible to predict whether a compound in the solid state can be represented by more than one polymorph, and it is also impossible to predict the properties of any of these crystalline forms. In particular, in the context of the present invention, it has been found that a compound of formula (I) can exist in the form of a stable polymorph, called form 2, which is preferred due to its stability compared to form 1 and form 3, which reduces the degree of crystallization that takes place in the compounds of the formula (I), since metastable forms change over time to a stable form. Such crystallization is disadvantageous because it can lead to thickening and possible solidification of the formulation and/or the formation of large crystals that can cause plugging in application equipment such as sprayers in agricultural machinery. In this regard, the polymorph called form 2 is preferred.

The present invention also relates to methods of obtaining polymorphs according to the present invention either directly (that is, without taking as a basis other solid forms of the compound of formula I), or by

From the transformation of other solid forms of compounds of formula I.

Analysis of the solid phase for the presence of crystals can be carried out using conventional methods known in the art. For example, it is advisable and generally accepted to use X-ray powder diffraction methods. Other techniques that may be used include differential scanning calorimetry (055), thermogravimetric analysis (TA), and Raman or infrared spectroscopy,

NMR, gas chromatography or NRI C. X-ray diffraction on single crystals is particularly suitable for determining crystal structures.

Polymorphs according to the present invention can be used in unchanged form, but it is more preferable to introduce them into agrochemical compositions using traditional methods. Accordingly, a further aspect of the present invention provides an agrochemical composition comprising a polymorph of the present invention as defined above and at least one agriculturally suitable carrier or diluent. In one embodiment, the composition of the present invention additionally contains at least one herbicide. Preferably, the ratio of at least one herbicide and antidote in the mixture is from 100:1 to 1:100, in particular, from 20:1 to 1:20.

In the next aspect of this invention, a method of protecting crops of useful plants from the harmful effects of a herbicide is presented, which includes the application of the polymorphs of this invention in relation to the place of growth of useful plants.

In yet another aspect of the present invention, a method of controlling weeds in crops of useful plants is presented, which includes treating useful plants, their seeds, or cuttings, or places of growth of useful plants at the same time or at different times with the herbicide and polymorphs of the present invention.

Any method of application to the weed/useful plant crop or their growth site that is commonly used in agriculture can be used, for example application by spraying or spreading, usually after suitable dilution of the composition of the present invention.

The term "plant" as used herein includes seedlings, shrubs and trees.

The term "growth site" as used in this document includes not only areas where weeds can already grow, but also areas where weeds will still appear, as well as sown areas for crops of useful plants. Sown areas include land on which crops are already growing and land intended for cultivation of these crops.

Crops of useful plants, in relation to which the compositions of the present invention can be applied or the methods of the present invention are applied, include perennial agricultural crops, for example, citrus fruits, varieties of cultivated grapes, nuts, varieties of oil palm, olives, pome fruits, drupes and plants, rubber and annual cultivated crops such as cereals such as barley and wheat, cotton, rapeseed, maize (including sweet corn), rice, sorghum, soybeans, sugar beet, sugar cane, sunflower, decorative plants and vegetables, in particular, cereals and corn.

Compositions and methods according to the present invention can also be applied to turf, pastures, grazing lands, right-of-way, etc. In particular, they can be used in relation to golf courses, lawns, parks, sports grounds, racetracks, etc.

Plants should also be understood as those that have been given tolerance to herbicides or classes of herbicides (for example, АЙ 5-, (15-, ЕРБР5Б-, PPO- and НРПО -inhibitors) using traditional breeding methods or genetic engineering. For example, a plant that has been given tolerant to imidazolinones, such as imazamox, through traditional breeding methods, is the field cabbage (canola). Examples of plants that have been made tolerant to herbicides using genetic engineering methods include, for example, glyphosate- and glufosinate-resistant maize varieties, commercially available under the trade names KoipairKeaauFd and

Gibepui! ipkF)

Plants should also be understood as those that have been given resistance to harmful insects by means of genetic engineering methods, for example, Wee corn (resistant to the corn borer), Wee cotton (resistant to the cotton boll weevil), and varieties of Wee potatoes (resistant to the Colorado potato beetle ). Examples of Vi corn are Vi 176 ICF corn hybrids (bZupdepia Zeedv5).

Examples of transgenic plants that contain one or more genes encoding resistance to insects and express one or more toxins are KposkKOcKe (maize), Mieii SagatF (maize),

MySOTtIMZ3ZVF (cotton), VoiYidagaF (cotton), Mem/I eakyu (varieties of potatoes), Maiigesagaf and

Rgoiehsiaf. Plants should also be understood as those that have been given resistance to harmful insects by means of genetic engineering methods, for example, Wee corn (butterfly resistant

From corn), VI cotton (resistant to the cotton weevil), as well as varieties of Vi potato (resistant to the Colorado potato beetle). Examples of corn Vi are corn hybrids VI 176 ICF (Zupdepia

Zeeazkh). Examples of transgenic plants that contain one or more genes encoding resistance to insecticides and express one or more toxins are KposkOShshKe (maize), miveia

Sagat (maize), MYSOTIMZ3ZVF (cotton), VoidagaF (cotton), Mem/i eayb? (varieties of potatoes),

MaishgesSagaFf and Rgoiehsiafb. Both plant crops and their seed material can be resistant to herbicides and at the same time resistant to being eaten by insects (transgenic objects with "packaged" genes). For example, a seed may be able to express the insecticidal protein StguZ and at the same time be tolerant to glyphosate. Features include those that enhance plant defense against insects, arachnids, nematodes, and slugs and snails by means of plant-produced toxins, particularly those produced in plants by genetic material from VasiShiv5 and Pygypdiepzi5 (eg, by genes StuIA(At1), StuIiA(B), StuIA(c),

StUPA, StuPA, StuPIV2, Studs, Stu2AB, StuZVB and StiUE, as well as their combinations). Traits also include those that provide plant defense against fungi, bacteria and viruses through systemic acquired resistance (SAC), systemin, phytoalexins, elicitors and resistance genes, and appropriately expressed proteins and toxins.

Both plants and their seed material can be resistant to herbicides and at the same time resistant to being eaten by insects (transgenic objects with "packaged" genes). For example, a seed may be able to express the insecticidal protein Stuz and at the same time be tolerant to glyphosate.

Plants should also be understood as those obtained by traditional methods of breeding or genetic engineering and which have so-called introduced characteristics (for example, improved storage stability, higher nutritional value and improved taste).

Plants and plant varieties obtained by means of genetic engineering methods, if necessary in combination with traditional methods, and their parts can be treated with polymorphs and compositions according to the present invention. Plant varieties are plants endowed with new properties ("traits") that have been obtained using traditional breeding, mutagenesis or recombinant DNA technologies. These can be varieties, bio- or genotypes. Depending on the types of plants or varieties of plants, their place of growth and conditions of growth (soil, climate, growing season, nutrition), processing according to this invention can also lead to super-additive or "synergistic" effects. Thus, for example, reduced application rates and/or broadening of the spectrum of action and/or increased activity of substances and compositions that can be used according to the present invention, improved plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to the salt content of the soil or water, increased flowering productivity, improved harvestability, accelerated ripening, increased crop size, improved quality and/or increased nutritional value of harvested produce, improved storage stability and/or processability of harvested produce are possible , which exceeds the effects that were actually expected. Preferred transgenic plants or plant varieties (obtained by genetic engineering) to be processed according to the present invention include all plants that have received genetic material through genetic modification that endows these plants with particularly preferred beneficial characteristics. Examples of such traits are improved plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or soil or water salinity, increased flowering performance, improved harvestability, accelerated ripening, increased crop size, improved quality and/or increased nutritional value of harvested products, improved storage stability and/or ability to process harvested products. Other examples of such traits are improved plant protection against animal pests and harmful microorganisms, such as insects, mites, phytopathogenic fungi, bacteria and/or viruses, and increased plant tolerance to specific compounds with herbicidal activity. Examples of transgenic plants that can be mentioned are important crops such as cereals (wheat, rice), maize, varieties of soybeans, varieties of potatoes, sugar beets, tomatoes, varieties of peas and other varieties of vegetable crops, cotton, tobacco, oilseed rape, as well as fruit plants (with the fruits of apple trees, pear trees, citrus fruits and grapes), but especially corn, varieties of soybeans, varieties of potatoes, cotton, tobacco and oilseed rape should be highlighted.

The term "weed" as used herein means any undesirable plant and thus includes not only the agronomically important weeds described below, but also self-sowing crops.

The compositions according to the present invention are suitable for all traditional methods of application in agriculture, such as, for example, pre-emergence application, post-emergence application

From the appearance of seedlings and seed germination. Depending on the intended application, the polymorph according to the present invention can be used for pre-treatment of the seeds of a cultivated plant (treatment of seeds or cuttings) or it can be introduced into the soil before or after sowing. However, it can also be applied alone or with a pre- or post-emergence herbicide. Treatment of plants or seeds with polymorph, respectively, can be carried out, in principle, regardless of the time of herbicide application. Treatment of plants by simultaneous application of herbicide and polymorph (for example, in the form of a tank mixture) is usually preferable. The rate of application of the polymorph in relation to the herbicide to be applied mainly depends on the method of application. For field treatment, as a rule, 0.001-5.0 kg polymorph/ha, preferably 0.01-0.5 kg polymorph/ha and, as a rule, 0.005-2 kg herbicide/ha, but preferably 0.001-1 kg/ha are used. Ha. As a rule, 0.001-10 g of polymorph/kg of seeds, preferably 0.05-2 g of polymorph/kg of seeds are used for seed treatment.

Compositions of the present invention (comprising the polymorphs of the present invention and preferably the herbicide) are preferably formulated in a variety of ways using formulation components such as carriers, solvents and surfactants, for example as described hereinbelow.

Compound compositions can be in different physical forms. Compositions containing the polymorphs of the present invention, but without the herbicidal active ingredient, can be, for example, in the form of powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent dragees, aqueous dispersions , oil dispersions, suspoemulsions, encapsulated suspensions, suspension concentrates, emulsified granules, impregnated polymer films or in other forms known, for example, from

Mapiai! op Oyemeiortepi apa Ove oi EAO 5resiiisaiopv og Riapi Rgoiesip Rgodisiv, Bii Eayop, 1999. In the event that one or more herbicides are combined with the polymorph according to the present invention, they can be presented in a liquid or solid state: the naming convention provides that such compositions will be named according to the herbicidal active ingredient present, rather than the antidote polymorph of compound Y, and in this regard, additional types of formulations are also possible. Compound compositions can be presented in the form of concentrates, which are diluted before use, although it is also possible to obtain ready-to-use compositions. Dilution can be carried out, for example, with the help of water, liquid fertilizers, micronutrients, biological organisms, oil or solvents.

Composite compositions can be obtained, for example, by mixing the polymorph and optionally the herbicide with the components of the composition in order to obtain compositions in the form of finely divided solids, granules or dispersions. Active ingredients may also be formulated with other components, such as finely divided solids, mineral oils, vegetable or animal oils, modified vegetable or animal oils, organic solvents, water, surfactants, or combinations thereof. Active ingredients can also be contained in very small microcapsules consisting of a polymer. Microcapsules typically range from 0.1 to 500 microns in diameter. Typically, they will contain the active ingredients in an amount of about 25 to 95% by weight of the weight of the capsule. The active ingredients can be in the form of a monolithic solid substance or in the form of finely dispersed particles in a solid or liquid dispersion. Encapsulated membranes contain, for example, natural or synthetic rubbers, cellulose, copolymers of styrene and butadiene, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other known polymers. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of the main substance, but the microcapsules themselves are not encapsulated.

Composition components suitable for obtaining compositions according to the present invention are known under Reg. 5e. Water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid can be used as liquid carriers. (eg, butyl acetate, ethyl acetate, isoamyl acetate, amyl acetate), diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, M,M-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, a-limonene, ethyl lactate, ethylene glycol , ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hec sadecane, hexylene glycol, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyluetone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, meta-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, ortho-xylene, phenol, polyethylene glycol (PES), propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, para-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene , perchlorethylene, methanol, ethanol, isopropanol and high molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, M-methyl-2-pyrrolidinone, etc. Water is usually the preferred vehicle for diluting concentrates. Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soybean meal, pumice, wood flour, ground shellac walnuts, lignin, and similar substances, as described, for example, in SEC 180.1001. (c) 8. (a).

A large number of surfactants can be used successfully in formulations, particularly in formulations that require dilution with a carrier prior to use.

Surfactants may be anionic, cationic, nonionic, or polymeric, and may be used as emulsifiers, wetting or suspending agents, or for other purposes. Common surfactants include, for example, salts of alkyl sulfates such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products such as tridecyl alcohol ethoxylate; soaps such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters such as sorbitol oleate; quaternary amines such as lauryltrimethylammonium chloride; esters of polyethylene glycol and fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphate esters; as well as additional substances described, for example, in "MeSshispeopye Oeiegdepibv apa

Etiiviyetv Appia!", MO Rybiizpipu Sogr., Viddeumood, Mem Uegweu, 1981.

Additional components that may be commonly used in such formulations include crystallization inhibitors, viscosity modifiers, suspending agents, colorants, antioxidants, foaming agents, light absorbing agents, mixing aids, antifoams, complexing agents, neutralizing or pH modifying agents. and buffers, corrosion inhibitors, deodorizers, wetting agents, absorption enhancers, trace nutrients, plasticizers, slip aids, lubricants, dispersants, thickeners, antifreezes, microbiocides, and liquid and solid fertilizers. An example of such an auxiliary agent is ammonium sulfate.

Compound compositions according to the present invention may additionally include an additive containing oil of vegetable or animal origin, mineral oil, complex alkyl esters of such oils or mixtures of such oils and derived oils. The amount of oil additive in the composition according to the present invention is usually 0.01-10 95, based on the spray mixture.

For example, an oil additive can be added to the sprayer tank at the required concentration after the spray mixture has been prepared. Preferred oil additives include mineral oil or oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil such as AMISOF (EPope-

Rocheps Sapada Ips.), complex alkyl esters of oils of vegetable origin, for example, methyl derivatives, or oil of animal origin, such as fish oil or beef tallow. A preferred additive contains, for example, as active ingredients essentially 8095 by weight of complex fish oil alkyl esters and 1595 by weight of methylated rapeseed oil, as well as 595 by weight of conventional emulsifiers and pH modifiers. Particularly preferred oil additives contain complex alkyl esters of Monofatty acids, in particular, methyl derivatives of Sig fatty acids, for example, complex methyl esters of lauric acid, palmitic acid and oleic acid are important. Such esters are known as methyl laurate (СА5Б-111-82-0), methyl palmitate (САБ-112-39-0) and methyl oleate (САБ-112-62-9). The preferred methyl ester derivative of a fatty acid is Etegu? 2230 and 2231 (Sodpiz StbN). These and other oil derivatives are also known from Sotrepait oi Negbiside Adiimapiv, Bii Eaiiop, Zociipegp Shipoiz Opimegeiu, 2000. Another

Is Adidog the preferred aid? (Zupdepia AC), which is a methylated adjuvant based on rapeseed oil.

The application and performance of oil additives can be further enhanced by combination with surfactants, such as nonionic, anionic or cationic surfactants. Examples of suitable anionic, nonionic and cationic surfactants are listed on pages 7 and 8 of the patent document

MO 97/34485. Preferred surfactants are anionic surfactants of the dodecylbenzylsulfonate type, in particular, their calcium salts, as well as nonionic surfactants of the fatty alcohol ethoxylate type. Particular preference is given to ethoxylated C1 and 222 fatty alcohols with a degree of ethoxylation from 5 to 40. Examples of commercially available surfactants are Separoa types (Siagiapi

AC). Also preferred are organosilicon surfactants, in particular heptamethyltriloxanes modified with polyalkyloxides, which are commercially available, for example as

Zimei I -779, as well as perfluorinated surfactants. The concentration of surface-active substances in relation to the entire additive, as a rule, is from 1 to 30 95 by weight.

Examples of oil additives consisting of mixtures of oil, or mineral oils, or their derivatives with surface-active substances are Edepogi ME 502, Tigtrosnagde? (Zupdepia AS,

Switzerland) or Asia (UK, Great Britain).

If necessary, it is also possible to use the mentioned surface-active substances in the compositions by themselves, that is, without oil additives.

In addition, the addition of an organic solvent to the oil additive/surfactant mixture can further enhance the action. Suitable solvents are, for example, boime5509? (E5BBO) or Agotaiis Boimepi? (Ekhhop Sogrogayop). The concentration of such solvents can range from 10 to 80 to 95% by weight of the total weight. Oil additives, which are presented in a mixture with solvents, are described, for example, in O5-A-4834908. The commercially available oil additive disclosed herein is known as MEXE? (WABE

Sogrogayop). An additional oil additive that is preferred according to the present invention is ZSOKEZ? (Zupdepia Stor Rgoiesiiop Sapada).

In addition to the oil additives listed above, in order to enhance the effect of the compositions according to the present invention, it is also possible to add compositions with alkylpyrrolidones (for example, because Adgitah?) to the spray mixture. Formulations based on synthetic latexes can also be used, such as, for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene (for example, Vopa?, Socgie? or EtegaLide?). Solutions that contain propionic acid, for example, EidoKet Rep-e-iIgaie-, can also be added to the spray mixture as a means of enhancing the effect.

Formulated compositions of the present invention typically contain from 0.1 to 99% by weight, particularly from 0.1 to 95% by weight of the polymorph and herbicide and from 1 to 99.9% by weight of a formulation aid which preferably includes from 0 to 25 95 by weight of surfactant. Since commercial products will mostly be formulated as concentrates, the end user will usually use diluted formulations.

Various methods and techniques are suitable for the use of polymorphs or compositions containing them to protect cultivated plants from the harmful effects of herbicides, such as, for example, the following: i) Seed treatment

Etching of seeds with polymorph composed in the form of a wettable powder by shaking in a vessel until uniform distribution on the surface of the seed is achieved (dry etching). In this case, approximately 1 to 500 g of polymorph (from 4 g to 2 kg of wettable powder) per 100 kg of seed is used.

Seed treatment or sprouted seed treatment are of course the preferred methods of application, as the polymorph treatment is completely directed at the target crop. As a rule, from 1 to 1000 g of polymorph is used, preferably from 5 to 250 g of polymorph per 100 kg of seed, and depending on the methods, deviations in the direction of increase or decrease from the specified limit values of concentration (repeated etching) are possible, which also allows adding other active compounds or micronutrients. i) Application in the form of a tank mixture

A liquid processed mixture of polymorph and herbicide is applied (the ratio of the inverse quantities from 10: 1 to 1: 100), and the herbicide application rate is from 0.005 to 5.0 kg per hectare. Such tank mixtures are used before or after sowing. ii) Application in relation to the furrow for seeds

Zo Polymorph is introduced into the furrow for seeds for sowing in open ground in the form of a wettable powder or in the form of granules. After the seed furrow is closed, the herbicide is applied in the usual way using the pre-emergence application method. them) Controlled release of the polymorph

Ensure the absorption of the polymorph in the solution on granules of a mineral carrier or polymerized granules (urea/formaldehyde) and dry. Optionally, you can apply a coating that ensures the release of the polymorph over a certain period of time (coated granules).

In particular, the preferred compositions have the following components (95 percent by weight; active mixture of active compounds means a mixture of a compound of formula I with a herbicide):

Powdered preparations

Active mixture 0.1-10 95, mainly active compounds: 0.1-5 vol.

Solid media: 99.995 to 90905, preferably 99.9 to 99 95.

Concentrates of suspensions

Active mixture 5-75 96, mostly active compounds: 10-50 95.

Water: 94-24 95, mostly 88-30 Vol.

Surfactant 1-40 95, mainly substance: 2-30 90.

Wettable powders

Active mixture 0.5-90 95, mainly active compounds: 1-80 9.

Surfactant 0.5-20 95, mainly substance: 10-15 95.

Solid carrier: 5-95 95, preferably 15-90 95.

Pellets

Active mixture 0.1-30 95, mainly active compounds: 0.1-15 Vol.

Solid carrier: 99.5-70 965, mostly 97-85 9.

Examples of compositions for mixtures of polymorphs according to the present invention with herbicides (95-95 by weight; EO - ethylene oxide)

Composition 1. Wettable powders a) Br) c) a) a mixture of active compounds Bo 2590 509 809o sodium lignosulfonate ayu - Zoo - sodium lauryl sulfate 2 Zoo - ayu sodium disobutyl naphthalene sulfonate - boju Bo bean polyglycol ether of octylphenol (7-8 mol EO) - 19o 2 - highly dispersed silicic acid 19o Zoo Bo 109o kaolin 8895 b2oo ZB -

The mixture of active compounds is thoroughly mixed with auxiliaries and the resulting mixture is thoroughly ground in a suitable mill to obtain wettable powders that can be diluted with water to obtain suspensions of any desired concentration.

Composition 2. Coated granules a) Br) c) a mixture of active compounds 0.195 Bo 1590 highly dispersed silicic acid 0.990 2 2 inorganic carrier (diameter 0.1-1 mm), o o o o for example, CaCO3 or 5iO2 99.07e Z W

The mixture of active compounds is dissolved in methylene chloride and applied to the support by spraying, and the solvent is then evaporated in massio.

Composition 3. Coated granules a) Br) c) a mixture of active compounds 0.195 Bo 1590 polyethylene glycol MUM 200 1.090 2 Zoo highly dispersed silicic acid 0.990 19o 2 inorganic carrier (diameter 0.1-1 mm), o o o o for example, CaCO3 or 5iO2 З8 , ote Za Vo

A finely divided mixture of active compounds in a mixing device is evenly applied to a carrier moistened with polyethylene glycol. In this way, non-dust-like coated granules are obtained.

Composition 4. Extruded granules a) Br) c) a) a mixture of active compounds 0.195 Zoo Bo 1595 sodium lignosulfonate 1.595 2 Zoo ayu carboxymethyl cellulose 1.495 2 2 2 kaolin 97096 9395 9095 7990

The mixture of active compounds is mixed and ground with auxiliary means, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

Composition 5. Dust-like preparations a) Br) c) a mixture of active compounds 0.195 19o Bo talc 39.990 4990 3590 kaolin 60.09 BO 609

Ready-to-use powdered preparations are obtained by mixing a mixture of active compounds with carriers and grinding the mixture in a suitable mill.

Composition 6. Suspension concentrates a) B) c) a) a mixture of active compounds Zoo 109o 2590 BO ethylene glycol Bo Bo Bo Bo polyglycol ether of nonylphenol (15 mol 19 g

EO) more than more sodium lignosulfonate Zoo Zoo ayu Bo carboxymethyl cellulose 19o 19o 19o 19o 3795 aqueous formaldehyde solution 0.2 0.290 0.2 0.2 silicone oil emulsion 0.890 0.895 0.89o 0.8 to water 8790 7990 6296 3890

A finely divided mixture of active compounds is directly mixed with auxiliary means to obtain a suspension concentrate, from which suspensions of any desired concentration can be obtained by diluting with water.

It is often more practical to formulate the polymorph and herbicide separately and then combine them as a "tank mix" in water in the application equipment at the desired mixture ratio shortly before application.

The compositions and compositions of the present invention can also be used in combination with other active ingredients, for example, other herbicides, and/or insecticides, and/or acaricides, and/or nematocides, and/or molluscicides, and/or fungicides, and/or regulators plant growth. These mixtures and the use of these mixtures for the control of weeds and/or the growth of undesirable plants form still further aspects of the present invention.

In the event that the polymorph of the present invention, in particular, polymorph form 2, is combined with at least one herbicide, the following herbicides are particularly preferred: acetochlor, acifluorfen, acifluorfen sodium, aclonifen, acrolein, alachlor, aloxidim, allyl alcohol, ametrine, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amitrole, ammonium sulfamate, anilophos, asulam, atrazine, aviglycin, azafenidine, azimsulfuron, VSRS, beflubutamide, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulfuron-methyl, benzulid, bentazone, benzphendisone, benzobicyclone, benzofenap , bicyclopyrone, bifenox, bilanaphos, bispyribac, bispyribac-sodium, borax, bromacil, bromobutide, bromophenoxime, bromoxynil, butachlor, butafenacil, butamiphos, butraline, butroxidim, butylate, cacodylic acid, calcium chlorate, cafenestrol, carbetamide, carfentrazone, carfentrazone-ethyl , SOBEA, SERS, chlorflurenol, chlorflurenol-methyl, chloridazone, chlorimuron, chlorimuron-ethyl, chloroacetic acid, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal, chlorthal-dimethyl, cinidone-ethyl, cinmethylin, cynosulfuron, cisanilide, clethodim, clodinafop, clodinafop-propargyl, clomazone, clomeprop, clopyralid, cloransulam, cloransulam-methyl, SMA, 4-CPV, CPME, 4-CPP, SRRS, cresol, cumiluron,

Zo cyanamide, cyanazine, cycloate, cyclosulfamuron, cycloxide, cyhalofop, cyhalofop-butyl, 2,А-О, 3,4-ОА, daimuron, dalapon, dazomet, 2,4-О08, 3,4-О8, 2,4 -OEV, desmedifam, desmethrin, dicamba, dichlobenil, ortho-dichlorobenzene, para-dichlorobenzene, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclosulam, difenzoquat, difenzoquat methyl sulfate, diflufenican, diflufenzopir, dimefuron, dimepiperate, dimethachlor, dimethamethrin, dimethenamid, dimethenamid-P, dimethipine, dimethylarsinic acid, dinitramine, dinoterb, diphenamide, dipropethrin, diquat, diquat dibromide, dithiopyr, diuron, OMOS, 3,4-OR, O5MA,

EVER, endothal, ERTS, esprocarb, etalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethephon, etofumesate, ethoxyphene, ethoxysulfuron, ethobenzanide, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fentrazamide, iron sulfate, flamprop -M, fluzasulfuron, florasulam, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, fluazolate, flucarbazone, flucarbazone-sodium, flusetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetralin, flumetsulam, flumiclorac, flumiclorac -pentyl, flumioxazin, flumipropin, rluometuron, fluoroglycofen, fluoroglycofen-ethyl, fluoxaprop, flupoxam, flupropacil, flupropanate, flupirsulfuron, flupirsulfuron-methyl-sodium, flurenol, fluridone, flurochloridone, fluroxypyr, rlurtamone, fluthiacet, fluthiacet-methylam, fomesaf , fosamine, glufosinate, glufosinate-ammonium, glyphosate, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, HO-252, hexazinone, imazametabenz, imazametabenz-methyl, imazamox, im azapic, imazapyr, imazaquin, imazetapir, imazosulfuron, indanophan, indaziflam, methyl iodide, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ipfencarbazone, isoproturon, isouron, isoxaben, isoxachlortol, isoxaflutol, isoxapyrifop, carbutylate, lactofen, lenacil, linuron,

MAA, MAMA, MSRA, MSORA-thioethyl, MSRV, mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfuron, mesosulfuron-methyl, mesotrione, metam, metamifop, metamitron, metazachlor, metazosulfuron, metabenzthiazuron, metazol, methylarsonic acid, methyldimron, methyl isothiocyanate, metobenzuron, metobromuron, metolachlor, C-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, MK-616, molinate, monolinuron, monosulfuron, monosulfuron-ether, M5MA, naproanilide, napropamide, naptalam, MOA-402989, neburon, nicosulfuron, nipyraclofen, n-methylglyphosate, nonanoic acid, norflurazon, oleic acid (fatty acids), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxacyclomefon, oxyfluorfen, paraquat, paraquat dichloride, pebulate, pendimethalin, penoxulam, pentachlorophenol , pentanochlor, pentoxazone, pentaxamide, petroleum oils, fenmedipham, phenmedipham-ethyl, picloram, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, pretilachlor, primisulfu ron, primisulfuron-methyl, prodiamine, profluazole, propoxide, prohexadione-calcium, prometon, promethrin, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propizamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyraflufen- ethyl, pyrasulfotol, pyrazolinate, pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxifene, pyribenzoxime, pyributycarb, pyridafol, pyridate, pyrifthalide, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, piroxulam, quinclorac, quinmerac, quinoclamine, quizalofop, quizalofop-P, quizalofop-ethyl, quizalofop-P-ethyl, rimsulfuron, saflufenacil, sethoxidim, siduron, simazine, symetryn, ZMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosate, sulfosulfuron , sulfuric acid, vegetable oils, 2,3,6-

TVA, TSA, TSA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxidim, terbacil, terbumeton, terbuthylazine, terbutrin, tenilchlor, thiazafluron, thiazopyr, thifensulfuron, thiencarbazone, thifensulfuron-methyl, thiobencarb, thiocarbazil, topramezon, tralkoxidim, triafamone, trialate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, tricamba, trikhlopir, triethazine, trifloxysulfuron, trifloxysulfuron-sodium, trifluralin, triflusulfuron, triflusulfuron-methyl, trifop, trifop-methyl, trihydroxytriazine, trinexapak-ethyl, tritosulfuron, ethyl ester of IZ -(2-chloro-4-

Zo fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy|-2- pyridyloxyacetic acid (SAB KM 353292-31-6) , 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic acid (SAB EM 943832-60-8) and 4-hydroxy-3-|((2- (3-Methoxypropyl)-6-(difluoromethyl)-3-pyridinylcarbonyl|-bicyclo|3.2.Zoct-3-en-2-one.

Particularly preferred combinations are polymorph form 2 and ametryn, atrazine, bicyclopyrone, cinosulfuron, clodinafop-propargyl, clomazone, dicamba, dimetachlor, diquat, fluazifop-p-butyl, fomesafen, glyphosate, mesotrione, molinate, napropamide, C-metolachlor, nicosulfuron, paraquat, pinoxaden, pretilachlor, primisulfuron, promethrin, prosulfocarb, prosulfuron, pyridate, pyriphthalide, tralkoxide, triasulfuron, and trifloxysulfuron-sodium.

Although compositions containing a polymorph of the present invention and another herbicide are clearly disclosed above, one skilled in the art will appreciate that the present invention encompasses the three-component mixture as well as the many combinations containing the two-component mixtures indicated above.

For the avoidance of doubt, even if not expressly stated above, the admixture components may also be in the form of any acceptable agrochemically acceptable ester or salt, as mentioned for example in Te Rebwiiside Mapaai,

Twipeepii Eaiiop, ViyibNi Stor Rgoiesip Soipsii, 2003.

Various aspects and embodiments of the present invention will now be illustrated in more detail by way of example and the following figures, in which the following is shown:

Figure 1 shows powder X-ray patterns of polymorphs M-(2-methoxybenzoyl) /-4-

Imethylaminocarbonyl) amino|benzenesulfonamide, which were named Form 1, Form 2 and Form 3, where the diffraction lines of Form 2 and C are those expected from the single crystal structure and the diffraction lines of Form 1 were obtained by powder X-ray diffraction analysis.

In fig. 2 shows powder X-ray patterns of (a) form 2, (b) form 3 and (c) 50"7C suspension analyzed after 2 days.

In fig. C shows powder X-ray patterns of (a) form 1, (b) form 2, (c) form 3 and (a) 50"C suspension analyzed after 2 days, (c) 60"C suspension analyzed after 2 days.

In fig. 4 shows powder X-ray patterns of (a) Form 2, (6) a 60"C suspension analyzed after 8 days, and (c) a 50"7C suspension analyzed after 8 days. because in fig. 5 shows powder X-ray patterns of (a) form 2, (b) form 3, (c) 60"С hanging,

analyzed after 8 days, and (e) 507C suspension analyzed after 8 days.

EXAMPLES

1. Obtaining polymorphs

The compound of formula (I) was prepared as described in US Pat. No. 5,215,570.

And. Obtaining polymorph form 1

The compound of formula (1) obtained as described in US patent 52155070 was taken up in ice water and the precipitated product was separated and dried to give polymorph form 1. 16. Preparation of polymorph form 2

55 ml of acetone was added to 4.6 g of polymorph form 1 and heated to reflux temperature (56°C). 3 ml of water was added to form a pale yellow solution, which was allowed to cool slowly. The resulting crystals were isolated by filtration and dried. O5C - the analysis confirmed the presence of the form 2 polymorph with a melting point of 215760. 1c. Transformation of form 1 into form 2 by applying a suspension seed

300 g of form 1 polymorph was mixed with 1500 g of 3095 water/acetone and heated to 60°C. 3 g of form 2 polymorph was added to the suspension as a seed. O5C was not detected.

Crystals were collected by filtration under reduced pressure at 60°C, moisture was separated from them on a filter and then dried to constant weight in a vacuum oven at 40°C. Drying in an oven took 4 hours, after which 200 g of polymorph form 2 of 97905 purity (as assessed by O5C) was obtained. 14. Obtaining polymorph form 2 crystals for single crystal analysis

0.5 g of polymorph form 2 and 2 g of 5095 ethyl acetate/acetonitrile were mixed. The resulting solution was left for 120 days. During this time, the solution level decreased, and crystals became visible. The tube was capped and the remaining solvent was allowed to evaporate before collecting and analyzing the crystals.

That. Obtaining polymorph form Z

0.2 g of polymorph form 1 was dissolved in 15-20 ml of acetone at 45"C. Water was added to provide 2595 water in the water/acetone composition. The resulting precipitate was stirred at 45"C. In the samples taken after 30 minutes, the presence of polymorph form 1 was detected. U

From the samples taken after 5, 7 and 20 days, the presence of polymorph form 3 was detected. 2. Analysis of polymorphs

After preparation using the methods detailed above, the samples were analyzed by powder X-ray diffraction, and/or single crystal X-ray diffraction, and/or differential scanning calorimetry (055).

The analysis by powder X-ray diffraction of the solid material was carried out using a Vhikeg 08 powder diffractometer. The samples were fixed in sample holders

Regrech and samples were leveled. The specimen holder was rotated and x-rays were captured from 4" to 34" of 2-theta, with a scan time of 25-30 minutes depending on image intensity.

Intensity data for the single crystal were collected on a diffractometer of Ohio Hsairag RH OpKga using SiCo irradiation ((Х-1.54056 А) with a graphite monochromator. The crystal was fixed in MMUN oil at room temperature for data collection. The data was decoded using the SKUZTAI 5 software package .

OS was performed using Mensheg Toiedo O5C 820 rg 0O5C1. Approximately 5 mg of sample was loaded and heated from 257°C to 250°C at a rate of 10°C/minute on a resv820 or from 40°7°C to 250°C at a rate of 10°C/minute on an O5C1. There were holes in the cover of the OS crucible to allow the escape of any gas formed during the heating of the sample. 3. Stability of polymorphs

Approximately 0.1 g of each of Form 1, Form 2 and Form C was added to 10 ml of ethanol at 50°C and 60°C until a solid (suspension) formed in the solution. During the stirring, the temperature was maintained and the crystalline form was studied after 2 and 8 days.

At 50°C and 60°C after 2 days, form 2 and form C were still present, as seen in fig. 1. There were no data on the presence of form 1.

With additional suspension for a total of 8 days, complete transformation of form 2 was detected at both temperature values, see fig. 3.

Although the present invention has been described with reference to preferred embodiments and examples thereof, the scope of the present invention is not limited to such described embodiments. As will be apparent to those skilled in the art, modifications and adaptations may be made to the above-described invention without departing from the spirit and scope of the invention as defined and limited by the appended claims.

All publications cited herein are hereby incorporated by reference in their entirety for all purposes to the same extent as if each individual publication were specifically and individually indicated as being so incorporated by reference.

Claims (14)

FORMULA OF THE INVENTION 1. Crystalline polymorph of the compound of formula I, which has the following lattice parameters: a-19.38(5), p-7.34(5), c-22.95(5), o-90.00, B-90 ,00, y-90,00 and volume-3264,8(5) Az. 2. The crystalline polymorph according to claim 1, where the polymorph is characterized by a powder X-ray pattern expressed in angles 26, where the powder X-ray pattern includes: (a) at least one value of the angle 26, which is 9.0:0.2; and (p) one value of the angle 26, which is 21.750.2; and (c) at least three values of angle 26 selected from the group consisting of 7.750.2, 11.9:20.2, 13.450.2, 15.020.2, 15.6:50.2, 16.1-0, 2 and 18.0:50.2. 3. The crystalline polymorph according to claim 1 or claim 2, which has a melting point of 216x5 "C. 4. A crystalline polymorph of the compound of formula I, where the polymorph is characterized by a powder X-ray pattern expressed in angles 28, where the powder X-ray pattern includes: (a) at least one value of the angle 26, which is 9.0:0.2; and (p) one value of angle 29, which is 21.750.2; and (c) at least three values of angle 26 selected from the group consisting of 7.750.2, 11.950.2, 13.450.2, 15.020.2, 15.6:50.2, 16.1-0.2, and 18, 0:50.2. 5. The crystalline polymorph according to claim 4, which has a melting point of 21625 "С. 6. The crystalline polymorph of the compound of formula I, which has the following lattice parameters: а-7.96(5), р-23.56(5), с-9.11(5), о-90.00, D-92 ,58(5), y-90,00 and volume-1708,2(5) Az. 7. The crystalline polymorph according to claim 6, where the polymorph is characterized by a powder X-ray pattern expressed in angles 26, where the powder X-ray pattern includes: (a) one value of the angle 26, which is 16.9:0.2; and (p) one value of angle 26, which is 18.9:0.2; and (c) at least three values of angle 26 selected from the group consisting of 7.5520.2, 12.350.2, 13.40.2, 14.450.2, 14.950.2, 15.8:-0.2, 18 ,3:50.2, 20.9:50.2, 21.9:50.2, 22.650.2 and 23.8:0.2. 8. The crystalline polymorph according to claim 6 or claim 7, which has a melting point of 20255 "С. 9. A crystalline polymorph of the compound of formula I, where the polymorph is characterized by a powder X-ray pattern expressed in angles 28, where the powder X-ray pattern includes: (a) one value of the angle 26, which is 16.9:0.2; and (p) one value of angle 26, which is 18.9:0.2; and (c) at least three values of angle 26 selected from the group consisting of 7.5520.2, 12.350.2, 13.40.2, 14.450.2, 14.950.2, 15.8:-0.2, 18.350 ,2, 20.950.2, 21.9:50.2, 22.650.2 and 23.8:50.2. 10. The crystalline polymorph according to claim 9, which has a melting point of 2025 "С. 11. An agricultural composition comprising a polymorph according to any one of claims 1-10 and at least one agriculturally suitable carrier or diluent. 12. The composition according to claim 11, which additionally contains at least one herbicide. 13. A method of protecting crops of useful plants from the harmful effects of a herbicide, which includes the use of a polymorph according to any of claims 1-10 or a composition according to claim 11 or claim 12 in relation to the place of growth of useful plants. 14. A method of weed control in crops of useful plants, which includes treating useful plants, their seeds or cuttings, or places of growth of useful plants at the same time or at different times with a herbicide and a polymorph according to any of claims 1-10. x Chng. 1 IK N Y EN : SHY SHE t y 4 Her BELTS y spike Oi yo shin shi shi From the Farm? 57 you OPN LIVO U Z VO V, with ZhK voy A m She o nn ee NN Nv EK NN i NN J ferny3 0020000 NE OO OR BY OIMZVIMTEKZHIya, id ish 8. Hey I PoFerma write nin i ny NN A NN B 2- theta scale "Fig. 2 j 1 M 4 p ny A NN PE a EE Z E NE N V M NYA 5 N Ni U y ХIi vyh K pa 7 N i g. 7 y On EN N ny i still EE nn p EE I pe - 5 : : : and Not shh And and ! B y y x B : n - 2-theta-scale fig. 3 she id UA d2-teta-nkala Fig. 4 to me and in! E in | ; : ! ! ho and eat: Eh! heh Ne M n- 2-theta-shkalyaaya "Chin, 5 of 1: 1 th : B : : I : EN KU : i and B ! IS ! | E U E yah N I N what nya their 2-theta-scale