EA042688B1 - HERBICIDE COMPOSITION CONTAINING METAL CHELATE AND MESOTRION POLYMORPHS AND HERBICIDE, AND METHOD FOR ITS PRODUCTION - Google Patents

Description

The field of technology to which the invention belongs

The present invention relates to a herbicidal composition containing polymorphs of a metal chelate and mesotrione herbicide, as well as to a method for its preparation.

State of the art

Cyclohexanedione compounds exhibit herbicidal activity. Mesotrione is a cyclohexane-1,3-dione herbicide designed to selectively control a wide range of weeds in maize cultivation. The term mesotrione as used herein means 2-(2'nitro-4'-methylsulfonylbenzoyl)-1,3-cyclohexanedione, including any enol or tautomeric forms of the molecule. In addition, it includes all tautomeric, racemic and optical isomers derived from salts and various substituted forms of mesotrione. In addition, it includes all agriculturally acceptable salts derived from mesotrione.

Mesotrione is a synthetic analogue of a naturally occurring herbicidal product derived from the horsetail plant (Callistemon citrinus). Mesotrione acts as a phydroxyphenylpyruvate dioxygenase inhibitor, which ultimately affects carotenoid biosynthesis. The selectivity in the case of maize is due to differential metabolism (to the 4-hydroxy derivative) and also possibly due to slower uptake by the leaves. It is used for both pre-emergence and post-emergence control of broadleaf weeds such as Xanthium strumarium, Ambrosia trifida, Abutilon theophrasti and Chenopodium, Amaranthus as well as Polygonum spp. and some grassy weeds in the case of maize.

Mesotrione is rapidly taken up by weed species after foliar application and is distributed in plants by both acropetal and basipetal movement. Maize is mesotrione tolerant due to selective metabolism by the cultivated plant. The slower uptake of mesotrione compared to susceptible weed species may also favor its use as a selective herbicide for maize applications.

It has been found that aqueous formulations of active ingredients such as mesotrione that are insoluble or partially soluble in water may have a number of disadvantages such as chemical degradation, crystal formation, agglomeration, thickening or gel formation, serum formation, settling, sedimentation and so on. This problem is exacerbated when the active ingredient has the ability to remain in different crystalline forms or polymorphs.

Mesotrione exhibits polymorphism. US 8,063,253 and US 8,980,796 disclose various mesotrione polymorphs and methods for preparing the various polymorphs.

US 8,063,253 discloses that the mesotrione Form I polymorph is the thermodynamically stable form and Form II is the metastable form. The metastable form may gradually convert to the thermodynamically stable Form I. A formulation containing these forms may lead to storage stability problems as well as when the formulation is used in the field.

US 8980796 discloses mesotrione polymorph 3 having improved physical and biological properties.

US 5,912,207 discloses that herbicidal cyclohexanedione compounds, such as mesotrione, have the disadvantage that they are degradable in water and in certain solvents. Metal chelates have been prepared to overcome the disadvantages associated with degradation of mesotrione in aqueous formulations as well as under specific solvent conditions.

The interconversion of polymorphs, the dramatic difference in their physical properties, and their unpredictable properties in water and other solvents make it difficult to obtain a mesotrione-based formulation having the desired physical and biological properties.

The inventors' attempt to develop mesotrione chelate formulations in combination with other active ingredients has led to stability problems and handling disadvantages such as settling, thickening and sedimentation. The disadvantages found are associated with the large particle size of the mesotrione chelate. This requires additional effort to obtain an active ingredient having the desired uniform particle size, and during such processes, morphological changes in the particles can occur, which result in formulation deficiencies.

Another common problem for agrochemical composition is related to the toxicological profile of the product. In some cases, the products are unacceptable due to the potential for eye irritation that may occur when handling the formulation. This property can lead to restrictive product labeling based on composition, which limits the suitability of the product for its intended use.

The EPA signal word for the marketed combination of mesotrione and Smetolachlor (trade name: Camix) is a Warning. Compositions classified in this way may cause an undesirable degree of eye irritation by the composition.

Therefore, it has been difficult to develop ways to improve existing mesotrione formulation products without the disadvantages of existing formulations.

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Objectives of the invention

The aim of the present invention is to obtain polymorphs of mesotrione chelate.

Another object of the present invention is to provide a process for the preparation of mesotrione chelate polymorphs.

Another object of the present invention is to provide stable herbicidal formulations containing mesotrione chelate polymorphs.

Another object of the present invention is to provide a stable herbicidal composition containing mesotrione chelate polymorphs having an improved toxicological profile.

The aim of the present invention is to obtain polymorphs of copper chelate and mesotrione.

Brief description of the invention

The present invention provides a herbicidal composition containing metal chelate and mesotrione polymorphs and a chloroacetanilide herbicide.

In addition, the present invention relates to a method for preparing a herbicidal composition containing metal chelate and mesotrione polymorphs and a chloroacetanilide herbicide.

Detailed description

The present inventors have surprisingly found that mesotrione chelate exists in various polymorphic forms. These crystalline forms exhibit various properties, which are characterized by X-ray powder diffraction, as well as other physical properties. In addition, it has been found that two polymorphs of a metal chelate and mesotrione can be prepared using suitable methods, which are suitable for obtaining stable formulations. These new polymorphs, as well as methods for their preparation, are described below.

Surprisingly, the inventors of the present invention have found that various methods for producing metal chelate and mesotrione provide different polymorphs of the metal chelate and mesotrione.

In addition, the authors of the present invention unexpectedly noted that the compositions containing the polymorph form of the metal chelate and mesotrione, provide less eye irritation.

The two innovative polymorphs of the present invention are referred to as copper chelate mesotrione form I and copper mesotrione chelate form II.

The present invention also provides a process for producing metal chelate and mesotrione polymorphs.

In addition, methods are provided for preparing Form I copper chelate and mesotrione and Form II copper chelate and mesotrione.

Most surprisingly, the present inventors have found that form I of copper mesotrione chelate is suitable for the preparation of herbicidal compositions, especially liquid compositions.

Accordingly, herbicidal compositions are provided comprising Form I copper chelate and mesotrione and Form II copper chelate and mesotrione.

Accordingly, a form I chelate of copper and mesotrione is provided.

In one embodiment, the present invention provides a Form I chelate of copper and mesotrione that exhibits a characteristic powder X-ray diffraction pattern.

In another embodiment, a form I copper chelate of mesotrione is provided which shows an x-ray diffraction pattern, expressed in 2θ degrees (±0.2°), showing at least three of the following reflections: 9.1; 10.6; 11.8; 13.7; 15.9; 16.6; 18.3; 21.4; 22.1; 22.4; 24.1 and 27.7.

In another embodiment of the present invention, a Form I copper chelate of mesotrione is provided which shows an x-ray diffraction pattern, expressed in 2θ degrees (±0.2°), showing at least five of the following reflections: 9.1; 10.6; 11.8; 13.7; 15.9; 16.6; 18.3; 21.4; 22.1; 22.4; 24.1 and 27.7.

In yet another embodiment of the present invention, a form I copper chelate of mesotrione is provided which shows an x-ray diffraction pattern, expressed in 2θ degrees (±0.2°), showing all of the following reflections: 9.1; 10.6; 11.8; 13.7; 15.9; 16.6; 18.3; 21.4; 22.1; 22.4; 24.1 and 27.7.

In another embodiment, a form I copper chelate of mesotrione is provided, characterized by all of the following reflectances and interplanar spacing d values as depicted in the table below.

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Angle (20±0.2°) Values of interplanar distance (d), A 9.1 10.6 I.8 13.7 15.9 16.6 18.3 9.7 8.4 7.5 6.5 5.6 5.3 4.8 21.4 4.2 22.1 4.0 22.4 4.0 24.1 3.7 27.7 3.2

Brief description of graphic materials

In FIG. 1 shows a typical X-ray powder diffraction pattern of copper chelate form I and mesotrione in accordance with the present invention.

In FIG. 2 shows a typical FT-IR spectrum of Form I copper chelate and mesotrione in accordance with the present invention.

In FIG. 3 shows a typical X-ray powder diffraction pattern of copper chelate and mesotrione form II in accordance with the present invention.

In FIG. 4 shows a typical FT-IR spectrum of form II copper chelate and mesotrione in accordance with the present invention.

During the study of polymorphic forms of copper chelate and mesotrione, another polymorphic form was discovered, called form II. In contrast to form I copper chelate and mesotrione, it has been found that form II copper chelate is suitable for preparing solid formulations in particular. Form II of the copper chelate and mesotrione according to the present invention can be identified using an x-ray powder diffraction pattern.

In one embodiment, a form II copper chelate of mesotrione is provided that shows an x-ray diffraction pattern, expressed in degrees of 2Θ (±0.2°), showing at least 3 of the following reflections: 7.6; 9.1; 10.7; 11.8; 13.7; 15.4; 18.8; 21.0; 22.3; 23.8; 27.7; 28.7 and 29.5.

In another embodiment, a form II copper chelate of mesotrione is provided which shows an x-ray diffraction pattern, expressed in degrees of 2Θ (±0.2°), showing all of the following reflections: 7.6; 9.1; 10.7; 11.8; 13.7; 15.4; 18.8; 21.0; 22.3; 23.8; 27.7; 28.7 and 29.5.

In one embodiment, a form II copper chelate of mesotrione is provided having the following reflections expressed as 2Θ angle values and interplanar spacing d values as shown in the table below.

Angle (20±0.2°) Values of interplanar distance (d), A 7.6 I,5 9.1 9.6 10.7 8.3 I,8 7.4 13.7 6.4 15.4 5.8 18.8 4.8 21.0 4.2 22.3 4.0 23.8 3.7 27.7 3.2 28.7 3.1 29.5 3.0

In one embodiment of the present invention, a process for preparing a metal chelate mesotrione polymorph is provided.

In one embodiment, a process is provided for preparing a metal chelate mesotrione polymorph, said process comprising the steps of:

a) obtaining a dispersion of mesotrione using a suitable base and water;

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b) allowing the metal chelate and mesotrione polymorph to precipitate by adding a metal salt solution, and

c) filtration and isolation of the metal chelate polymorph and mesotrione.

In one embodiment of the present invention, the base used in step (a) is selected from alkali or alkaline earth metal hydroxides, carbonates, bicarbonates, or ammonium base.

In another embodiment, the base used in step (a) is selected from sodium hydroxide or ammonium hydroxide.

In another embodiment, metal ions that are useful in the formation of the metal chelate polymorphs of the present invention include transition metal ions such as Mn ⁺² , Co ⁺² , Cu ⁺² , Zn ⁺² , Fe ⁺² , Ni ⁺² and Fe ⁺³ .

In another embodiment, metal salts that are suitable for the formation of the metal chelate polymorphs of the present invention include the metal salts of Mn, Co, Cu, Zn, Fe, Ni, and Fe.

In yet another embodiment, the metal ions of particular interest are selected from Zn ⁺² , Fe ⁺² and Cu ⁺² .

In another embodiment, a process is provided for preparing Form I copper chelate and mesotrione, said process comprising the steps of:

a) obtaining a dispersion of mesotrione using sodium hydroxide and water;

b) allowing the metal chelate and mesotrione form I to precipitate by adding a copper salt solution and

c) filtration and isolation of Form I copper chelate and mesotrione.

In one embodiment, the pH of the dispersion in step (a) ranges from about 6 to about 10.

In one embodiment, in step (b), a suitable copper salt is selected from chlorides, sulfates, nitrates, carbonates and phosphates.

Form I chelate of copper and mesotrione is particularly preferred for the preparation of liquid formulations. In particular, it has been found that form I of the copper chelate of mesotrione is suitable in terms of ease of preparation of the composition, handling of the composition, especially when stored for a long period of time. In addition, formulations containing form I copper chelate and mesotrione have been found to be preferred in terms of dilution and formulation use. Physical characteristics such as bulk density and particle size demonstrate these advantages.

Form I chelate of copper and mesotrione exhibits a characteristic bulk density. The bulk density of Form I copper chelate and mesotrione is from about 0.51 to about 0.535 g/ml.

Form I chelate of copper and mesotrione has a characteristic particle size. The median diameter or average particle size distribution (D50 and D90) recorded for Form I copper chelate and mesotrione is shown in the table below. Samples (a) and (b) were obtained in accordance with the method described in example 1.

No. p / p Sample name Particle size (µm) D(0.5) D(0.9) 1 Form Ι-a of copper chelate and mesotrione 7.94 13.02 2 Form Ι-b of copper chelate and mesotrione 7.62 13.22

The above listed characteristic physical properties of form I copper chelate and mesotrione demonstrate the advantages of preparing and using herbicidal formulations containing form I copper chelate and mesotrione. The inventors of the present invention have found that, due to the smaller particle size, form I of the copper chelate and mesotrione is suitable for the preparation of a liquid formulation, while avoiding repeated and laborious milling to obtain the desired particle size. In addition, it was unexpectedly found that in the preparation of solid compositions containing form I copper chelate and mesotrione, it was possible to completely avoid the use of an intensive grinding process. In addition, it has been found that by avoiding multiple grinding processes, the possibility of morphological changes of the mesotrione chelate to a lesser extent leads to a physically and chemically stable composition.

According to the present invention, a method is provided for the preparation of form II copper chelate and mesotrione.

In one embodiment, a process is provided for preparing Form II copper chelate and mesotrione, said process comprising the steps of:

a) obtaining a dispersion of mesotrione using ammonium hydroxide and water;

b) allowing Form II copper chelate and mesotrione to precipitate by adding a copper salt solution and

c) filtration and isolation of Form II copper chelate and mesotrione.

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In one embodiment, the pH of the dispersion in step (a) is from about 6 to about 9.

In one embodiment, in step (b), a suitable copper salt is selected from chlorides, sulfates, nitrates, carbonates and phosphates.

Form II of copper chelate and mesotrione exhibits a characteristic bulk density. The bulk density of form II copper chelate and mesotrione is from about 0.61 to about 0.65 g/ml.

Form II of copper chelate and mesotrione has a characteristic particle size. The median diameter or average particle size distribution (D50 and D90) reported for Form II copper chelate and mesotrione is shown in the table below. Samples (a) and (b) were obtained in accordance with the method described in example 2.

No. p / p Sample name Particle size (µm) D(0.5) D(0.9) 1 P-form of copper chelate and mesotrione 17.58 34.08 2 Form Π-b of copper chelate and mesotrione 16.74 27.33

From the above data, it can be concluded that form II of copper chelate and mesotrione is suitable for obtaining, in particular, solid compositions, and may not require any milling process. In addition, the present inventors have found that the use of an innovative Form II copper chelate in formulations helps to prevent any undesirable changes in the crystalline nature of mesotrione, thus providing stable formulations.

The present invention also relates to formulations containing metal chelate and mesotrione polymorphs.

In one embodiment, compositions are provided containing Form I copper chelate and mesotrione and Form II copper chelate and mesotrione.

In one embodiment, herbicidal compositions are provided containing Form I copper chelate and mesotrione.

In another embodiment, herbicidal formulations containing Form I copper chelate and mesotrione and additives are provided that are suitable for formulating plant protection products.

The present invention also relates to a process for the preparation of herbicidal compositions containing polymorphs of copper chelate and mesotrione.

In one embodiment, the present invention relates to a process for preparing a herbicidal formulation comprising a copper chelate mesotrione polymorph, said process comprising the steps of:

a) obtaining a dispersion of mesotrione using a suitable base and water;

b) adding a metal salt solution to form a metal chelate and mesotrione polymorph;

c) adding other agrochemical auxiliaries, if necessary;

d) optionally adding one or more other active ingredients, and

e) homogenizing the mixture.

In another embodiment, a method is provided for preparing a herbicidal formulation comprising a copper chelate mesotrione polymorph, said method comprising the steps of:

a) obtaining a dispersion of mesotrione using a suitable base and water;

b) adding a copper salt solution to form copper chelate form I and mesotrione;

c) adding other agrochemical auxiliaries, if necessary;

d) optionally adding one or more other active ingredients, and

e) homogenizing the mixture.

In yet another embodiment, a process is provided for preparing a herbicidal formulation comprising copper chelate form I and mesotrione, said process comprising the steps of:

a) obtaining a dispersion of mesotrione using sodium hydroxide and water;

b) ensuring precipitation of form I copper chelate and mesotrione by adding a copper salt solution;

c) filtration of Form I copper chelate and mesotrione, if necessary;

d) adding other agrochemical auxiliaries, if necessary;

e) optionally adding one or more other active ingredients, and

f) homogenizing the mixture.

In another embodiment, a process is provided for preparing a herbicidal formulation comprising copper chelate form I and mesotrione, said process comprising the steps of:

a) obtaining a dispersion of mesotrione using sodium hydroxide and water;

b) ensuring precipitation of form I copper chelate and mesotrione by adding a copper salt solution;

c) adding other agrochemical auxiliaries, if necessary;

d) optionally adding one or more other active ingredients, and

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e) homogenizing the mixture.

In yet another embodiment, a method is provided for preparing a herbicidal formulation comprising a Form II metal chelate and mesotrione, said method comprising the steps of:

a) obtaining a dispersion of mesotrione using ammonium hydroxide and water;

b) adding a metal salt solution to form a form II metal chelate and mesotrione;

c) adding other agrochemical auxiliaries, if necessary;

d) optionally adding one or more other active ingredients, and

e) homogenizing the mixture.

In yet another embodiment, a process is provided for preparing a herbicidal composition comprising Form II copper chelate and mesotrione, said process comprising the steps of:

a) obtaining a dispersion of mesotrione using ammonium hydroxide and water;

b) adding a copper salt solution to form a form II metal chelate and mesotrione;

c) adding other agrochemical auxiliaries, if necessary;

d) optionally adding one or more other active ingredients, and

e) homogenizing the mixture.

In yet another embodiment, a process is provided for preparing a herbicidal composition comprising Form II copper chelate and mesotrione, said process comprising the steps of:

a) obtaining a dispersion of mesotrione using ammonium hydroxide and water;

b) allowing Form II copper chelate and mesotrione to precipitate by adding a copper salt solution and

c) filtering the form II copper chelate and mesotrione, if necessary;

d) adding other agrochemical auxiliaries, if necessary;

e) optionally adding one or more other active ingredients, and

f) homogenizing the mixture.

Form I of the copper mesotrione chelate of the present invention is of particular interest in mesotrione formulations in combination with one or more other plant protection products.

In one embodiment, the mesotrione copper chelate form I of the present invention is of particular interest in mesotrione-based formulations in combination with one or more other plant protection products, the mesotrione concentration ranging from about 0.01 to about 30% by weight of the composition.

In one embodiment, the present invention relates to herbicidal compositions containing form I copper chelate and mesotrione and a second active ingredient, together with suitable additives.

In another embodiment, the present invention relates to herbicidal combinations containing Form I copper chelate and mesotrione and a second active ingredient.

The second active ingredient is preferably a herbicide.

In one embodiment, the second herbicide that can be combined with copper chelate form I and mesotrione of the present invention is selected without limitation from isoxazolidinone herbicides, urea herbicides, triazine herbicides, hydroxybenzonitrile herbicides, organophosphate herbicides, thiocarbamate herbicides. , herbicides based on pyridazine; herbicides based on chloroacetanilide; benzothiazole herbicides; carbanylate herbicides; herbicides based on cyclohexenoxime; picolinic acid herbicides; herbicides based on pyridine; herbicides based on quinolinecarboxylic acid; chlortriazine herbicides, aryloxyphenoxypropionic herbicides, oxadiazolone herbicides; phenylurea herbicides, sulfonanilide herbicides; triazolopyrimidine herbicides, amide herbicides, pyridazine herbicides, dinitroaniline herbicides, or combinations thereof.

In a preferred embodiment, the second herbicide is selected from a triazine herbicide. With regard to the present invention, the term triazine refers to chemical compounds from the group of their equivalents, metabolites, salts, esters, isomers and derivatives. Examples of triazine herbicides include chlorazine, cyanazine, cyprazine, eglinazine, ipazine, mesoprazine, procyazine, proglinazine, propazine, sebutylazine, simazine, terbutylazine, trietazine, dipropetrin and fUcaojing and trihydroxytriazine.

Accordingly, a herbicidal formulation is provided comprising a Form I copper-mesotrione chelate and a triazine herbicide, together with other suitable adjuvants. The composition contains from about 0.01 to 30% by weight of Form I copper chelate and mesotrione and from about 1 to about 70% by weight of a triazine herbicide.

In another embodiment, the herbicide that may be present along with the copper and mesotrione chelate form I of the present invention is selected from an organophosphate herbicide. With regard to the present invention, the term organophosphorus refers to chemical compounds from the group of organophosphorus substances, their equivalents, metabolites, salts, esters, isomers and derivatives. Examples of organophosphate herbicides include amiprofos-methyl, amiprofos, anilofos, bensulide, bilanaphos, EVER, fosamine, butamiphos, claciphos, 2,4-DEP, DMPA, glufosinate, glufosinate-P, glyphosate, piperophos, huangcaoling and shuangjiaancaolin.

In another preferred embodiment, the second herbicide is selected from a chloroacetanilide herbicide. With regard to the present invention, the term chloroacetanilide refers to chemical compounds from the group of chloroacetanilide, their equivalents, metabolites, salts, esters, isomers and derivatives. Examples of chloroacetanilide herbicides include acetochlor, alachlor, butachlor, butenachlor, delachlor, diethatyl, dimetachlor, ethachlor, etaprochlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor, propisochlor, prinachlor, terbuchlor, tenylchlor, xylachlor.

In particular, the second herbicide is S-metolachlor.

Accordingly, a herbicidal formulation is provided comprising a Form I copper chelate and mesotrione and a chloroacetanilide herbicide along with other suitable adjuvants. The composition contains from about 0.01 to 20% by weight of Form I copper chelate and mesotrione and from about 1 to 70% by weight of a chloroacetanilide herbicide.

In another embodiment, according to the present invention, a formulation is provided comprising a Form I copper chelate and mesotrione, a chloroacetanilide herbicide and a triazine herbicide, together with other suitable excipients. The composition contains from about 0.01 to 20% by weight of Form I copper chelate and mesotrione, from about 1 to about 70% by weight of chloroacetanilide herbicide, and from about 1 to about 70% by weight of triazine herbicide.

In another embodiment, the present invention provides a composition comprising Form I copper chelate and mesotrione and S-metolachlor.

The present inventors have found that a composition containing Form I copper chelate and mesotrione and S-metolachlor causes mild eye irritation.

Compositions containing form I copper chelate and mesotrione according to the present invention include compositions based on both solid and liquid substances, such as powders, granules, dry formulations, solutions, emulsions, suspoemulsions, suspensions and microencapsulations in polymeric substances.

Preferably Form I of the copper chelate and mesotrione is suitable for liquid based formulations.

In one embodiment of the present invention, the Form I copper chelate and mesotrione formulations further comprise an antidote.

In one embodiment of the present invention, the antidote is selected from the group consisting of quinoline derivatives; benoxacor; dichlormide; fenchlorazole ethyl; fenclorim; flurazol; fluxofenima; furilazole; ethyl isoxadifen; mefenpyr; mefenpyr diethyl, oxabethrinil, cyometrinil, dimron, dimepiperate, cloquintoset-mexil and cyprosulfamide.

In one embodiment, a herbicidal formulation is provided comprising Form II copper chelate and mesotrione.

In another embodiment, a herbicidal formulation is provided comprising Form II copper chelate and mesotrione and additives suitable for a crop protection formulation.

Form II of the copper mesotrione chelate of the present invention is of particular interest in mesotrione formulations in combination with one or more other plant protection products.

In one embodiment, the mesotrione copper chelate form II of the present invention is of particular interest in mesotrione formulations in combination with one or more other plant protection products, wherein the mesotrione concentration ranges from about 0.01 to about 30% by weight of the composition.

In a preferred embodiment, a herbicidal formulation is provided comprising Form II copper chelate and mesotrione and a triazine herbicide, together with other suitable excipients. The composition contains from about 0.01 to about 30% by weight of Form II copper chelate and mesotrione and from about 1 to about 70% by weight of a triazine herbicide.

The compositions according to the present invention additionally contain conventional adjuvants suitable for the agrochemical formulation selected from solvents/carriers, surfactants, emulsifiers, dispersants, antifoams, antifreeze agents, coloring agents, wetting agents, anti-caking agents, structurants. , biocides, viscosity modifiers and binders. The content of the composition of these adjuvants is not particularly limiting and can be determined by a person skilled in the art in accordance with standard protocols.

The present invention further relates to a method for controlling undesirable weed species, said method comprising applying an effective amount of a composition containing a mesotrione chelate polymorph to the weeds or to their location.

In one embodiment, a method is provided for controlling undesirable weed species, the method comprising applying an effective amount of a composition containing Form I or Form II copper chelate and mesotrione to the weeds or to their location.

In another embodiment, a method is provided for controlling undesirable weed species, said method comprising applying an effective amount of a composition comprising Form I or Form II copper chelate and mesotrione along with one or more active ingredients to the weeds or to their location.

The compositions of the present invention may be sold as a pre-blended composition or set of ingredients, so that the individual components of the compositions may be mixed prior to spraying.

Therefore, in one aspect, the present invention provides a kit containing mesotrione and a component containing a suitable base and water.

In one embodiment, instructions are given for mixing the components of the kit prior to use.

Thus, in this embodiment, the kit according to the present invention also contains instructions for use.

In another embodiment, the kit contains mesotrione and a component containing a suitable base and water, as well as a third component containing at least one co-pesticide.

The authors of the present invention have succeeded in obtaining innovative polymorphs, as well as in their use to obtain the preferred stable herbicide formulations. The following specific examples further illustrate the present invention.

Examples

Example 1. Method for obtaining form I of copper chelate and mesotrione.

A suspension of mesotrione was obtained by adding 522 g of mesotrione to 2 liters of water. The pH of the slurry was raised to a value in the range of 7-10 with 20% sodium hydroxide solution. The mixture was stirred for one hour followed by the addition of a 30% copper sulfate solution. The reaction mixture was stirred for 2-3 hours and the pH of the mixture was maintained in the range of 4.8-5.2. The resulting slurry of Form I copper chelate and mesotrione was filtered, washed with hot water and dried under vacuum (555 g). The sample was analyzed by p-XRD and the resulting spectra are shown in FIG. I.

Example 2 Process for the preparation of Form II copper chelate and mesotrione.

A suspension of mesotrione was obtained by adding 345 g of mesotrione to 1.4 liters of water. The pH of the suspension was raised to a value in the range of 6-9 using an ammonia solution. The mixture was stirred for one hour followed by the addition of a 20% copper sulfate solution. The reaction mixture was stirred for 23 hours, and the pH of the mixture was maintained in the range of 4.5-5.5. The resulting slurry of form II copper chelate and mesotrione was filtered, washed with hot water and dried under vacuum (372 g). The sample was analyzed by p-XRD and the resulting spectra are shown in FIG. III.

Example 3 A suspoemulsion formulation of mesotrione and S-metolachlor according to the present invention was prepared as follows.

a) Obtaining (35)% suspension concentrate (SC) of mesotrione:

Ingredients % (w/w) Form I copper chelate and mesotrione 35 propylene glycol 6.0 DM water (enough) 59.0 Total 100

Procedure: Form I copper chelate and mesotrione were mixed with the listed ingredients and the mixture was homogenized by stirring and subjected to wet milling to achieve the desired particle size.

b) Preparation of (65)% oil-in-water (EW) emulsion of S-metolachlor:

Ingredients % (w/w) S-metolachlor 66.67 Block copolymer EO RO 2.65 DM water (enough) 30.68 Total 100

Procedure: S-metolachlor was mixed with the listed ingredients and homogenized by vigorous stirring to form an oil-in-water emulsion.

c) Preparation of a suspoemulsion (SE) formulation of mesotrione + S-metolachlor:

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Ingredients % (w/w) 65 EW S-metolachlor 58.5 35 SC form I copper chelate and mesotrione 10.86 Benoxacor 2.0 Block copolymer EO RO 8.0 propylene glycol 3.0 DM water (enough) 15.59 Total 100

Procedure: EW S-metolachlor was mixed with benoxacor, EO PO block copolymer and water. Then SC form I mesotrione chelate was added and mixed. The mixture was further homogenized by stirring until it became homogeneous. The formulation was found to be stable and no settling or thickening was observed during storage.

Example 4 A suspoemulsion formulation of mesotrione and S-metolachlor and atrazine according to the present invention was prepared as follows.

a) Obtaining (35)% suspension concentrate (SC) of mesotrione:

Ingredients % (w/w) Form I copper chelate and mesotrione 35.0 Block copolymer EO RO 6.0 DM water (enough) 59.0 Total 100

Procedure: Form I copper chelate and mesotrione were mixed with the listed ingredients and the mixture was homogenized by stirring.

b) Preparation of (65)% oil-in-water (EW) emulsion of s-metolachlor:

Ingredients % (w/w) S-metolachlor 66.67 Block copolymer EO RO 2.65 DM water (enough) 30.68 Total 100

Procedure: S-metolachlor was mixed with the listed ingredients and homogenized by stirring to form an oil-in-water emulsion.

c) Preparation of (58)% Atrazine Suspension Concentrate (SC):

Ingredients % (w/w) Atrazine 58.0 Block copolymer EO RO 5.0 DM water (enough) 37.0 Total 100

Procedure: Atrazine was mixed with the listed ingredients, homogenized by mixing to obtain a homogeneous suspension.

d) Preparation of the suspoemulsion (SE) formulation of S-metolachlor, mesotrione and atrazine:

Ingredients % (w/w) 65 EW S-metolachlor 45.23 35 SC form I copper chelate and mesotrione 8.40 58% SC atrazine 18.97 Benoxacor 2.0 Block copolymer EO RO 9.0 propylene glycol h, o DM water (enough) 13.40 Total 100

Procedure: EW S-metolachlor was mixed with water, benoxacor, EO PO block copolymer and propylene glycol followed by the addition of SC form I copper chelate and mesotrione and SC atrazine. Water was added and homogenized by stirring until a homogeneous suspension was obtained. The formulation was found to be stable and no settling or precipitation was observed during storage.

Example 5 A suspoemulsion formulation of mesotrione and S-metolachlor according to the present invention was prepared as follows.

a) Obtaining (35)% suspension concentrate (SC) of mesotrione:

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Ingredients % (w/w) mesotrione 35.0 copper sulfate 13.00 Sodium hydroxide (20% alkaline solution) 20.00 Block copolymer EO RO 6.00 DM-water (in sufficient 26.00 quantity) Total 100

Procedure: Mesotrione was mixed with the listed ingredients and the mixture was homogenized by agitation to form SC Form I copper chelate and mesotrione, which was further wet milled to the desired particle size.

b) Preparation of (65)% oil-in-water (EW) emulsion of S-metolachlor:

Ingredients % (w/w) S-metolachlor 66.67 Block copolymer EO RO 2.65 DM water (enough) 30.68 Total 100

Procedure: S-metolachlor was mixed with the listed ingredients and homogenized by stirring to form an oil-in-water emulsion.

c) Preparation of a suspoemulsion (SE) formulation of mesotrione + S-metolachlor:

Ingredients % (w/w) 65 EW S-metolachlor 58.5 35 SC form I copper chelate and mesotrione 10.86 Benoxacor 2.0 Block copolymer EO RO 10.0 propylene glycol h, o DM water (enough) 15.64 Total 100

Procedure: EW S-metolachlor was mixed with benoxacor, EO PO block copolymer, propylene glycol and water. Then SC form I of copper chelate and mesotrione was added and mixed. The mixture was further homogenized by stirring until it became homogeneous. The formulation was found to be stable and no settling or thickening was observed during storage.

Study of acute eye irritation.

A composition containing Form I copper chelate and mesotrione and S-metolachlor prepared in accordance with the present invention (Example 3) was tested for eye irritation. This study was performed to evaluate the effect of acute eye irritation of the composition.

Research recommendations.

This study was conducted in accordance with EPA, 1998: US Environmental Protection Agency (EPA), Health Exposure Testing Guideline, OCSPP 870.2400, Acute Eye Irritation (EPA 712-C-98-195) (August 1998).

OECD, 2012: Organization for Economic Co-operation and Development (OECD) Guidelines for Testing Chemicals, OECD 405, Acute eye irritation/corrosion, adopted by the Council on 2 October 2012.

In an acute eye irritation study on three adult female New Zealand albino rabbits, a single application per eye of 0.1 ml of the composition prepared in accordance with Example 3 of the present invention was performed on the right eye of the rabbit, while the opposite eye remained untreated and acted as a control. . Initially, one rabbit was tested. Based on the results obtained 24 hours after application of the test article (TIA), the irritation response was confirmed by simultaneously testing two additional rabbits. Observations were made 1, 24, 48, and 72 hours after TIA. They also checked their general health.

Individual evaluation of eye reactions after application. control eye. Female gender.

rabbit number 1 2 3 Plot Left Left Left

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applications Reaction Time watch Time watch Time watch 1 24 48 72 1 24 48 72 1 24 48 72 Turbidity: degree of intensity 0 0 0 0 0 0 0 0 0 0 0 0 Iris 0 0 0 0 0 0 0 0 0 0 0 0 Connective membrane of the eye (redness) 0 0 0 0 0 0 0 0 0 0 0 0 Connective membrane of the eye (chemosis) 0 0 0 0 0 0 0 0 0 0 0 0

Treated eye:

rabbit number 1 2 3 Area of application Right Right Right Reaction Time watch Time watch Time watch 1 24 48 72 1 24 48 72 1 24 48 72 Turbidity: degree of intensity 0 0 0 0 0 0 0 0 0 0 0 0 Iris 0 0 0 0 0 0 0 0 0 0 0 0 Connective membrane of the eye (redness) 1 2 1 0 1 1 0 0 1 1 0 0 Connective membrane of the eye (chemosis) 1 1 0 0 1 0 0 0 1 0 0 0

Individual observation of the cornea 24 hours after application using fluorescein staining.

control eye. Female gender.

rabbit number Eye control Day Reaction to fluorescein staining Details of the observation of the corneal response in the control eye 1 Left 1 negative No corneal epithelium damage was found. 2 negative No corneal epithelium damage was found. 3 negative No corneal epithelium damage was found. 2 Left 1 negative No corneal epithelium damage was found. 2 negative No corneal epithelium damage was found. 3 Left 1 negative No corneal epithelium damage was found. 2 negative No corneal epithelium damage was found.

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Claims (4)

Processed eye. rabbit number Eye control Day Reaction to staining with fluorescein dye Details of the observation of the corneal response in the control eye 1 Right 1 Positive 25% damage to the corneal epithelium was found 2 Positive 10% damage to the corneal epithelium was found 3 negative Epithelial damage cornea not found 2 Right 1 Positive 10% damage to the corneal epithelium was found 2 negative Epithelial damage cornea not found 3 Right 1 Positive 10% damage to the corneal epithelium was found 2 negative Epithelial damage cornea not found Based on the results of this study, the indication of classifications for the tested composition is as follows. Globally Harmonized System of Classification and Labeling of Chemicals (GHS 2015): not classified as an eye irritant. EPA toxicity categories (December 2002): Category III. The present invention is more specifically explained by the examples given above. However, it should be understood that the scope of the present invention is in no way limited by the examples. Any person skilled in the art will understand that the present invention includes the above examples and, in addition, can be modified and changed without deviating from the new ideas and advantages of the present invention, the inclusion of which is intended in the scope of the invention. CLAIM 1. A herbicidal composition comprising metal chelate and mesotrione polymorphs and a chloroacetanilide herbicide, wherein said metal chelate and mesotrione polymorph is form I of copper chelate and mesotrione, which shows an x-ray diffraction pattern expressed in degrees of angle 2Θ (±0.2°) , which shows at least three of the following reflections: 9.1; 10.6; 11.8; 13.7; 15.9; 16.6; 18.3; 21.4; 22.1; 22.4; 24.1 and 27.7, wherein said chloroacetanilide herbicide is selected from acetochlor, alachlor, butachlor, butenachlor, delachlor, diethatyl, dimetachlor, ethachlor, etaprochlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor, propisochlor, prinachlor, terbuchlor, tenylchlor, xylachlor. 2. The herbicidal composition of claim 1, wherein said chloroacetanilide herbicide is S-metolachlor or metolachlor. 3. A method for producing a herbicidal composition according to claim 1, said method comprising the steps of: a) obtaining a dispersion of mesotrione using sodium hydroxide and water; b) allowing Form I of the copper chelate and mesotrione to precipitate by adding a copper salt solution, and c) adding a chloroacetanilide herbicide selected from acetochlor, alachlor, butachlor, butenachlor, delachlor, dietatyl, dimetachlor, ethachlor, etaprochlor, metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor, propisochlor, prinachlor, terbuchlor, tenylchlor, xylachlor. 4. The method of claim 3, wherein said method further comprises step d) adding an agrochemical adjuvant. -