DESC:FIELD OF INVENTION
The present invention relates to solvate of methyl [2E]-2-{2-[6-(2-cynophenoxy) pyrimidine-4-yloxy] phenyl}-3-methoxyacrylate with organic acid, a process for its preparation. The present invention also relates to compositions comprising said solvate and method of using thereof.

BACKGROUND OF THE INVENTION
Methyl [2E]-2-{2-[6-(2-cynophenoxy) pyrimidine-4-yloxy] phenyl}-3-methoxyacrylate also known as azoxystrobin is represented by formula 1.

Formula 1
It is a systemic fungicide commonly used in agriculture. The substance is used as an active agent for protecting plants and fruit/vegetables from fungal diseases.

US5145856 disclose pyrimidine compounds including azoxystrobin and process for preparation of the same.

WO2008093325 disclose crystalline polymorphic and amorphous forms of the compound (E)-2-{2-[6-(2-cyanophenoxy) pyrimidin-4-yloxy] phenyl}-3-methoxy-acrylate (azoxystrobin). It also discloses processes for producing mixtures of the polymorphs, Form A & B, a process for preparing amorphous azoxystrobin and compositions containing these forms. It is disclosed in this art that Form B is less stable when contacted with a solvent and gets converted to stable Form A affecting storage stability of the composition. Amorphous form of azoxystrobin is extremely unstable and gets converted to Form B and eventually to Form A at room temperature, due to storage problem it is difficult to apply in production. Marketed compositions of azoxystrobin and mixtures show drawbacks like strong coalescence, poor fluidity, slow drying and filtration rates, due to crystal transformation. Further these uncontrollable crystalline changes cause many problems to post processing formulation and preparation of stable and effective fungicidal compositions of azoxystrobin.

The crystal solvates of azoxystrobin when used for formulation it is found to produce stable formulation. The present invention thus provides novel, solvates of azoxystrobin and process for preparation of the same. The present invention also provides a stable formulation comprising solvates of azoxystrobin. Therefore, the present invention overcomes the problems of the art as discussed above and exhibits better stability and operational convenience.

OBJECTS OF THE INVENTION
It is an object of the present invention to provide a novel solvate of methyl [2E]-2-{2-[6-(2-cynophenoxy) pyrimidine-4-yloxy] phenyl}-3-methoxyacrylate (azoxystrobin).

It is another object of the present invention to provide a process for the preparation of solvate of azoxystrobin.

It is an object of the present invention is to provide a composition comprising solvate of azoxystrobin and method of using said composition in agriculture.

It is another object of the present invention to provide a process for preparation of agrochemical compositions comprising solvate of azoxystrobin.

SUMMARY OF THE INVENTION
In an aspect the present invention provides a solvate of azoxystrobin.

In another aspect the present invention provides a solvate of azoxystrobin organic acid.

In another aspect the present invention provides a process for the preparation of a solvate of azoxystrobin comprising:
a) admixing azoxystrobin with an organic acid; and
b) subjecting said admixture to activation method or solution method resulting in solvate of azoxystrobin.
In another aspect the present invention provides a composition comprising said solvate of azoxystrobin.

In another aspect the present invention provides a composition comprising combination of said solvate of azoxystrobin and at least one pesticide.

In another aspect the present invention provides a process for preparation of a composition comprising said solvate of azoxystrobin.

In yet another aspect the present invention provides a method of using said solvate of azoxystrobin for controlling fungi.

In another aspect the present invention provides a method of controlling fungi comprising contacting fungi or their locus with a fungicidally effective amount of a solvate of azoxystrobin.

In another aspect the present inventio provides use of solvate of azoxystrobin controlling fungi in agriculture.

BRIEF DESCRIPTION OF DRAWINGS
Certain aspects of embodiment described herein with the reference of drawings for clear understanding are intended to illustrate, but not limit, the invention, wherein:

Fig.1 is X-ray powder diffraction (PXRD) diffractogram of solvate of azoxystrobin with propionic acid.

Fig.2 is Fourier transform infra-red spectrometer (FTIR) spectrum of solvate of azoxystrobin with propionic acid.

Fig.3 is a Differential scanning calorimetry (DSC) thermogram of solvate of azoxystrobin with propionic acid.

DETAILED DESCRIPTION OF THE INVENTION
For the purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of materials/ingredients used in the specification are to be understood as being modified in all instances by the term "about". The term "about" used to qualify the amounts of active agent shall be interpreted to mean "approximately" or "reasonably close to" and any statistically insignificant variations therefrom.

Thus, before describing the present invention in detail, it is to be understood that this invention is not limited to particularly exemplified systems or process parameters that may of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments of the invention only and is not intended to limit the scope of the invention in any manner. The use of examples anywhere in this specification including examples of any terms discussed herein is illustrative only, and in no way limits the scope and meaning of the invention or of any exemplified term. Likewise, the invention is not limited to various embodiments given in this specification.

It must be noted that, as used in this specification, the singular forms “a,” “an” and “the” include plural referents unless the content clearly dictates otherwise. The terms “preferred” and “preferably” refer to embodiments of the invention that may afford certain benefits, under certain circumstances.

As used herein, the terms “comprising” “including,” “having,” “containing,” “involving,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to.
In the context of the present invention the term ‘solvate’ is defined as an aggregate that consists of a solute or molecule with one or more solvent molecules.

The term ‘locus’ as used herein shall denote the vicinity of a desired crop in which fungal control is desired. The locus includes the vicinity of desired crop plants wherein the fungal infestation has occurred or is expected to occur. The term crop shall include a multitude of desired crop plants or an individual crop plant growing at a locus.

The term ‘control’ indicates eradication of the investigated fungi. A 100% control signifies total eradication of the fungi under investigation.
The term “fungicidally effective amount” of active component, as used herein, shall denote an amount that can be used to control harmful fungi.

The present invention provides a solvate of azoxystrobin, compositions comprising said solvate and processes for preparation thereof.

In an embodiment the present invention provides a solvate of azoxystrobin organic acid.

In an embodiment the present invention provides a solvate of azoxystrobin with propionic acid.

In an embodiment the X-ray powder diffraction pattern of solvate of azoxystrobin with propionic acid is represented in Fig. 1.

In an embodiment the present invention provides solvate of azoxystrobin with propionic acid characterized by an X-ray powder diffraction pattern expressed in 2? (±0.2°) having at least three peaks at about 7.32, 7.57, 8.34, 11.78, 12.23, 13.31, 13.66, 14.48, 15.59, 16.64, 18.18, 18.89, 20.31, 21.27, 22.61, 23.72, 24.51, 26.45, 25.95, 28.40, 28.70, 30.61, 31.40, 32.93, and 34.22 ± 0.2.

In another embodiment the solvate of azoxystrobin with propionic acid characterized by an X-ray powder diffraction pattern expressed in 2?(±0.2°) having peaks at about 7.57, 8.34, 11.78, 13.31, 14.48, 16.64, 18.18, 20.31, 22.61, 23.72, 24.51 and 26.45.

In an embodiment, the FTIR spectrum of solvate of azoxystrobin with propionic acid is represented in Fig. 2.

In another embodiment the solvate of azoxystrobin with propionic acid exhibits FTIR spectrum having at least three characteristic absorbance peaks (± 4 cm-1) at about 3061, 3036, 2951, 2234, 1884, 1711, 1626, 1589, 1566, 1488, 1445, 1414, 1377, 1274, 1257, 1230, 1207, 1185, 1156, 1126, 1101, 1056, 996, 960, 945, 886, 838, 815, 771, 761, 747, 723, 697, 656, 617, 557, 510, 477 and 456.

In an embodiment the FTIR spectrum solvate of azoxystrobin with propionic acid having characteristic absorbance peaks (± 4 cm-1) at about 1884, 1414, 1274, 1257, 1230, 1207, 1185, 960, 945, 886, 838, 761, 697 and 656.

In an embodiment, the DSC thermal profile of solvate of azoxystrobin with propionic acid is represented in Fig. 3.

In another embodiment the solvate of azoxystrobin with propionic acid exhibits DSC thermogram containing an onset temperature in the range of about 68-74°C.

In an embodiment the solvate of azoxystrobin with propionic acid exhibits DSC thermogram containing an onset temperature in the range of about 110-116°C.

In an embodiment the solvate of azoxystrobin with propionic acid exhibits DSC thermogram containing an onset temperature in the range of about 68-74°C and 110-116°C.

In another embodiment the solvate of azoxystrobin with propionic acid exhibits DSC thermogram, characterised by endothermic peaks in the range of 72-78°C and 111-117°C.

In an embodiment the solvate of azoxystrobin with propionic acid is characterized by at least one selected from
i) an X-ray diffraction pattern expressed in 2?(±0.2°) having peaks at about 7.32, 7.57, 8.34, 11.78, 12.23, 13.31, 13.66, 14.48, 15.59, 16.64, 18.18, 18.89, 20.31, 21.27, 22.61, 23.72,24.51, 26.45, 25.95, 28.40, 28.70, 30.61, 31.40, 32.93, and 34.22;
ii) FTIR spectrum having characteristic absorbance peaks (± 4 cm-1) at about 3061, 3036, 2951, 2234, 1884, 1711, 1626, 1589, 1566, 1488, 1445, 1414, 1377, 1274, 1257, 1230, 1207, 1185, 1156, 1126, 1101, 1056, 996, 960, 945, 886, 838, 815, 771, 761, 747, 723, 697, 656, 617, 557, 510, 477 and 456 ± 4 cm-1 or
iii) DSC thermogram characterised by onset temperature in the range of 68-74°C and 110-116°C.

The present invention further provides solvate of azoxystrobin with propionic acid having a volume average particle size distribution D50 up to 300 µm (micrometers).

According to an embodiment of the present invention, the particles of solvate of azoxystrobin with propionic acid have a D50 (the median for a volume distribution, has been defined as the diameter where half of the population lies below this value) up to 300 µm (micrometres).

The present invention further provides solvate of azoxystrobin with propionic acid prepared wherein said azoxystrobin propionic acid solvate is having a volume average particle size distribution D90 up to 500 µm (micrometres).

In an aspect the present invention provides a process for the preparation of solvate of azoxystrobin with organic acid.

In an embodiment the invention provides a process for the preparation of solvate of azoxystrobin comprising
a) admixing azoxystrobin with an organic acid; and
b) subjecting said admixture to activation method or solution method resulting in said solvate of azoxystrobin.

In an embodiment the activation method of step b) comprise melting, grinding, crushing or milling techniques, applying shear forces or other frictional forces, applying heat, micro-wave irradiation, sonication, electromagnetic radiation and photo-chemical reaction to the admixture of azoxystrobin and an organic acid.

In an embodiment the solution method of step b) comprise dissolving azoxystrobin in an organic acid followed by effecting crystallization.

In an embodiment the solution method of step b) comprise dissolving azoxystrobin and/or an organic acid in a solvent followed by effecting crystallization.

In an embodiment organic acid is selected from C1-C10 saturated and unsaturated acids such as propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, acrylic acid, trans-3-methyl-2-hexenoic acid, 6-heptenoic acid, lactic acid and the like.

In one embodiment the organic acid is propionic acid.

In an embodiment, the molar ratio of azoxystrobin and organic acid in the solvate may vary in the range about 10:1 to 1:10, particularly 3:1 to 1:3, especially 1:1.

In an embodiment, the molar ratio of azoxystrobin and propionic acid in the solvate may vary in the range about 4:1 to 1:4, particularly 3:1 to 1:3, especially 1:1.

In an embodiment, the molar ratio of solvate of azoxystrobin with propionic acid is 1:1.

In another aspect of the present invention, the process for preparation of solvates of azoxystrobin comprises
a) admixing azoxystrobin with an organic acid; and
b) grinding or crushing or milling or applying shear forces or other frictional forces to the mixture to obtain solvate.

In another aspect of the present invention, the process for preparation of solvates of azoxystrobin comprises:
a) admixing azoxystrobin with organic acid; and
b) subjecting the mixture to heat or micro-wave irradiation or sonication or electromagnetic radiation or photo-chemical reaction.

In an embodiment, the process for the preparation of solvates of azoxystrobin comprising:
a) preparing a concentrated solution of azoxystrobin in organic acid;
b) triturating or precipitating to obtain the solvate.

In another embodiment, the process for preparation of solvates of azoxystrobin comprises:
a) dissolving azoxystrobin in an organic acid;
b) altering the temperature to produce the solvate.

In an embodiment, the process for the preparation of solvate of azoxystrobin comprising:
a) dissolving azoxystrobin in an organic acid;
b) cooling the solution; and
c) effecting crystallisation resulting in solvates of azoxystrobin with organic acids.

The organic acid, in step a) is selected from C1-C10 saturated and unsaturated acids such as, propionic, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, decylic acid, acrylic acid, trans-3-Methyl-2-hexenoic acid, 6-heptenoic acid, lactic acid, and the like.

In an embodiment of the present invention, in step a) the organic acid used is 0.05 to 50 molar equivalents to that of azoxystrobin.

The solvent in step a) can be selected from the group comprising aliphatic alcohols, ketones, esters, ethers, polar protic solvents, polar aprotic solvents, halogenated solvents, aliphatic hydrocarbon, aromatic hydrocarbon, water and mixture thereof.

In an embodiment, in step a) azoxystrobin is dissolved at reflux temperature or at temperature from about 25°C to about 250°C.

In an embodiment the solution of azoxystrobin in step b) is cooled to a temperature which varies from about -20°C to about 50°C for a period of 15 minutes to 6 hours.

In an embodiment, in step c) the crystallization is carried out at a temperature from about -15°C to about 40° C.

In an embodiment, in step c) the crystallization is carried out by gradual cooling.

In an embodiment, in step c) the crystallization is optionally initiated by seeding the solution with solvate of azoxystrobin with organic acid.
In an embodiment, in step c) the crystallization of solvate of azoxystrobin with organic acid is carried out for a period of 5 minutes to 48 hours.

In an embodiment, in step c) the crystals of solvate of azoxystrobin with organic acid are isolated by filtration.

In another aspect the present invention provides agrochemical composition comprising solvate of azoxystrobin with organic acid.

In an embodiment of the present invention, there is provided an agrochemical composition comprising the solvate of azoxystrobin with organic acid and at least one agronomically acceptable adjuvants/excipient.

In an embodiment there is provided a formulation comprising the solvate of azoxystrobin with organic acid and at least one agronomically acceptable excipient.

These formulations can be produced in a known manner for example by mixing the solvate of azoxystrobin with organic acid with auxiliaries suitable for the formulation of these active ingredients such as solvents/carriers, optionally with adjuvants such as surfactants, emulsifiers, dispersing agents, anti-foaming agents, anti-freezing agents, colorants, wetting agents, anticaking agents, biocides, viscosity modifiers and binding agents. The formulation may contain stabilizers. Such stabilizers may include carboxylic acids, such as citric acid and butenedioic acid or inorganic components such as sodium hydroxide, potassium hydroxide, and sodium dihydrogen phosphate dihydrate which may also act as a pH modifier. The composition content of these adjuvants is not particularly limiting and may be determined by a skilled technician in the art according to the conventional protocols.

In an embodiment the surfactants that can be additionally added to the compositions are selected from nonionic and/or anionic surfactants.

Examples of nonionic surfactants comprise alkylphenol alkoxylates, alcohol alkoxylates, fatty amine alkoxylates, polyoxyethylene glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates, fatty acid polyglycol esters, isotridecyl alcohol, fatty amides, methylcellulose, fatty acid esters, alkyl polyglycosides, glycerol fatty acid esters, polyethylene glycol, polypropylene glycol, polyethylene glycol/polypropylene glycol block copolymers, polyethylene glycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol/polypropylene glycol ether block copolymers (polyethylene oxide/polypropylene oxide block copolymers) and mixtures thereof. Preferred nonionic surfactants are fatty alcohol ethoxylates, alkyl polyglycosides, glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, lanolin ethoxylates, fatty acid polyglycol esters and ethylene oxide/propylene oxide block copolymers and mixtures thereof

Examples of anionic surfactants include alkylaryl sulfonates, phenyl sulfonates, alkyl sulfates, alkyl sulfonates, aryl alkyl sulfonates, alkyl ether sulfates, alkylaryl ether sulfates, alkyl polyglycol ether phosphates, polyaryl phenyl ether phosphates, alkyl sulfosuccinates, olefin sulfonates, paraffin sulfonates, petroleum sulfonates, taurides, sarcosides, salts of fatty acids, alkylnaphthalenesulfonic acids, naphthalenesulfonic acids and lignosulfonic acids, condensates of sulfonated naphthalenes with formaldehyde or with formaldehyde and phenol and, if appropriate, urea, and also condensates of phenolsulfonic acid, formaldehyde and urea, lignosulfite waste liquors and lignosulfonates, alkyl phosphates, alkylaryl phosphates, for example tristyryl phosphates, and also polycarboxylates, such as, for example, polyacrylates, maleic anhydride/olefin copolymers, including the alkali metal, alkaline earth metal, ammonium and amine salts of the substances mentioned above and mixtures thereof. Preferred anionic surfactants are those which carry at least one sulfonate group, and in particular their alkali metal and their ammonium salts and mixtures thereof.

In an embodiment the solvent suitable for use in the compositions of the present invention include water, aromatic solvents (for example Solvesso products, xylene, mix-xylene), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), ketonic solvents, glycols, acetates (glycol diacetate), carbonates such as propylene carbonates, fatty acid dimethylamides (for example N, N dimethyl octanamide, N, N dimethyl decanamide, Hallcomid, rhodiasolv adma10, fatty acids fatty acid esters and amino carboxylic acid esters (polarclean). In principle, solvent mixtures can also be used.

In an embodiment, the compositions comprise rheology modifier (or a viscosity modifying additive or a structuring agent). Suitable compounds are all those compounds usually employed for this purpose in agrochemical compositions. Examples include bentonites, attapulgites, polysaccharides, such as xanthan gum and kelzan gum.

In another embodiment, the compositions comprise antifreeze agents. Suitable antifreeze agents are liquid polyols, for example ethylene glycol, propylene glycol or glycerol.

The surface-active substances present in formulation are suitable for use as emulsifiers. Examples are ethoxylated nonylphenols, polyethylene glycol ethers of linear alcohols, conversion products of alkylphenols with ethylene oxide and/or propylene oxide, ethylene oxide-propylene oxide block copolymers, polyethylene glycols and polypropylene glycols (Emulsogen PC), furthermore fatty acid esters, alkyl sulphonates, alkyl sulphates, aryl sulphates, ethoxylated arylalkylphenols, such as tristyryl-phenol-ethoxylate, furthermore ethoxylated and propoxylated arylalkylphenols as well as sulphated or phosphated arylalkylphenol-ethoxylates or -ethoxy- and –propoxylates.

In yet another embodiment, the composition can comprise dispersing agents. All substances commonly used as dispersing agents in plant protection products are suitable for this purpose. Preferred dispersants are of anionic or nonionic nature and selected, for example, from polyethylene glycol/polypropylene glycol block copolymers, polyethylene glycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol/polypropylene glycol ether block copolymers, alkylaryl phosphates, for example tristyryl phosphates, lignosulfonic acids, condensates of sulfonated naphthalenes with formaldehyde or with formaldehyde and phenol and, if appropriate, urea, and also condensates of phenolsulfonic acid, formaldehyde and urea, lignosulfite waste liquors and lignosulfonates, polycarboxylates, such as, for example, polyacrylates, maleic anhydride/olefin copolymers including the alkali metal, alkaline earth metal, ammonium and amine salts of the substances mentioned above.

In another embodiment of the present invention, the composition can comprise wetting agents. Preferred wetting agents are of anionic or nonionic nature and selected, for example, from naphthalenesulfonic acids including their alkali metal, alkaline earth metal, ammonium and amine salts, fatty alcohol ethoxylates, alkyl polyglycosides, glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates and fatty acid polyglycol esters.
In an embodiment of the present invention the composition can comprise a humectant selected from polyols like sucrose, glycerin or glycerol, triethylene glycol, tripropylene glycol, and propylene glycol.

In an embodiment, the composition of the present invention may be combined with at least another active ingredient such as those selected from but not limited to herbicide, insecticide, fungicide, biological agent, plant growth activator, fertilizers or combinations thereof.

In an embodiment the present invention provides a combination of solvate of azoxystrobin with organic acid and at least one another active ingredient.

In an embodiment there is provided a formulation comprising the solvate of azoxystrobin with organic acid and at least one another active ingredient and at least one agronomically acceptable excipient.

In an embodiment the composition comprising the solvate of azoxystrobin organic acid and at least one other pesticides.

In an embodiment, the present invention provides a method of using the composition for controlling fungi comprising solvate of azoxystrobin with organic acid and/or at least one pesticide.

In an embodiment, the pesticide may be selected from:
(a) herbicides selected from a isoxazolidinone herbicide, a urea herbicide, a triazine herbicide, a hydroxybenzonitrile herbicide, a thiocarbamate herbicide, a pyridazine herbicide, chloroacetanilide herbicides; benzothiazole herbicides; carbanilate herbicides, cyclohexene oxime herbicides; picolinic acid herbicides; pyridine herbicides; quinolinecarboxylic acid herbicides; chlorotriazine herbicides, aryloxyphenoxypropionic herbicides, oxadiazolone herbicides; phenylurea herbicides, sulfonanilide herbicides; triazolopyrimidine herbicides, amide herbicides, pyridazine herbicides, dinitroaniline herbicides or combinations thereof;
(b) fungicides selected from amide fungicides, acylamino acid fungicides, anilide fungicides, benzamide fungicides, sulfonamide fungicides, strobilurin fungicides, aromatic fungicides, benzimidazole fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides (imidazoles triazoles), copper fungicides, dithiocarbamate fungicides, imidazole fungicides, organophosphorus fungicides, oxazole fungicides, pyrazole fungicides, pyridine fungicides or combinations thereof; and
(c) insecticides selected from arsenical insecticides, botanical insecticides, carbamate insecticides, benzofuranyl methylcarbamate insecticides, dimethylcarbamate insecticides, insecticides, dinitrophenol insecticides, fluorine insecticides, formamidine insecticides, fumigant insecticides, inorganic insecticides, insect growth regulators, benzoylphenylurea chitin synthesis inhibitors, macrocyclic lactone insecticides, neonicotinoid insecticides, nereistoxin analogue insecticides, organochlorine insecticides, organophosphorus insecticides, organothiophosphate insecticides, heterocyclic organothiophosphate insecticides, phenyl organothiophosphate insecticides, phosphonate insecticides, phosphonothioate insecticides, phosphoramidate insecticides, phosphoramidothioate insecticides, phosphorodiamide insecticides, oxadiazine insecticides, oxadiazolone insecticides, phthalimide insecticides, physical insecticides, pyrazole insecticides, pyrethroid insecticides, pyrethroid ether insecticides, pyrimidinamine insecticides, pyrrole insecticides, quaternary ammonium insecticides, sulfoximine insecticides, tetramic acid insecticides, tetronic acid insecticides, thiazole insecticides, thiazolidine insecticides and thiourea insecticides.

In another embodiment of the present invention, the active ingredient to be combined with the solvates of azoxystrobin with propionic acid of the present invention is selected from an conazole fungicide such as climbazole, clotrimazole, imazalil, oxpoconazole, prochloraz, triflumizole, azaconazole, bromuconazole, cyproconazole, diclobutrazol, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imibenconazole, ipconazole, ipfentrifluconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, uniconazole-P.

The composition comprising combination of solvates of azoxystrobin with propionic acid with another pesticide where another pesticide can be used in an amount from about 0.1% to about 40% by weight of active agent.

Accordingly, there is provided a composition comprising solvates of azoxystrobin with propionic acid with conazole fungicide such and agronomically acceptable excipients. The composition comprises from about 20% to about 99% by weight of the solvates of azoxystrobin with propionic acid from about 0.1% to about 40% by weight of a conazole fungicide.

In an embodiment, the herbicide that can be combined with solvates of azoxystrobin with propionic acid of the present invention is preferably selected from cyproconazole, tebuconazole, propiconazole, prothioconazole and derivatives thereof.

In another aspect the present invention provides use of solvate of azoxystrobin with organic acid for controlling fungi.

In another aspect, the present invention provides a method of using solvate of azoxystrobin with organic acids for effectively controlling fungi.

In an embodiment there is provided a method of controlling or preventing pathogenic damage caused by fungi in a plant, a part of a plant and/or plant organ that grow at a later point in time, which comprises applying on the plant, part of the plant, plant organ, or a surrounding area thereof a composition comprising fungicidally effective amount of solvate of azoxystrobin with organic acid, in any desired, sequence or simultaneously.

Accordingly, there is provided a method of combating or controlling fungi, the method comprising contacting fungi or their locus with a fungicidally effective amount of solvate of azoxystrobin with organic acid.

In an embodiment, the agrochemical composition of the invention can be used to control various fungi species for example, Cochliobolus sativus, Erysiphe graminis, Leptosphaeria nodorum, Puccinia spp., Pyrenophora spp., Rhynchosporium secalis, Septoria spp, Rhizoctonia solani, Helminthosporium oryzae, Hemileia vastatrix, Cercospora spp., Monilinia spp., Podosphaera spp., Sphaerotheca spp., Tranzschelia spp., Alternaria spp., Aphanomyces spp., Ascochyta spp., Bipolaris and Drechslera spp., Blumeria graminis spp., Botrytis cinerea, Botryodiplodia spp., Bremia lactucae, Corynespora spp., Colletotricum spp., Curvularia spp., Diplodia spp., Exserohilum spp., Fusarium spp., Verticillium spp., Gaeumanomyces Gibberella spp., Macrophomina spp., Michrodochium spp, Mycosphaerella spp., Phaeoisaripsis spp. Phakopsara spp., Phoma spp., Phytophthora spp., Plasmopara viticola, Penecilium spp., Pseudocercosporella herpotrichoides spp., Pseudoperonospora spp., Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum, Entyloma oryzae, Pyriculana grisea, Pythium spp., Thievaliopsis spp., Tilletia spp., Ustilago spp., Venturia spp.

The agrochemical composition of the present invention can be suitable for controlling such disease on a number of plants and their propagation material including, but not limited to the following target crops: cereals (wheat, barley, rye, oats, maize (including field corn and sweet corn), rice, sorghum and related crops); beet (sugar beet and fodder beet); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, sunflowers); cucumber plants (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); vegetables (spinach, lettuce, asparagus, cabbages, carrots, eggplants, onions, pepper, tomatoes, potatoes, paprika, okra); plantation crops (bananas, fruit trees, rubber trees, tree nurseries), ornamentals (flowers, shrubs, broad-leaved trees and evergreens, such as conifers); as well as other plants such as vines, bushberries (such as blueberries), caneberries, cranberries, peppermint, rhubarb, spearmint, sugar cane and turf grasses including, but not limited to, cool-season turf grasses (for example, bluegrasses (Poa L.), such as Kentucky bluegrass (Poa pratensis L.), rough bluegrass (Poa trivialis L.), Canada bluegrass (Poa compressa L.) and annual bluegrass (Poa annua L.); bentgrasses (Agrostis L.), such as creeping bentgrass (Agrostis palustris Huds.), colonial bentgrass (Agrostis tenius Sibth.), velvet bentgrass (Agrostis canina L.) and redtop (Agrostis alba L.); fescues (Festuca L.), such as tall fescue (Festuca arundinacea Schreb.), meadow fescue (Festuca elatior L.) and fine fescues such as creeping red fescue (Festuca rubra L.), chewings fescue (Festuca rubra var. commutata Gaud.), sheep fescue (Festuca ovina L.) and hard fescue (Festuca longifolia); and ryegrasses (Lolium L.), such as perennial ryegrass (Lolium perenne L.) and annual (Italian) ryegrass (Lolium multiflorum Lam.)) and warm-season turf grasses (for example, Bermudagrasses (Cynodon L. C. Rich), including hybrid and common Bermudagrass; Zoysiagrasses (Zoysia Willd.), St. Augustinegrass (Stenotaphrum secundatum (Walt.) Kuntze); and centipedegrass (Eremochloa ophiuroides (Munro.) Hack.).

In an embodiment the agrochemical composition comprising the solvate of azoxystrobin with organic acid can be formulated in different forms for example dispersible granules, wettable powders, soluble powders, dry flowables, emulsion, dispersion, suspension concentrate, encapsulation in polymeric materials, oil dispersions, emulsifiable concentrate, soluble liquid concentrate, micro emulsions, flow able concentrate, or suspo-emulsion.

The methods of application of present invention can be of either a pre-mix or tank mix of active ingredients with auxiliaries suitable for the formulation or it can be a sequential application of one after the other.

In an aspect, the composition of the present invention may be presented in the form of a multi-pack fungicidal product or as a kit-of-parts for fungicidal treatment of plants.

In an embodiment the present invention provides a kit-of-parts for controlling the fungi in plants, its habitat, a crop field, the soil or any material thereabout, said kit-of-parts comprising: fungicidally effective amount of solvate of azoxystrobin organic acid and an instruction manual comprising instructions of using said composition for controlling the fungi in plants, its habitat, a crop field, the soil or any material thereabout.

General Experimental Conditions:
X-ray Powder Diffraction (XRPD)
X-ray powder diffraction pattern were obtained on P-XRD (D2 PHASER), Bruker.

Differential Scanning Calorimeter (DSC)
Differential Scanning calorimetry was performed on DSC (DSC-3), Mettler-Toledo.

Fourier Transform Infrared (FTIR)
The FT-IR spectra were obtained on FTIR (Spectra 100), Perkin Elmer with a resolution of 4cm-1.

The invention will now be described further by reference to the following examples which are intended to illustrate, but not limit, the scope of the appended claims.

Example 1
Preparation of Azoxystrobin-Propionic acid solvate:
Azoxystrobin (50 g, 0.124 moles) is added to propionic acid (148.5 g, 2.00 moles) and the resulting mixture is heated to 80-90 °C for 3 hours. The solution is gradually cooled to 0-5 °C and stirred for 3 hours. The resulting solid is filtered and dried under vacuum to obtain white crystalline product (56 g).

Azoxystrobin content in the compound: 84.68 % (% w/w) by HPLC.

propionic acid content in the compound:15.54% (% w/w) by HPLC. This corresponds to azoxystrobin and propionic acid solvate in molar ratio of 1:1.

Example 2
Preparation of Azoxystrobin-Propionic acid solvate:
Azoxystrobin (5 g, 0.0124 moles) and propionic acid (1.01 g, 0.0136 moles) were grinded together in a mortar and pestle for 30 min. Excess of propionic acid was removed by evaporation. The azoxystrobin propionic acid solvate was obtained as white crystalline product (5.1 g).

Example 3: SC composition of solvate of azoxystrobin with propionic acid
Table 1: SC composition of azoxystrobin propionic acid solvate.
Ingredients Quantity (% w/w)
Azoxystrobin propionic acid solvate 27.65
polyoxyethylene alkyl ether 3.00
Propylene glycol 10.00
Xanthan gum 12.5
Water Q. S.
Total 100.00

Propylene glycol, polyoxyethylene alkyl ether in given quantity were stirred to obtain a mixture. Water was added to the mixture under stirring. To the mixture was added solvate of azoxystrobin with propionic acid and the mixture was subjected to homogenization. The mixture was milled to obtain desired particle size. To the mixture was added xanthan gum gel and the homogenized mixture was then set for uniform gelling.

Example 4: Stability studies of SC composition
The formulation obtained in Example 2 was analyzed for physico-chemical studies as per CIPAC guidelines.

The physico-chemical analysis of solvate of azoxystrobin with propionic acid is as given below in Table 2.

Table 2: Physico-chemical analysis of solvate of azoxystrobin with propionic acid.
Sr. no. Parameters Results
AMB-14 days AHS-14 days
1 Appearance White homogeneous suspension free from hard lump & Extraneous matter. White homogeneous suspension free from hard lump & Extraneous matter
2 Active content (%w/w) 27.34 27.15
3 1 % pH 3.64 3.67
4 Specific gravity 1.0931 1.0946
5 Suspensibility (%) 98.11 97.81
6 Wet sieve (% Retention) 0.1 0.1
7 Persistence Foam (ml) Nil Nil

Stability features associated with the composition developed according to the present invention was studied. It was found that the composition remained stable when tested at ambient conditions i.e. room temperature and pressure. The compositions passed 14 days Accelerated Heat Stability (AHS) test and remained flowable suspension in off-white appearance. The concentration of active ingredient azoxystrobin remained constant in both room temperature and AHS study. The composition showed good suspensibility in both room temperature and AHS study. The composition also passed wet sieve testing as no crystals were observed to be retained on wet sieve.

Therefore, inventors of the present invention found that an agrochemical composition from azoxystrobin propionic solvate resulted into a stable composition.

Example 5: SC composition of solvate of azoxystrobin with propionic acid-cyproconazole
Table 1: SC composition of azoxystrobin propionic acid solvate.

Ingredients Quantity
(% w/w)
Azoxystrobin propionic acid solvate 20.00
Cyproconazole 8.00
polyoxyethylene alkyl ether 3.00
Propylene glycol 10.00
Xanthan gum 12.5
Water Q. S.
Total 100

Propylene glycol, polyoxyethylene alkyl ether were stirred to obtain a mixture. To this mixture was added defoamer and water under stirring. To the mixture was added solvate of azoxystrobin with propionic acid and cyproconazole and the resulting mixture was subjected to homogenization. The mixture was milled to obtain desired particle size. To the mixture was added xanthan gum gel and the homogenized mixture was then set for uniform gelling.

Example 6: Invitro study of antifungal activity of solvate of azoxystrobin with propionic acid and Azoxystrobin against fungus rhizoctonia solani.

Azoxystrobin and solvate of azoxystrobin with propionic acid active ingredients were tested at the same dosage of 125 g/ha (X) and a lower dose of 12.5 g/ha (0.1X) for rhizoctonia solani fungi control.

Table 3: Invitro study of azoxystrobin and azoxystrobin propionic acid solvate against fungus rhizoctonia solani
Sample Different concentrations Concentration as per field dose % growth inhibition
Azoxystrobin
(azoxystrobin content 100%) 1X 125 99.0
0.1X 12.5 75.1
Azoxystrobin propionic acid solvate (azoxystrobin content 84.3%) 1X 148.28 99.0
0.1X 14.83 80.5

From the above experiment it has been observed that solvate of azoxystrobin with propionic acid (Example 1) showed good fungi control for rhizoctonia solani fungus at lower application rate of (0.1 X).
,CLAIMS:1. A solvate of azoxystrobin with propionic acid which exhibits an X-ray powder diffraction pattern expressed in 2? (±0.2°) having characteristic peaks at, at least three of the following positions 7.32, 7.57, 8.34, 11.78, 12.23, 13.31, 13.66, 14.48, 15.59, 16.64, 18.18, 18.89, 20.31, 21.27, 22.61, 23.72, 24.51, 26.45, 25.95, 28.40, 28.70, 30.61, 31.40, 32.93, and 34.22.
2. The solvate as claimed in claim 1 wherein said azoxystrobin propionic acid solvate exhibits an X-ray powder diffraction pattern having characteristic peaks expressed in 2? (±0.2°) at about 7.57, 8.34, 11.78, 13.31, 14.48, 16.64, 18.18, 20.31, 22.61, 23.72, 24.51 and 26.45.3.
3. The solvate as claimed in claim 1 wherein said azoxystrobin propionic acid solvate exhibits an FTIR spectrum having characteristic absorbance peaks expressed in (± 4 cm-1) at about 3061, 3036, 2951, 2234, 1884, 1711, 1626, 1589, 1566, 1488, 1445, 1414, 1377, 1274, 1257, 1230, 1207, 1185, 1156, 1126, 1101, 1056, 996, 960, 945, 886, 838, 815, 771, 761, 747, 723, 697, 656, 617, 557, 510, 477 and 456 cm-1
4. The solvate as claimed in claim 3 is characterized by having FTIR spectrum with characteristic absorbance peaks (± 4 cm-1) at about 1884, 1414, 1274, 1257, 1230, 1207, 1185, 960, 945, 886, 838, 761, 697 and 656 cm-1.
5. The solvate as claimed in claim 1 is characterized by DSC having an endothermic peak in the range of 72-78°C and 111-117°C.
6. A process for preparation of solvate of azoxystrobin with propionic acid comprising:
a. admixing azoxystrobin with propionic acid; and
b. subjecting said admixture to activation method or solution method resulting in said propionic acid solvate of azoxystrobin.
7. The process as claimed in claim 6 wherein said process comprising
a) dissolving azoxystrobin in propionic acid and
b) effecting crystallization.
8. The process as claimed in claim 6 wherein said process comprising:
a) admixing azoxystrobin with propionic acid; and
b) grinding or crushing or milling or applying shear forces or other frictional forces or subjecting the mixture to heat or micro-wave irradiation or sonication or electromagnetic radiation or photo-chemical reaction to the mixture to obtain solvate.
10. Solvate of azoxystrobin with propionic acid as claimed in claim 1 wherein the molar ratio of azoxystrobin to propionic acid is 3:1 to 1:3.
11. Solvate of azoxystrobin with propionic acid as claimed in claim 1 wherein the molar ratio of azoxystrobin to propionic acid is 1:1.
12. An agrochemical composition comprising solvate of azoxystrobin with propionic acid.
13. The composition as claimed in claim 12 further comprising at least one another pesticide.
14. A process for formulating an agrochemical composition comprising solvate of azoxystrobin with propionic acid said process comprising preparing a azoxystrobin propionic acid solvate with or without the addition of agrochemically acceptable excipient and further processing the mixture into a suitable form.
15. A method of controlling or combatting fungi, said method comprising contacting fungi or their locus with a fungicidally effective amount of solvate of azoxystrobin with propionic acid.