Improved pesticidal compositions

Abstract

Improved Pesticidal Compositions This invention relates to aqueous compositions comprising certain dispersants, prothioconazole and mancozeb as well as processes to make such compositions.

Description

[0001] 111625 FF

[0002] 1

[0003] Improved Pesticidal Compositions

[0004] The present invention relates to improved pesticidal compositions for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi. More specifically the present invention relates to pesticidal aqueous compositions containing mancozeb and prothioconazole.

[0005] Mancozeb (manganese ethylenebis(dithiocarbamate) (polymeric) complex with zinc salt) and its method of manufacture is described in US3379610. Prothioconazole ((RS)-2-[2-(1-chlorocyclopropyl)- 3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-1 ,2,4-triazole-3-thione) and its method of manufacture is described in WO96 / 16048. WO 2018 / 083577 discloses a fungicidal combination of prothioconazole, mancozeb and benzovindiflupyr and uses thereof. WO 2018 / 211383 discloses liquid compositions comprising prothioconazole, mancozeb and a transition metal salt. WO 2021 / 199079 discloses liquid compositions comprising prothioconazole, mancozeb, picoxystrobin, an additive blend comprising an acrylic copolymer and / or hexamethylenetetramine. WO 2021 / 099866 discloses solid compositions comprising mancozeb, prothioconazole and a blend of high and low molecular weight formaldehydearomatic sulfonic acid condensates. WO2021 / 074831 discloses compositions comprising mancozeb, prothioconazole and a de-complexing agent. WO2023 / 180909 discloses solid compositions comprising mancozeb, prothioconazole and a sulfonate. WO2024 / 032875 discloses compositions comprising mancozeb and a naphthalene sulfonate ammonium salt. WO2024 / 033949 discloses compositions comprising mancozeb, difenoconazole and a saccharide suspending agent. WO2024 / 138252 discloses compositions comprising mancozeb and an aliphatic ethoxylated alcohol and a block copolymer of polyethylene glycol. CN11972409 discloses compositions comprising mancozeb and an amphoteric polymer surfactant. CN118020785 discloses solid and oil-based compositions comprising mancozeb, prothioconazole, pyraclostrobin and a sulfonate. CN118435956 discloses solid compositions comprising mancozeb, prothioconazole and a sulfonate.

[0006] There remains a need for improved liquid formulations containing mancozeb and prothioconazole which formulations are chemically and physically stable, particularly when stored in concentrated form and then upon subsequent dilution that are applicable under typical field conditions whilst maintaining good biological efficacy. In addition, there remains a need for improved liquid formulations which can demonstrate an enhanced and / or prolonged biological efficacy when used in the field. The present invention is aimed at solving some of the problems that exist in the prior art.

[0007] According to the present invention, there is provided a composition comprising,

[0008] (i) prothioconazole;

[0009] (ii) mancozeb;

[0010] (iii) a sulfonate or mixture of sulfonates; and

[0011] (iv) water, wherein the sulfonate or mixture of sulfonates are present at a percentage of from about 9% to 111625 FF

[0012] 2

[0013] According to a second aspect of the invention, there is provided a method of controlling or preventing infestation of useful plants by phytopathogenic fungi comprising applying a composition according to the invention, to said plants, to parts thereof or the locus thereof.

[0014] Surprisingly, it has now been found that the addition of a sulfonate dispersant or mixtures thereof in a particular range to certain compositions comprising prothioconazle and mancozeb significantly reduces the level of flocculation (i.e, preventing a cake formation) and improves the chemical stability of the mancozeb active ingredient component (i.e, eliminates or limits degradation) and thus the useful storage life and viability of fungicidal liquid compositions for crop protection applications containing these active ingredients.

[0015] Surprisingly, it has also been found that the compositions as described herein have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.

[0016] The compositions according to the invention are primarily used as a fungicide. The term “fungicide” as used herein means a compound that controls, modifies, or prevents the growth of fungi. The term “fungicidally effective amount” as used herein means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.

[0017] As used herein the term “tank-mix” means that the formulation components or additional active ingredients are mixed in the spray tank at the time of spray application.

[0018] As used herein the term “built-in” refers to formulation components (for example dispersants) that are incorporated into the formulation or formulation concentrate.

[0019] As used herein the term “active ingredient” refers to pesticidal agents that are referred to using their common name, for example, from "The Pesticide Manual", 19th Ed., British Crop Protection Council.

[0020] As used herein the term “anti-foam agent” refers to a chemical additive that reduces and hinders the formation of foam in a composition (including during field application), such as a pesticidal formulation. Anti-foaming agents which may be used in accordance with the present invention include, but are not limited to, polydimethylsiloxanes (eg, XIAMETER™ ACP-1500, Dow, Inc; Antifoam MSA, Univar; Xiameter ACP-0001 , Dow Brasil; Xiameter ACP-0100, Dow Chemical) or a silicone anti-foam emulsion (eg, SAG 1572, Momentive Performance Materials Inc., USA).

[0021] As used herein the term “dispersant or dispersing agent” refers typically to a surfactant substance, which when added to a suspension of solid particles in a liquid better enables the separation of the particles to avoid their settling or clumping together.

[0022] As used herein the term “non-ionic dispersant or dispersing agent” refers typically to polymeric dispersants that rely on physical repulsive forces of the polymer chains as well as osmotic pressure to avoid the settling or clumping together of solid particles.

[0023] As used herein the term “ionic dispersant or dispersing agent” refers typically to dispersants that rely on electrostatic repulsion to avoid the settling or clumping together of solid particles. Examples of ionic dispersants are the sulfonate dispersing agents used in accordance with the present invention. 111625 FF

[0024] 3

[0025] Such sulfonate dispersing agents include, but are not limited to, lignosulfonate salts (e.g, Ufoxane 3A, Borregard AS; Borresperse NA, Borregard AS; Polyfon™ H, Reax® 100M, Ingevity; Marasperse CBOS-4 powder, LignoTech), alkyl or polyalkyl naphthalene sulfonate salts (e.g SupragilOWP, Supragil®MNS / 90, AgniqueOANS 4DNP, AgniqueOANS 3DNP-U), naphthalene sulfonate salts condensed with formaldehyde (e.g, Morwet D-425, Nouryon Surface Chemistry AB, Sweden CAS no.: 9084-06-4 ((CioHsOsS^CF^COn’xNa)), Tersperse® 2020 from Indorama, Tamol®N &NN grades from BASF), phenol sulfonate salts condensed with formaldehyde (e.g Tamol® PP, DN range available from BASF), cresol sulfonates salts condensed with formaldehyde (Dispersogen ™ 1494 liq available from Clariant), and alkylbenzene sulfonate salts (eg, Rhodacal® DS-10 available from Syensqo).

[0026] The skilled person would appreciate that as used herein for the compositions of the invention a concentration of for example from about 9% to 30% w / v (weight / volume) of the total composition could also be expressed as from about 90 g / L to 300 g / L (grams per litre).

[0027] As used herein the term “suspension concentrate (SC)” refers to a formulation which is a stable suspension of a solid pesticidal active ingredient (for example prothioconazole) compound or mixture of compounds in a liquid, usually intended for dilution with water (in a spray tank or other vessel) before use. The compositions of the present invention may be made up to 100% by w / w (weight / weight) with the addition of water.

[0028] The compositions of the present invention may relate to concentrates designed to be added to a farmer’s spray tank of water or they may be applied directly without further dilution.

[0029] Preferably compositions according to the invention may be selected from an SC (suspension concentrate); an SL (soluble liquid); a DC (dispersible concentrate); an EW (emulsion in water); a SE (suspension-emulsion); and a CS (capsule suspension). More preferably, the composition is a SC (suspension concentrate) or a DC (dispersible concentrate). More preferably, the composition is a SC (suspension concentrate).

[0030] Preferably, in the composition of the invention the sulfonate or mixture of sulfonates are selected from the group consisting of lignosulfonates, aryl sulfonates, alkyl or polyalkyl aryl sulfonates and alkyl sulfonates. More preferably, the sulfonate or mixture of sulfonates are selected from the group consisting of aryl sulfonates, alkyl or polyalkyl aryl sulfonates and alkyl sulfonates. Even more preferably, the sulfonate or mixture of sulfonates are selected from the group consisting of alkyl or polyalkyl naphthalene sulfonate salts, naphthalene sulfonate salts condensed with formaldehyde, phenol sulfonate salts condensed with formaldehyde, cresol sulfonates salts condensed with formaldehyde and alkylbenzene sulfonate salts (preferably all with a molecular weight range of from 200 to less than 5,000 g mol’1, more preferably with a molecular weight range of from 200 to 4,999 g mol-1). More preferably, the sulfonate or mixture of sulfonates are selected from the group consisting of alkyl / polyalkyl naphthalene sulfonate salts and naphthalene sulfonate salts condensed with formaldehyde (with a molecular weight range of from 200 to less than 5,000 g mol1, more preferably with a molecular weight range of from 200 to 4,999 g mol1). Even more preferably, the sulfonate is a sodium salt of naphthalene sulfonic acid polymer with formaldehyde (with a molecular weight range of from 1 ,000 to less than 5,000 g mol-1, more preferably with a molecular weight range of from 200 to 4,999 g mol-1).

[0031] In another series of embodiments, the sulfonate or mixture of sulfonates have a molecular weight range of from 200 to 50,000 g mol1. Preferably, the sulfonate or mixture of sulfonates have a molecular 111625 FF

[0032] 4 weight range of from 200 to 10,000 g mol’1, more preferably, the sulfonate or mixture of sulfonates have a molecular weight range of from 200 to less than 5,000 g mol-1(e.g 200 to 4,999 g mol-1), even more preferably, the sulfonate or mixture of sulfonates have a molecular weight range of from 1 ,000 to less than 5,000 g mol1(e.g 1 ,000 to 4,999 g mol1).

[0033] The sulfonate is present at a percentage of from about 9% to 30% w / v (weight / volume) of the total composition (90 g / L to 300 g / L).

[0034] Preferably, from about 9% to 20% w / v of the total composition (90 g / L to 200 g / L). More preferably, from about 9% to 18% w / v of the total composition (90 g / L to 180 g / L). Even more preferably, from about 9% to 15% w / v of the total composition (90 g / L to 150 g / L). Even more preferably still, from about 9% to 14% w / v of the total composition (90 g / L to 140 g / L).

[0035] In one series of embodiments the sulfotate is present at a percentage of at least 9% w / v (90 g / L), 10% w / v (100 g / L) , 11 % w / v (110 g / L) , 12% w / v (120 g / L) , 13% w / v (130 g / L) or 14%w / v (140 g / L) of the total composition.

[0036] In another series of embodiments the sulfotate is present at a percentage of from 10% w / v to 14%w / v of the total composition (100 g / L to 140 g / L).

[0037] Preferably, the composition comprises a sulfonate or mixture of sulfonates, wherein the sulfonate or mixture of sulfonates are the sole dispersant or dispersants in the composition. Preferably, the prothioconazole is present at a percentage (%) of from about 0.5% to 10% w / v (weight / volume) of the total composition (5 g / L to 100 g / L). More preferably, from about 1 % to 7% w / v of the total composition (10 g / L to 70 g / L). Even more preferably, from about 2% to 4% w / v of the total composition (20 g / L to 40 g / L).

[0038] Preferably, the mancozeb (assuming 100% purity) is present at a percentage (%) of from about 30% to 60% w / v (weight / volume) of the total composition (300 g / L to 600 g / L). More preferably, the mancozeb (assuming 100% purity) is present at a percentage (%) of from about 35% to 55% w / v of the total composition (350 g / L to 550 g / L). Even more preferably, the mancozeb (assuming 100% purity) is present at a percentage (%) of from about 40% to 50% w / v of the total composition (400 g / L to 500 g / L).

[0039] The skilled person would appreciate that the w / v% concentration of mancozeb will depend upon the assumed purity of mancozeb, for example where the mancozeb has an assumed purity of 100% and is present at 45% w / v (450 g / L) this would be equivalent to 52.33 %w / v (523.3 g / L) at 86% purity of mancozeb.

[0040] Preferably, the composition of the present invention further comprises (v) a compound selected from the group consisting of: bixafen, fenpyrazamine, copper sulfate, copper hydroxide, triclopyricarb, acibenzolar, acibenzolar-S- methyl, copper oxychloride, copper oxide, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furametpyr, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, pyrisoxazole, simeconazole, tebucon- azole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, fenarimol, nuarimol, dodemorph, fenpropidin, fenpropimorph, spiroxamine, tridemorph, boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, penthiopyrad, thifluzamide, azoxystrobin, bifemetstrobin, 111625 FF

[0041] 5 dimoxystrobin, fenaminstrobin, flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, chlorothalonil, cyclobutrifluram, famoxadone, fenamidone, fluazinam, fluoxytioconazole, fluxapyroxad, fenhexamid, pyribencarb, triforine, isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen, isoflucypram, fluindapyr, mandestrobin, pyraziflumid, inpyrfluxam, mefentrifluconazole, ipfentrifluconazole, penflufen, florylpicoxamid, metarylpicoxamid, isofetamid, ethyl 1-[[4-[[2- (trifluoromethyl)-l ,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate, ethyl 1 -[[4-[(Z)-2- ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate, methyl N-[[4-[1-(4- cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate, methyl N-[[4-[1-(2,6- difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate, fluopyram, flufenoxadiazam, metyltetraprole, enoxastrobin, coumoxystrobin, (5S)-3-[3-(3-chloro-2-fluoro-phenoxy)- 6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine, (5R)-3- [3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6- dihydro-4H-1 ,2,4-oxadiazine, 2-tert-butyl-4-(3-chloro-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2- difluoro-ethyl]pyrazole-3-carboxamide, methyl (2R)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy- 3-(1 ,2,4-triazol-1-yl)propanoate, methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4- triazol-1 -yl)propanoate, N'-[5-bromo-2-methyl-6-[(1 S)-1 -methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N- methyl-formamidine, N'-[5-bromo-2-methyl-6-[(1 R)-1 -methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N- methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl- formamidine, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl- formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl- formamidine, N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N- isopropyl-N’-[5-methoxy-2-methyl-4-(2, 2, 2-trifluoro-1 -hydroxy-1 -phenyl-ethyl)phenyl]-N-methyl- formamidine, N’-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N- isopropyl-N-methyl-formamidine, N-ethyl-N’-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2- yl]phenyl]-N-methyl-formamidine, N-ethyl-N’-[5-methoxy-2-methyl-4-[(2-trifuoromethyl)tetrahydrofuran-

[0042] 2-yl]phenyl]-N-methyl-formamidine, N-[(1 R)-1 -benzyl-3-chloro-1 -methyl-but-3-enyl]-8-fluoro-quinoline-

[0043] 3-carboxamide, N-[(1 S)-1 -benzyl-3-chloro-1 -methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-

[0044] [(1 R)-1 -benzyl-3,3,3-trifluoro-1 -methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1 S)-1 -benzyl- 3 ,3 , 3-trifl u o ro- 1 -methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1 R)-1 -benzyl-1 ,3-dimethyl-butyl]- 7,8-difluoro-quinoline-3-carboxamide, N-[(1 S)-1 -benzyl-1 ,3-dimethyl-butyl]-7,8-difluoro-quinoline-3- carboxamide, 8-fluoro-N-[(1 R)-1 -[(3-fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3-carboxamide, 8-fluoro-N-[(1 S)-1-[(3-fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3-carboxamide, N-[(1 R)-1- benzyl-1 ,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1 S)-1 -benzyl-1 ,3-dimethyl-butyl]-8- fluoro-quinoline-3-carboxamide, N-((1 R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3- carboxamide, N-((1 S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide, 1-(6,7- dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1 -(6,7- dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline, 4,4-difluoro-3,3-dimethyl- 1-(6-methylpyrazolo[1 ,5-a]pyridin-3-yl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1 ,5- a]pyridin-3-yl)isoquinoline, 1 -(6-chloro-7-methyl-pyrazolo[1 ,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl- isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1 -(4,5- 111625 FF

[0045] 6 dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1- (4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3- dimethyl-isoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H- cyclopenta[e]benzimidazole, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1- yl)propan-2-ol, 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1 -(1 , 2 ,4-tri azo I- 1 -yl)propan-2-ol, 3- [2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile, 3-[2-(1- chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile, (5-methyl-2- pyridyl)-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methanone, (3-methylisoxazol-5-yl)-[4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methanone, 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]phenyl]acetamide, ethyl 1-[[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2- thienyl]methyl]pyrazole-4-carboxylate, 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenyl]acetamide, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide and N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1 , 2, 4-oxadiazol-3-yl] benzamide.

[0046] More preferably, the composition of the present invention further comprises (v) a compound selected from the group consisting of: bixafen, acibenzolar, acibenzolar-S-methyl, copper sulfate, copper hydroxide, copper oxychloride, copper oxide, cyproconazole, difenoconazole, hexaconazole, propiconazole, tebuconazole, epoxiconazole, fenpropidin, fenpropimorph, azoxystrobin, bifemetstrobin, dimoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, chlorothalonil, fluazinam, fluxapyroxad, isopyrazam, sedaxane, boscalid, flufenoxadiazam, benzovindiflupyr, pydiflumetofen, isoflucypram, fluindapyr, inpyrfluxam, mefentrifluconazole, florylpicoxamid, metarylpicoxamid, metyltetraprole, (5S)-3- [3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6- dihydro-4H-1 ,2,4-oxadiazine, (5R)-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2- chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine, 2-tert-butyl-4-(3-chloro-2-fluoro- phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]pyrazole-3-carboxamide, methyl (2R)-2-[2- chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propanoate and methyl 2-[2-chloro-4- (4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propanoate. Even more preferably, the composition of the present invention further comprises (v) a compound selected from the group consisting of benzovindiflupyr and pydiflumetofen. In one embodiment, the composition of the present invention further comprises (v) benzovindiflupyr. In another embodiment, the composition of the present invention comprises (v) pydiflumetofen.

[0047] Preferably, the further compound (v) is present at a percentage (%) of from about 0.5% to 10% w / v (weight / volume) of the total composition (5 g / L to 100 g / L). More preferably, from about 0.5% to 5% w / v of the total composition (5 g / L to 50 g / L). Even more preferably, from about 0.5% to 2.5% w / v of the total composition (5 g / L to 25 g / L).

[0048] The compositions of the present invention may include other ingredients such as a surfactant, an emulsifier, a solvent, a polymer, an anti-foam agent, an anti-bacterial agent, a colourant and a perfume, which are well known to the man skilled in the art. Standard formulation publications disclose such formulation components suitable for use with the present invention (for example, Chemistry and Technology of Agrochemical Formulations, Ed. Alan Knowles, published by Kluwer Academic Publishers, The Netherlands in 1998; and Adjuvants and Additives: 2006 Edition by Alan Knowles, 111625 FF

[0049] 7

[0050] Agrow Report DS256, published by Informa UK Ltd, December 2006). The compositions may also comprise other ingredients for improving formulation compatibility; such as hydrotropes and viscosity reducing aids, as discussed in WO2012 / 052545, which may be suitable for use with the composition of the present invention.

[0051] Preferably, the compositions of the invention further comprise (vi) an anti-foam agent. More preferably, the anti-foam agent is polydimethylsiloxane.

[0052] Typically in the compositions of the invention each additional formulation ingredient will be present at a percentage (%) of from 0.001 % to 15 % w / v (0.01 g / L to 150 g / L), preferably from about 0.01 % to about 10% w / v (0.1 g / L to 100 g / L), more preferably from about 0.01 % to about 6% w / v of the total composition (0.1 g / L to 60 g / L).

[0053] Preferably, the compositions according to the invention further comprise 1 to 10% w / v of an antifreeze (for example, 1 ,2-propylene glycol) of the total composition (10 g / L to 100 g / L), and more preferably, 2 to 8% w / v of an antifreeze (for example, 1 ,2-propylene glycol) of the total composition (20 g / L to 80 g / L). Even more preferably the compositions according to the invention further comprise from 3 to 7 % w / v of 1 ,2-propylene glycol of the total composition (30 g / L to 70 g / L). Even more preferably still, from 4 to 6 % w / v of 1 ,2-propylene glycol of the total composition (40 g / L to 60 g / L).

[0054] Preferably, the compositions according to the invention further comprise 0.1 to 10% w / v of a thickening agent of the total composition (1 g / L to 100 g / L), which may be selected from a natural gum substance, such as guar gum or xanthan gum, or a montmorillonite-type clay (eg, Bentopharm™ 20, Wilfrid Smith, UK). More preferably, from 0.1 to 1 % w / v of the total composition.

[0055] Preferably, the compositions according to the invention further comprise 0.1 to 10% w / v of a preservative agent or agents (anti-bacterial agent or agents) of the total composition (1 g / L to 100 g / L), which may be selected from 1 ,2-benzisothiazol-3-one and / or 2-bromo-2-nitropropan-1 ,3-diol. More preferably, from 0.1 to 1 % w / v of the total composition.

[0056] Suitable agricultural carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to those skilled in the art.

[0057] In addition, other further biocidally active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further biocidally active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and / or plant growth regulators.

[0058] Pesticidal agents are referred to herein using their common name are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.

[0059] In addition, the compositions of the invention may also be applied with one or more systemically acquired resistance inducers (“SAR” inducer). SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.

[0060] Preferably, there is provided a composition, wherein the composition is transition metal free.

[0061] Preferably, there is provided a composition, wherein the composition is amine free. 111625 FF

[0062] 8

[0063] In a preferred embodiment there is provided a composition (preferably, a suspension concentrate) comprising,

[0064] (i) prothioconazole;

[0065] (ii) mancozeb;

[0066] (iii) a sulfonate or mixture of sulfonates;

[0067] (iv) water; and

[0068] (v) a compound selected from the group consisting of: bixafen, acibenzolar, acibenzolar-S-methyl, copper sulfate, copper hydroxide, copper oxychloride, copper oxide, cyproconazole, difenoconazole, hexaconazole, propiconazole, tebuconazole, epoxiconazole, fenpropidin, fenpropimorph, azoxystrobin, bifemetstrobin, dimoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, chlorothalonil, fluazinam, fluxapyroxad, isopyrazam, sedaxane, boscalid, flufenoxadiazam, benzovindiflupyr, pydiflumetofen, isoflucypram, fluindapyr, inpyrfluxam, mefentrifluconazole, florylpicoxamid, metarylpicoxamid, metyltetraprole, (5S)-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4- yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine, (5R)-3-[3-(3-chloro- 2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro- 4H-1 ,2,4-oxadiazine, 2-tert-butyl-4-(3-chloro-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2- difluoro-ethyl]pyrazole-3-carboxamide, methyl (2R)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2- hydroxy-3-(1 ,2,4-triazol-1-yl)propanoate and methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2- hydroxy-3-(1 ,2,4-triazol-1-yl)propanoate; wherein the sulfonate or mixture of sulfonates are present at a percentage of from about 9% to 30% w / v of the total composition.

[0069] More preferably, there is provided a composition (preferably, a suspension concentrate) comprising,

[0070] (i) prothioconazole;

[0071] (ii) mancozeb;

[0072] (iii) a sulfonate or mixture of sulfonates;

[0073] (iv) water; and

[0074] (v) a compound selected from the group consisting of: benzovindiflupyr and pydiflumetofen; wherein the sulfonate or mixture of sulfonates are the sole dispersant or dispersants in the composition, and wherein the sulfonate or mixture of sulfonates are selected from the group consisting of aryl sulfonates, alkyl or polyalkyl aryl sulfonates and alkyl sulfonates, and wherein the sulfonate or mixture of sulfonates are present at a percentage of from about 9% to 20% w / v of the total composition (preferably, 9% to 18% w / v of the total composition).

[0075] Even more preferably, there is provided a composition (preferably, a suspension concentrate) comprising,

[0076] (i) prothioconazole (preferably, present at a percentage of from about 0.5% to 10% w / v of the total composition); 111625 FF

[0077] 9

[0078] (ii) mancozeb (preferably, present at a percentage of from about 30% to 60% w / v of the total composition);

[0079] (iii) a sulfonate or mixture of sulfonates;

[0080] (iv) water; and

[0081] (v) a compound selected from the group consisting of: benzovindiflupyr and pydiflumetofen (preferably present at a percentage of from about 0.5% to 10% w / v of the total composition); wherein the sulfonate or mixture of sulfonates are the sole dispersant or dispersants in the composition, and wherein the sulfonate or mixture of sulfonates are selected from the group consisting of alkyl or polyalkyl naphthalene sulfonate salts and naphthalene sulfonate salts condensed with formaldehyde (preferably, a sodium salt of naphthalene sulfonic acid polymer with formaldehyde (with a molecular weight range of from 1 ,000 to less than 5,000 g mol1)) present at a percentage of from about 9% to 20% w / v of the total composition (preferably, 9% to 18% w / v, more preferably, 9% to 15% w / v of the total composition).

[0082] Even more preferably still, there is provided a composition (preferably, a suspension concentrate) comprising,

[0083] (i) prothioconazole (preferably, present at a percentage of from about 0.5% to 10% w / v of the total composition);

[0084] (ii) mancozeb (preferably, present at a percentage of from about 30% to 60% w / v of the total composition);

[0085] (iii) a sulfonate or mixture of sulfonates;

[0086] (iv) water,

[0087] (v) a compound selected from the group consisting of: benzovindiflupyr and pydiflumetofen (preferably present at a percentage of from about 0.5% to 10% w / v of the total composition); and

[0088] (vi) an anti-foam agent (preferably, the anti-foam agent is polydimethylsiloxane); wherein the sulfonate or mixture of sulfonates are the sole dispersant or dispersants in the composition, and wherein the sulfonate or mixture of sulfonates are selected from the group consisting of alkyl or polyalkyl naphthalene sulfonate salts and naphthalene sulfonate salts condensed with formaldehyde (preferably, a sodium salt of naphthalene sulfonic acid polymer with formaldehyde (with a molecular weight range of from 1 ,000 to less than 5,000 g mol-1)) present at a percentage of from about 9% to 20% w / v of the total composition (preferably, 9% to 18% w / v, more preferably, 9% to 15% w / v of the total composition).

[0089] In another embodiment, there is provided a composition (preferably, a suspension concentrate) comprising,

[0090] (i) prothioconazole;

[0091] (ii) mancozeb;

[0092] (iii) a sulfonate or mixture of sulfonates;

[0093] (iv) water; and 111625 FF

[0094] 10

[0095] (v) benzovindiflupyr; wherein the sulfonate or mixture of sulfonates are selected from the group consisting of lignosulfonates, aryl sulfonates, alkyl or polyalkyl aryl sulfonates and alkyl sulfonates (more preferably, the sulfonate or mixture of sulfonates are selected from the group consisting of aryl sulfonates, alkyl or polyalkyl aryl sulfonates and alkyl sulfonates, even more preferably, the sulfonate or mixture of sulfonates are selected from the group consisting of alkyl or polyalkyl naphthalene sulfonate salts, naphthalene sulfonate salts condensed with formaldehyde, phenol sulfonate salts condensed with formaldehyde, cresol sulfonates salts condensed with formaldehyde and alkylbenzene sulfonate salts, even more preferably still, the sulfonate or mixture of sulfonates are selected from the group consisting of alkyl or polyalkyl naphthalene sulfonate salts and naphthalene sulfonate salts condensed with formaldehyde, yet even more still, the sulfonate is a sodium salt of naphthalene sulfonic acid polymer with formaldehyde (with a molecular weight range of from 1 ,000 to less than 5,000 g mol1)), and wherein the sulfonate or mixture of sulfonates are present at a percentage of from about 9% to 20% w / v of the total composition (preferably, 9% to 18% w / v of the total composition).

[0096] Preferably, there is provided a composition (preferably, a suspension concentrate) comprising,

[0097] (i) prothioconazole;

[0098] (ii) mancozeb;

[0099] (iii) a sulfonate or mixture of sulfonates;

[0100] (iv) water; and

[0101] (v) benzovindiflupyr; wherein the sulfonate or mixture of sulfonates are the sole dispersant or dispersants in the composition, and wherein the sulfonate or mixture of sulfonates are selected from the group consisting of aryl sulfonates, alkyl or polyalkyl aryl sulfonates and alkyl sulfonates (preferably, the sulfonate or mixture of sulfonates are selected from the group consisting of alkyl or polyalkyl naphthalene sulfonate salts, naphthalene sulfonate salts condensed with formaldehyde, phenol sulfonate salts condensed with formaldehyde, cresol sulfonates salts condensed with formaldehyde and alkylbenzene sulfonate salts, more preferably, the sulfonate or mixture of sulfonates are selected from the group consisting of alkyl or polyalkyl naphthalene sulfonate salts and naphthalene sulfonate salts condensed with formaldehyde, even more preferably, the sulfonate is a sodium salt of naphthalene sulfonic acid polymer with formaldehyde (with a molecular weight range of from 1 ,000 to less than 5,000 g mol1)), and wherein the sulfonate or mixture of sulfonates are present at a percentage of from about 9% to 20% w / v of the total composition (preferably, 9% to 18% w / v of the total composition).

[0102] In another embodiment, there is provided a composition (preferably, a suspension concentrate) comprising,

[0103] (i) prothioconazole;

[0104] (ii) mancozeb;

[0105] (iii) a sulfonate or mixture of sulfonates; 111625 FF

[0106] 11

[0107] (iv) water; and

[0108] (v) pydiflumetofen; wherein the sulfonate or mixture of sulfonates are selected from the group consisting of lignosulfonates, aryl sulfonates, alkyl or polyalkyl aryl sulfonates and alkyl sulfonates (more preferably, the sulfonate or mixture of sulfonates are selected from the group consisting of aryl sulfonates, alkyl or polyalkyl aryl sulfonates and alkyl sulfonates, even more preferably, the sulfonate or mixture of sulfonates are selected from the group consisting of alkyl or polyalkyl naphthalene sulfonate salts, naphthalene sulfonate salts condensed with formaldehyde, phenol sulfonate salts condensed with formaldehyde, cresol sulfonates salts condensed with formaldehyde and alkylbenzene sulfonate salts, even more preferably still, the sulfonate or mixture of sulfonates are selected from the group consisting of alkyl or polyalkyl naphthalene sulfonate salts and naphthalene sulfonate salts condensed with formaldehyde, yet even more still, the sulfonate is a sodium salt of naphthalene sulfonic acid polymer with formaldehyde (with a molecular weight range of from 1 ,000 to less than 5,000 g mol-1)), and wherein the sulfonate or mixture of sulfonates are present at a percentage of from about 9% to 13% w / v of the total composition (preferably, 9% to 12% w / v of the total composition).

[0109] Preferably, there is provided a composition (preferably, a suspension concentrate) comprising,

[0110] (i) prothioconazole;

[0111] (ii) mancozeb;

[0112] (iii) a sulfonate or mixture of sulfonates;

[0113] (iv) water; and

[0114] (v) pydiflumetofen; wherein the sulfonate or mixture of sulfonates are the sole dispersant or dispersants in the composition, and wherein the sulfonate or mixture of sulfonates are selected from the group consisting of aryl sulfonates, alkyl or polyalkyl aryl sulfonates and alkyl sulfonates (preferably, the sulfonate or mixture of sulfonates are selected from the group consisting of alkyl or polyalkyl naphthalene sulfonate salts, naphthalene sulfonate salts condensed with formaldehyde, phenol sulfonate salts condensed with formaldehyde, cresol sulfonates salts condensed with formaldehyde and alkylbenzene sulfonate salts, more preferably, the sulfonate or mixture of sulfonates are selected from the group consisting of alkyl or polyalkyl naphthalene sulfonate salts and naphthalene sulfonate salts condensed with formaldehyde, even more preferably, the sulfonate is a sodium salt of naphthalene sulfonic acid polymer with formaldehyde (with a molecular weight range of from 1 ,000 to less than 5,000 g mol1)), and wherein the sulfonate or mixture of sulfonates are present at a percentage of from about 9% to 13% w / v of the total composition (preferably, 9% to 12% w / v of the total composition).

[0115] In another embodiment there is provided a composition (preferably, a suspension concentrate) comprising:

[0116] (i) prothioconazole;

[0117] (ii) mancozeb; 111625 FF

[0118] 12

[0119] (iii) at least one dispersant;

[0120] (iv) water; and

[0121] (v) a compound selected from the group consisting of: benzovindiflupyr and pydiflumetofen; wherein the at least one dispersant is solely a sulfonate or mixture of sulfonates selected from the group consisting of lignosulfonates, aryl sulfonates, alkyl or polyalkyl aryl sulfonates and alkyl sulfonates, and wherein the sulfonate or mixture of sulfonates are present at a percentage of from about 9% to 20% w / v of the total composition (preferably, 9% to 18% w / v of the total composition).

[0122] Preferably, there is provided a composition (preferably, a suspension concentrate) comprising,

[0123] (i) prothioconazole (preferably, present at a percentage of from about 0.5% to 10% w / v of the total composition);

[0124] (ii) mancozeb (preferably, present at a percentage of from about 30% to 60% w / v of the total composition);

[0125] (iii) at least one dispersant;

[0126] (iv) water; and

[0127] (v) benzovindiflupyr (preferably present at a percentage of from about 0.5% to 10% w / v of the total composition); wherein the at least one dispersant is solely a naphthalene sulfonate salts condensed with formaldehyde (preferably, a sodium salt of naphthalene sulfonic acid polymer with formaldehyde (with a molecular weight range of from 1 ,000 to less than 5,000 g mol-1)) present at a percentage of from about 9% to 15% w / v of the total composition.

[0128] In another preferred embodiment, there is provided a composition (preferably, a suspension concentrate) comprising,

[0129] (i) prothioconazole (preferably, present at a percentage of from about 0.5% to 10% w / v of the total composition);

[0130] (ii) mancozeb (preferably, present at a percentage of from about 30% to 60% w / v of the total composition);

[0131] (iii) at least one dispersant;

[0132] (iv) water; and

[0133] (v) pydiflumetofen (preferably present at a percentage of from about 0.5% to 10% w / v of the total composition); wherein the at least one dispersant is solely a naphthalene sulfonate salts condensed with formaldehyde (preferably, a sodium salt of naphthalene sulfonic acid polymer with formaldehyde (with a molecular weight range of from 1 ,000 to less than 5,000 g mol-1)) present at a percentage of from about 9% to 13% w / v of the total composition (more preferably, from about 9% to 12% w / v of the total composition). 111625 FF

[0134] 13

[0135] In another embodiment, there is provided a composition (preferably, a suspension concentrate) comprising,

[0136] (i) prothioconazole;

[0137] (ii) mancozeb;

[0138] (iii) a sulfonate or mixture of sulfonates; and

[0139] (iv) water, wherein the sulfonate or mixture of sulfonates are present at a concentration of from 90 g / L to 300 g / L (preferably from 90 g / L to 180 g / L, more preferably, from 90 g / L to 150 g / L, even more preferably from 90 g / L to 140 g / L, even more preferably still, from 90 g / L to 130 g / L, yet even more preferably still, from 90 g / L to 120 g / L).

[0140] Preferably, there is provided a suspension concentrate composition comprising,

[0141] (i) prothioconazole;

[0142] (ii) mancozeb;

[0143] (iii) a sulfonate or mixture of sulfonates; and

[0144] (iv) water, wherein the sulfonate or mixture of sulfonates are present at a concentration of from 90 g / L to 300 g / L (preferably from 90 g / L to 180 g / L, more preferably, from 90 g / L to 150 g / L, even more preferably from 90 g / L to 140 g / L, even more preferably still, from 90 g / L to 130 g / L, yet even more preferably still, from 90 g / L to 120 g / L).

[0145] More preferably, there is provided a suspension concentrate composition comprising,

[0146] (i) prothioconazole;

[0147] (ii) mancozeb;

[0148] (iii) a sulfonate or mixture of sulfonates,

[0149] (iv) water, and

[0150] (v) benzovindiflupyr or pydiflumetofen; wherein the sulfonate or mixture of sulfonates are present at a concentration of from 90 g / L to 300 g / L (preferably from 90 g / L to 180 g / L, more preferably, from 90 g / L to 150 g / L, even more preferably from 90 g / L to 140 g / L, even more preferably still, from 90 g / L to 130 g / L, yet even more preferably still, from 90 g / L to 120 g / L).

[0151] In another embodiment of the invention, the target density of the composition (formulation) is from 1 .3 g / cm3to 1 .4 g / cm3(1 ,300 g / L to 1 , 400 g / L). Preferably, the target density of the composition (formulation) is 1 .33 g / cm3(or 1 ,330 g / L).

[0152] The present invention further relates to a process for the preparation of a composition as disclosed herein, wherein the process comprises the steps of,

[0153] (a) mixing the components as defined herein together; 111625 FF

[0154] 14

[0155] (b) co-milling the product of step (a) until the average particle size is between 0.5 and 10 microns (preferably, between 1 and 5 microns);

[0156] (c) adding water.

[0157] Preferably, in the process of the invention in step (b) the co-milling is performed by passing the product of step (a) through a colloidal mill and subsequently a bead mill.

[0158] The present invention further relates to methods of controlling or preventing infestation of useful plants or plant propagation material and / or harvested food crops by phytopathogenic fungi comprising applying a composition as described herein, to said plants or plant propagation material and / or harvested food crops, to parts thereof or the locus thereof. Preferably, the invention relates to a method of controlling or preventing infestation of useful plants by phytopathogenic fungi comprising applying a composition as described herein, to said plants, to parts thereof or the locus thereof.

[0159] The compositions of the invention may be used for controlling a broad spectrum of plant diseases, such as foliar and / or soil-borne pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops. These pathogens may include:

[0160] Oomycetes, including Phytophthora species such as Phytophthora cactorum, Phytophthora capsici, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora, Phytophthora erythroseptica , Phytophthora fragariae, Phytophthora infestans, Phytophthora nicotianae, Phytophthora porri, and Phytophthora sojae; Pythium species such as Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare and Pythium ultimum; other Peronosporales such as Bremia lactucae, Hyaloperonospora parasitica, Hyaloperonospora brassicae, Sclerophthora macrospora, Sclerospora graminicola' Peronospora species including Peronospora destructor, Peronospora farinosa f. sp. spinaciae and Peronospora viciae f. sp. pisi; Plasmopara species including Plasmopara halstedii and Plasmopara viticola' Pseudoperonospora species including Pseudoperonospora cubensis and Pseudoperonospora humili; Peronosclerospora species including Peronosclerospora maydis, Peronosclerospora philippinensis and Peronosclerospora sorghi; Albuginales such as Albugo Candida, Albugo occidentalis , and Albugo tragopogonis; and Saprolegniales such as Aphanomyces species, including Aphanomyces cochliodes.

[0161] Ascomycetes, including Mycosphaerellales such as Actinothyrium graminis, Asperisporium caricae, Cercospora species including Cercospora arachidicola, Cercospora beticola, Cercospora brassicicola, Cercospora canescens, Cercospora cf. flagellaris, Cercospora janseana, Cercospora kikuchii, Cercospora lagenariae, Cercospora sojinae, Cercospora sorghi, Cercospora zeae-maydis; Dothistroma septosporum, Fulvia fulva, Mycosphaerella species including Mycosphaerella pomi and Mycosphaerella linicola; Neopseudocercosporella brassicae, Neopseudocercosporella capsellae, Nothopassalora personata, Nothophaeocrytopus gaeumannii, Passalora bataticola, Passalora koepkei, Pseudocercospora griseola, Pseudocercospora musaei, Pseudocercospora vitis, Pseudocercospora fijiensis, Ramularia species including Ramularia beticola and Ramularia collo-cygni; Ramulariopsis gossypii, Ramulariopsis pseudoglycines, Ramulispora sorghi, Scolecostigmina palmivora, Septoria species including Septoria apiicola, Septoria glycines and Septoria lycopersici; Zasmidium citri-griseum, and Zymosepotria tritici; Helotiales such as Blumeriella jaapii, Botrytis species including Botrytis cinerea, Botrytis aclada and Botrytis fabae; Botryotinia squamosa, Cadophora gregata, Civorinia allii, Claireedia 111625 FF

[0162] 15 homoeocarpa, Diplocarpon coronariae, Diplocarpon rosae, Drepanopeziza campestris, Gloeotinia temulenta, Hymenoscyphus fraxineus, Leptotrochila medicaginis, Marssonina graminicola, Monilinia species including Monilinia fructicola, Monilinia fructigena and Monilinia laxa; Neofabraea perennans, Neofabraea vagabunda, Oculimacula yallundae, Pezicula spp., Pseudopeziza medicaginis, Pseudopeziza tracheiphila, Pyrenopeziza species including Pyrenopeziza brassicae; Rhabdocline pseudotsugae, Rhynchosporium species including Rhynchosporium secalis; Sclerotinia species including Sclerotinia minor, Sclerotinia borealis and Sclerotinia sclerotiorum; Hypocreales such as Acremonium strictum, Albifimbria verrucaria, Claviceps africana, Claviceps purpurea, Fusarium species including Fusarium avenaceum, Fusarium culmorum, Fusarium fujikuroi, Fusarium graminearum, Fusarium incarnatum, Fusarium langsethiae, Fusarium moniliforme, Fusarium oxysporum, Fusarium oxysporum f.sp. cubense, Fusarium poae, Fusarium proliferatum , Fusarium pseudograminearum , Fusarium subglutinans, Fusarium sulphureum, Fusarium tricinctum and Fusarium verticillioides; Gliocladium spp., Neocosmospora phaseoli, Neocosmospora solani, Neonectria Candida, Paramyrothecium roridum, Sarocladium oryzae, Trichoderma species including Trichoderma harzianum, Trichoderma pseudokoningii and Trichoderma viride; Trichothecium roseum and Ustilaginoidea virens; Magnaporthales such as Gaeumannomyces avenae, Gaeumannomyces graminis, Gaeumannomyces graminis tritici, Gaeumannomyces wongoonoo, Magnaporthiopsis poae, Pyricularia species including Pyricularia grisea and Pyricularia oryzae; Pleosporales, such as Alternaria species including Alternaria allii, Alternaria alternata, Alternaria arachidis, Alternaria brassicae, Alternaria brassicicola, Alternaria citri, Alternaria dauci, Alternaria grandisi, Alternaria helianthicola, Alternaria linariae, Alternaria mali, Alternaria porri, Alternaria solani and Alternaria tomato; Boeremia coffeae, Ascochyta species including Ascochyta pisi and Ascochyta rabiei; Bipolaris maydis, Bipolaris oryzae, Bipolaris sorokiniana, Cochliobolus spp., Corynespora cassiicola, Curvularia species including Curvularia australiensis, Curvularia cactivora and Curvularia lunata; Didymella species including Didymella pinodella and Didymela pinodes; Xenodidymella applanata, Drechslera species including Drechslera glycines; Epicoccum nigrum, Exserohilum turcicum, Helminthosporium species including Helminthosporium solani; Hendersonia creberrima, Leptosphaerulina crassiasca, Neocamarosporium betae, Ophiosphaerella agrostidis, Ophiosphaerella herpotricha, Ophiosphaerella korrae, Ophiosphaerella narmari, Parastagonospora nodorum, Phaeosphaeria herpotrichoides, Phaerosphaeria maydis, Phoma spp., Plenodomus lindquistii, Plenodomus lingam, Pleospora spp., Pseudopyrenochaeta lycopersici, Pyrenophora species including Pyrenophora poae, Pyrenophora teres and Pyrenophora tritici-repentis; Remotididymella destructiva, Stagonospora tainanensis, Stagonosporopsis cucurbitacearum, Stemphylium species including Stemphylium botryosum, Stemphylium solani and Stemphylium vesicarium; Diaporthales such as Anisogramma anonmala, Apiognomonia errabunda, Cytospora platani, Diaporthe species including Diaporthe amygdali, Diaporthe helianthin, Diaporthe neoviticola and Diaporthe phaseolorum; Dicarpella spp., Discula destructiva, Gnomoniopsis fructicola, Greeneria uvicola, Juglanconis juglandina, Ophiognomonia clavigignenti-juglandacearum, Stenocarpella maydis and Tubakia dryina; Dothideales such as Aureobasidium species including Aureobasidium pullulans; Discosphaerina fulvida; Erysiphales such as Blumeria graminis, Brasiliomyces malachrae, Erysiphe species including Erysiphe betae, Erysiphe cruciferarum, Erysiphe diffusa, Erysiphe heraclei, Erysiphe necator and Erysiphe pisi; Golovinomyces 111625 FF

[0163] 16 cichoracearum, Golovinomyces orontii, Leveillula taurica, Oidium arachidisi, Oidium neolycoperisci, Phyllactinia guttata, Podosphaera species including Pososphaera aphanis, Podosphaera fuliginea, Podosphaera fusca, Podosphaera leucotricha, Podosphaera macularis, Podosphaera mors-uvae, Podosphaera pannosa, Podosphaera tridactyla and Podosphaera xanthii; Glomerellales such as Colletotrichum species including Colletotrichum acutatum, Colletotrichum cereale, Colletotrichum chrysanthemi, Colletotrichum cliviicola, Colletotrichum coccodes, Colletotrichum fragariae, Colletotrichum gloeosporioides, Colletotrichum graminicola, Colletotrichum lentis, Colletotrichum lindemuthianum, Colletotrichum musae, Colletotrichum orbiculare, Colletotrichum siamense and Colletotrichum truncaturrr, Glomerella cingluata, Glomerella gossypii, Musicillium theobromae, Plectosphaerella cucumerina, Verticillium species including Verticillium dahlia' Venturiales such as Venturia species including Venturia carpophila, Venturia effusa, Venturia inaequalis, Venturia oleaginea, and Venturia pyrina; Xylariales such as Eutypa lata, Microdochium albescens, Microdochium majus, Microdochium nivale, Microdochium paspali, Microdochium sorghi, Physalospora abdita, Rosellinia spp. and Seimatosporium mariae; Botryosphaeriales such as Botryosphaeria species including Botryosphaeria dothidea; Diplodia species including Diplodia seriata; Dothiorella aromatica, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllosticta ampelicida and Phyllosticta cucurbitacearum; Eurotiales such as Aspergillus species including Aspergillus flavus, Aspergillus fumigatus, Aspergillus niger and Aspergillus terreus; Penicillium species including Penicillium digitatum, Penicillium expansum and Penicillium italicum; Microascales such as Berkeleyomyces basicola, Thielaviopsis paradoxa, Ceratocystis species including Ceratocystis fimbriata, Ceratocystis manginecans and Ceratocystis platani; Scedosporium species including Scedosporium apiospermum and Scedosporium prolificans; Myriangiales such as Elsinoe species including Elsinoe ampelina and Elsinoe perseae; Ophiostomatales such as Leptographium lundbergii, Leptographium microsporum, Ophiostoma novo-ulmi, Ophiostoma piceae and Sporothrix spp.; Pezizomycetes such as Phymatotrichopsis omnivore and Polyscytalum pustulans; Phyllachorales such as Gibellina cerealis, Phyllachora maydis and Phyllachora pomigena; Amphisphaeriales such as Griphosphaeria corticola, Lepteutypa cupressi and Pestalotia rhododendri; Capnodiales such as Capnodium ramosum and Schizothyrium pomi; Chaetothyriales such as Phialophroa spp.; Cladosporiales such as Cladosporium species including Cladosporium oxysporum, Cladosporium cucumerinum and Cladosporium allii-cepae; Rhytismatales such as Lophodermium seditiosum and Naemacyclus spp.; Saccharomycetales such as Cephaloascus species including Cephaloascus fragrans; Geotrichum candidum, Candida species including Candida glabrata, Candida krusei, Candida lusitaniae, Candida parapsilosis, Candida albicans and Candida tropicalis; Sordariales such as Chaetomium spp. and Monosporascus cannonballus; Sordariomycetes such as Wongia garrettii and Wongia griffinii; Taphrinales such as Taphrina bullata and Taphrina deformans; Onygenales such as Ajellomyces capsulatus, Blastomyces dermatitidis, Coccidioides species including Coccidioides immitis; Epidermophyton spp., Histoplasma spp., Microsporum spp., Trichophyton spp., and Paracoccidioides species including Paracoccioides brasiliensis; and others such as Hymenula cerealis, Petriellidum spp., and Septocyta ruborum.

[0164] Basidiomycetes, including Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Cronartium ribicola, Gymnosporangium juniperi-virginianae, Gymnosporangium sabinae, 111625 FF

[0165] 17

[0166] Hemileia species including Hemileia vastatrix; Melampsora medusae, Melampsora Uni, Phakopsora ampelopsidis, Phakopsora pachyrhizi, Phragmidium mucronatum, Puccinia species including Puccinia allii, Puccinia arachidis, Puccinia asparagi, Puccinia cacabata, Puccinia coronata, Puccinia graminis, Puccinia helianthi, Puccinia hieracii, Puccinia hordei, Puccinia horiana, Puccinia melanocephala, Puccinia polys ora, Puccinia porri, Puccinia recondita, Puccinia sorghi, Puccinia striiformis, Puccinia striiformis f.sp. hordei, Puccinia striiformis f.sp. tritici and Puccinia triticina; Pucciniastrum coryli, Tranzschelia discolor, Uromyces species including Uromyces betae, Uromyces pisi and Uromyces viciae-fabae; Tilletiales such as Neovossia moliniae, and Tilletia species including Tilletia caries and Tilletia controversa; Ustilaginales such as Sporisorium reilianum and Ustilago species including Ustilago maydis, Ustilago segetum var. nuda, Ustilago segetum var. tritici and Ustilago striiformis; Urocystidales such as Urocystis species including Urocystis agropyri; Agaricales such as Marasmiellus inoderma, Mycena spp., Moniliophthora roreri and Moniliophthora perniciosa; Cantharellales such as Sclerotium spp. and Typhula species including Typhula incarnata and Typhula ishikariensis; Ceratobasidiales such as Waitea circinata, and Rhizoctonia species including Rhizoctonia cerealis, Rhizoctonia solani and Rhizoctonia theobromae; Atheliales such as Athelia rolfsii; Corticiales such as Corticium invisum and Laetisaria fuciformis; Cystodilobasidiales such as Itersonilia perplexans; Entylomatales such as Entyloma calendulae f.sp. dahliae and Entylomella microspore; Exobasidiales such as Exobasidium vexans; Hymenochaetales such as Phellinus igniarius; Russulales such as Stereum hirsutum; and Tremellales such as Cryptococcus species including Cryptococcus neoformans.

[0167] Zygomycetes, including Mucorales such as Choanephora cucurbitarum, Mucor spp., Rhizopus oryzae, Absidia corymbifera and Rhizomucor pusillus.

[0168] Blastocladiomycetes, including Physoderma maydis. as well as diseases caused by other species and genera closely related to those listed above.

[0169] In addition to their fungicidal activity, the compositions may also have activity against diseases caused by Actinobacteria such as Streptomyces scabiei; Proteobacteria such as Erwinia amylovora, Pectobacterium carotovorum, Xanthomonas species including Xanthomonas axonopodis, Xanthomonas campestris, Xanthomonas citri, Xanthomonas oryzae and Xanthomonas vesicatoria; Xylella fastidiosa, and Pseudomonas species including Pseudomonas syringae; Cercozoa such as Polymyxa betae, Polymyxa graminis and Spongospora subterranea; and Bigyra such as Labyrinthula zosterae. as well as diseases caused by other species and genera closely related to those listed above.

[0170] The compositions as disclosed herein are particularly effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g, Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula); Basidiomycetes (e.g, the genus Hemileia, Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia); Fungi imperfecti (also known as Deuteromycetes; e.g. Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Alternaria, Pyricularia and Pseudocercosporella); Oomycetes (e.g, Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium, Pseudosclerospora and Plasmopara).

[0171] In a preferred embodiment, there is provided, a method of combating, preventing or controlling pod anomaly in soybean, which comprises applying to the crop of soybean plants, the locus thereof, or propagation material thereof, a composition as defined herein. Preferably, the pod anomaly comprises 111625 FF

[0172] 18 phytopathogenic fungi selected from the group consisting of Cercospora spp., Colletotrichum spp., Corynespora spp. and Diaporthe spp. More preferably, the pod anomaly comprises phytopathogenic fungi selected from the group consisting of Cercospora spp., Colletotrichum spp., Corynespora spp., Diaporthe spp. and Fusarium spp. Even more preferably, the pod anomaly comprises phytopathogenic fungi selected from the group consisting of Cercospora spp., Colletotrichum spp., Corynespora spp., Diaporthe spp., wherein the Diaporthe species comprise at least Diaporthe miriciae and Diaporthe longicolla, and Fusarium spp. Even more preferably still, the pod anomaly comprises phytopathogenic fungi selected from the group consisting of Cercospora spp., Colletotrichum spp., wherein the Colletotrichum species comprise at least Colletotrichum cliviicola and Colletotrichum truncatum, Corynespora spp., Diaporthe spp., wherein the Diaporthe species comprise at least Diaporthe miriciae and Diaporthe longicolla, and Fusarium spp. Yet even more preferably still, the pod anomaly comprises phytopathogenic fungi selected from the group consisting of Cercospora spp., Colletotrichum spp., wherein the Colletotrichum species comprise at least Colletotrichum cliviicola and Colletotrichum truncatum, Corynespora spp., wherein the Corynespora spp. species comprise at least Corynespora cassiicola., Diaporthe spp., wherein the Diaporthe species comprise at least Diaporthe miriciae and Diaporthe longicolla, and Fusarium spp. Yet even more further preferably still, the pod anomaly comprises phytopathogenic fungi selected from the group consisting of Cercospora spp., Colletotrichum spp., wherein the Colletotrichum species comprise at least Colletotrichum cliviicola and Colletotrichum truncatum, Corynespora spp., wherein the Corynespora spp. species comprise at least Corynespora cassiicola., Diaporthe spp., wherein the Diaporthe species comprise at least Diaporthe miriciae and Diaporthe longicolla, and Fusarium spp., wherein the Fusarium spp. species comprise at least Fusarium fujikuroi and Fusarium incarnatum.

[0173] The term “locus” as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.

[0174] The term “plants” refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.

[0175] The term “plant propagation material” is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There can be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants can be protected before transplantation by a total or partial treatment by immersion. Preferably “plant propagation material” is understood to denote seeds.

[0176] The compositions according to the invention can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non-selective herbicides as well as insecticides, fungicides, bactericides, 111625 FF

[0177] 19 nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.

[0178] The rate at which the compositions of the invention are applied will depend upon the particular type of phytopathogen, etc, to be controlled, the degree of control required and the timing and method of application which can be readily determined by the person skilled in the art. In general, the compositions of the invention can be applied at an application rate of between 0.005 kilograms / hectare (kg / ha) and about 5.0 kg / ha, based on the total amount of active ingredient in the composition. An application rate of between about 0.1 kg / ha and about 1 .5 kg / ha is preferred, with an application rate of between about 0.1 kg / ha and 0.5 kg / ha being especially preferred.

[0179] In an aqueous composition comprising the fungicidal composition according to the invention (eg, a tank-mix composition), the one or more additional fungicidal active ingredients may be added separately prior to crop application.

[0180] EXAMPLES

[0181] The Examples which follow serve to illustrate the invention. The following examples demonstrate the effect of a sulfonate or mixture of sulfonates on the stability of compositions of the present invention.

[0182] Preparation Examples

[0183] Example 1 - General Preparation Method of Aqueous Formulations

[0184] The formulations as described below were prepared by mixing the active ingredients, dispersant, anti-foam agent, antifreeze and preservatives. This premix was pre-milled using a colloidal mill and then millied using a bead mill until an average particle size of 90% less than 4 pm and greater than 50% less than 1 .5 pm (as measured using laser diffraction particle size analyser) is achieved. After the pre-milling and milling steps the viscosity was adjusted with xanthan gum and water to achieve a range of 1 ,000 to 3,000 mPa.s (or 1 ,000 to 3,000 cps) as measured using a Brookfield viscometer with a spindle 63 at 30 rpm.

[0185] Table 1 - Comparison of dispersants in suspension concentrates (SC) of benzovindiflupyr, prothioconazole and mancozeb prepared by the above general method. 111625 FF

[0186] 20 111625 FF

[0187] 21

[0188] A.I - Active Ingredient

[0189] Reg. - Regular w - week

[0190] Table 2 - Comparison of Dispersants in suspension concentrates (SC) of pydiflumetofen, prothioconazole and mancozeb prepared by the above general method. 111625 FF

[0191] 22

[0192] Suspension concentrates (SC) of benzovindflupyr, prothioconazole and mancozeb were prepared by the following general methods:

[0193] Table 3a - Comparison of dispersants in suspension concentrates (SC) of prothioconazole and mancozeb prepared by the above general method. 111625 FF

[0194] 23

[0195] A.I - Active Ingredient

[0196] Reg. - Regular w - week 111625 FF

[0197] 24

[0198] Table 3b - Comparison of dispersants in suspension concentrates (SO of prothioconazole and mancozeb prepared by the above general method. 111625 FF

[0199] 25

[0200] A.I - Active Ingredient

[0201] Reg. - Regular w - week

[0202] Table 4a - Comparison of dispersants in suspension concentrates (SC) erf mancozeb (solo A.I) prepared by the above general method. 111625 FF

[0203] 26

[0204] A.I - Active Ingredient

[0205] Reg. - Regular w - week

[0206] Table 4b - Comparison of dispersants in suspension concentrates (SC) erf mancozeb (solo A.I) prepared by the above general method. 111625 FF

[0207] 27 111625 FF

[0208] 28

[0209] A.I - Active Ingredient

[0210] Reg. - Regular w - week

[0211] Example 2 - Process to make suspension concentrates (SC) of benzovindiflupyr, prothioconazole and mancozeb.

[0212] A mill-base of benzovindflupyr and prothioconazole is prepared as follows: a portion of the water is weighed into a vessel, following this the dispersant and a portion of the anti-foam and anti-bacterial agents are all weighed into the vessel under agitation. Benzovndiflupyr and prothioconazole technical are then added, and a higher mixing speed is initiated and continued until a homogenous suspension is obtained. This premix is then pre-milled using a colloidal mill for product homogenization and lumps redution, after that milled using the bead mill to achieve a average particle size of 90% less than 4|im and greater than 50% less than 1 .5|im as measured using laser diffraction particle size analyser. Details of the composition prepared using this method is given in Table 3 below:

[0213] Table 5. Benzovindiflupyr+Prothioconazole millbase composition (40% of Active Ingredient) 111625 FF

[0214] 29

[0215] After preparation of the mill base descirbed in table 5 mancozeb technical was added using a cowles impeller at low speed, to controll the foam formation and provide better mancozeb homogenization. The remaining water and / or xanthan gum are added and mixing is completed using a low-shear mixer until a homogenous, smooth liquid is produced, in this step is necessay measure the viscosity to control of the xanthan gum to be usage. Details of the final composition produced using this procedure are as follows:

[0216] Table 6. Final formulation F8 using the STL+PTZ millbase with incorporation of MZB in low agitation.

[0217] The skilled person would appreciate that in tables 1 , 2, 3a, 3b, 4a, 4b and 6 the target density of the formulation is 1 .33 g / cm3(or 1 ,330 g / L).

Claims

111625 FF30CLAIMS:1 . A composition comprising,(i) prothioconazole;(ii) mancozeb;(iii) a sulfonate or mixture of sulfonates; and(iv) water, wherein the sulfonate or mixture of sulfonates are present at a percentage of from about 9% to 30% w / v of the total composition.

2. The composition according to claim 1 , wherein the sulfonate or mixture of sulfonates are selected from the group consisting of lignosulfonates, aryl sulfonates, alkyl or polyalkyl aryl sulfonates and alkyl sulfonates.

3. The composition according to claim 1 or claim 2, wherein the sulfonate or mixture of sulfonates are selected from the group consisting of alkyl or polyalkyl naphthalene sulfonate salts and naphthalene sulfonate salts condensed with formaldehyde.

4. The composition according to any one of claims 1 to 3, wherein the sulfonate is a sodium salt of naphthalene sulfonic acid polymer with formaldehyde.

5. The composition according to any one of claims 1 to 4, wherein the sulfonate or mixture of sulfonates are present at a percentage of from about 9% to 18% w / v of the total composition.

6. The composition according to any one of claims 1 to 5, wherein the sulfonate or a mixture of sulfonates are the sole dispersant or dispersants in the composition.

7. The composition according to any one of claims 1 to 6, wherein the prothioconazole is present at a percentage of from about 0.5% to 10% w / v of the total composition.

8. The composition according to any one of claims 1 to 7, wherein the mancozeb is present at a percentage of from about 30% to 60% w / v of the total composition.

9. The composition according to any one of claims 1 to 8, further comprising (v) a compound selected from the group consisting of: bixafen, fenpyrazamine, copper sulfate, copper hydroxide, triclopyricarb, acibenzolar, acibenzolar-S-methyl, copper oxychloride, copper oxide, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furametpyr, hexaconazole, imazalil, imibenconazole,111625 FF31 ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, pyrisoxazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadime- nol, triflumizole, triticonazole, fenarimol, nuarimol, dodemorph, fenpropidin, fenpropimorph, spiroxamine, tridemorph, boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, penthiopyrad, thifluzamide, azoxystrobin, bifemetstrobin, dimoxystrobin, fenaminstrobin, flufenoxystrobin, flu ox astro bin, kresoxim-methyl, metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, chlorothalonil, cyclobutrifluram, famoxadone, fenamidone, fluazinam, fluoxytioconazole, fluxapyroxad, fenhexamid, pyribencarb, triforine, isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen, isoflucypram, fluindapyr, mandestrobin, pyraziflumid, inpyrfluxam, mefentrifluconazole, ipfentrifluconazole, penflufen, florylpicoxamid, metarylpicoxamid, isofetamid, ethyl 1-[[4-[[2-(trifluoromethyl)-1 ,3- dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate, ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3- trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate, methyl N-[[4-[1-(4-cyclopropyl- 2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate, methyl N-[[4-[1-(2,6- difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate, fluopyram, flufenoxadiazam, metyltetraprole, enoxastrobin, coumoxystrobin, (5S)-3-[3-(3-chloro-2-fluoro- phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4- oxadiazine, (5R)-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4- methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine, 2-tert-butyl-4-(3-chloro-2-fluoro- phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]pyrazole-3-carboxamide, methyl (2R)-2- [2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propanoate, methyl 2-[2- chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propanoate, N'-[5-bromo-2- methyl-6-[(1 S)-1 -methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5- bromo-2-methyl-6-[(1 R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl- formamidine, N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl- formamidine, N-isopropyl-N’-[5-methoxy-2-methyl-4-(2, 2, 2-trifluoro-1 -hydroxy-1 -phenyl- ethyl)phenyl]-N-methyl-formamidine, N’-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5- methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine, N-ethyl-N’-[5-methoxy-2-methyl- 4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine, N-ethyl-N’-[5-methoxy-2- methyl-4-[(2-trifuoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine, N-[(1 R)-1- benzyl-3-chloro-1 -methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1 S)-1 -benzyl-3- chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1 R)-1-benzyl-3,3,3-trifluoro- 1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1 S)-1-benzyl-3,3,3-trifluoro-1-methyl- propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1 R)-1-benzyl-1 ,3-dimethyl-butyl]-7,8-difluoro- quinoline-3-carboxamide,N-[(1 S)-1-benzyl-1 ,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, 8-fluoro-N-[(1 R)-1- [(3-fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3-carboxamide, 8-fluoro-N-[(1 S)-1-[(3- fluorophenyl)methyl]-1 ,3-dimethyl-butyl]quinoline-3-carboxamide, N-[(1 R)-1 -benzyl-1 ,3-111625 FF32 dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1 ,3-dimethyl-butyl]-8- fluoro-quinoline-3-carboxamide,N-((1 R)-1 -benzyl-3-chloro-1 -methyl-but-3-eny l)-8-fluoro-quinoline-3-carboxamide, N-((1 S)-1 - benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide, 1 -(6,7- dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1 -(6,7- dimethylpyrazolo[1 ,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline, 4,4-difluoro-3,3- dimethyl-1-(6-methylpyrazolo[1 ,5-a]pyridin-3-yl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(7- methylpyrazolo[1 ,5-a]pyridin-3-yl)isoquinoline, 1-(6-chloro-7-methyl-pyrazolo[1 ,5-a]pyridin-3- yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3- dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5- fluoro-4-methyl-benzimidazol-1 -yl)-3,3-dimethyl-isoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1 - isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole, 2-[6-(4-chlorophenoxy)-2-(triflu o romethy I) -3-py ridy I]- 1 -(1 , 2 ,4-tri azo I- 1 -yl)propan-2-ol, 2-[6-(4-bromophenoxy)-2-(triflu o romethy I) -3-py ridy I]- 1 -(1 , 2 ,4-tri azo I- 1 -yl)propan-2-ol, 3-[2-(1 -chlorocyclopropyl)-3-(2- fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile, 3-[2-(1-chlorocyclopropyl)-3-(3-chloro- 2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile, (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methanone, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]methanone, 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]acetamide, ethyl 1-[[5-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate, 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-l ,2,4-oxadiazol-3-yl]phenyl]acetamide, N-[(E)-methoxyiminomethyl]-4-[5- (trifluoromethyl)-l ,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-l , 2, 4-oxadiazol-3-yl] benzamide and N-[N-methoxy-C-methyl-carbonimidoyl]-4- [5-(trifluoromethyl)-1 , 2, 4-oxadiazol-3-yl] benzamide.

10. The composition according to any one of claims 1 to 9, further comprising (v) a compound selected from the group consisting of: bixafen, acibenzolar, acibenzolar-S-methyl, copper sulfate, copper hydroxide, copper oxychloride, copper oxide, cyproconazole, difenoconazole, hexaconazole, propiconazole, tebuconazole, epoxiconazole, fenpropidin, fenpropimorph, azoxystrobin, bifemetstrobin, dimoxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, chlorothalonil, fluazinam, fluxapyroxad, isopyrazam, sedaxane, boscalid, flufenoxadiazam, benzovindiflupyr, pydiflumetofen, isoflucypram, fluindapyr, inpyrfluxam, mefentrifluconazole, florylpicoxamid, metarylpicoxamid, metyltetraprole, (5S)-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4- yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine, (5R)-3-[3-(3-chloro- 2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro- 4H-1 ,2,4-oxadiazine, 2-tert-butyl-4-(3-chloro-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2- difluoro-ethyl]pyrazole-3-carboxamide, methyl (2R)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2- hydroxy-3-(1 ,2,4-triazol-1-yl)propanoate and methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2- hydroxy-3-(1 ,2,4-triazol-1-yl)propanoate.111625 FF3311. The composition according to any one of claims 1 to 10, further comprising (v) a compound selected from the group consisting of benzovindiflupyr and pydiflumetofen.

12. The composition according to any one of claims 1 to 11 , wherein the composition is a suspension concentrate.

13. The composition according to any one of claims 1 to 12, wherein the composition is transition metal free.

14. The composition according to any one of claims 1 to 13, wherein the composition is amine free.

15. The composition according to any one of claims 1 to 14, wherein the sulfonate or mixture of sulfonates have a molecular weight of from 200 to less than 5,000 g mol-1.

16. A method of controlling or preventing infestation of useful plants by phytopathogenic fungi comprising applying a composition according to one of claims 1 to 15, to said plants, to parts thereof or the locus thereof.

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