Fungicidal compositions

Abstract

The present invention relates to a fungicidal composition comprising: (a) pydiflumetofen; and (b) a combination of biocides comprising: i. 2-bromo-2-nitro-1,3-propanediol; ii. 1,2-benzisothiazol-3(2H)-one; and iii. a mixture of 5-chloro-2-methyl-1,2-thiazol-3-one and 2-methyl-1,2-thiazol-3- one. The present invention further relates to the use of the fungicidal composition for the control of phytopathogenic diseases on useful plants.

Description

[0001] 111634-FF

[0002] 1

[0003] FUNGICIDAL COMPOSITIONS

[0004] The present invention relates to aqueous fungicidal compositions, in particular suspoemulsion and suspension concentrate compositions, comprising pydiflumetofen as the fungicidally active ingredient, and to the use of such a composition in controlling phytopathogenic diseases on useful plants. More specifically, the invention relates to suspoemulsion and suspension concentrate compositions comprising pydiflumetofen and a selection of biocides.

[0005] Bacterial contamination in production plants is a critical concern across various industries, particularly in agrochemical, pharmaceutical, and food processing facilities. These environments often provide ideal conditions for bacterial growth, including moisture, nutrients, and suitable temperatures. Contamination can occur at multiple points in the production process, from raw material handling to final product packaging.

[0006] In particular, persistent bacteria issues in suspoemulsion (SE) and suspension concentrate (SC) formulation types are a significant concern in agrochemical product development and storage. These formulations, which consist of finely dispersed active ingredients in an aqueous medium, can provide an ideal environment for bacterial growth. The presence of water, organic compounds, and nutrients in these formulations can support microbial proliferation, particularly when products are stored for extended periods or under suboptimal conditions. Bacterial contamination in agrochemical compositions leads to the production of carbon dioxide, which in turn leads to a variety of other problems, including changes in viscosity, changes in pH, separation of formulation components, and thus product degradation.

[0007] Manufacturers often employ a combination of preservatives, pH adjustments, and packaging innovations to mitigate these issues. However, the increasing regulatory scrutiny on biocides and preservatives has made it more challenging to address bacterial contamination while meeting safety and environmental standards. Simply increasing the loading of biocides in agrochemical formulations to account for biocide loss through bacterial degradation would exceed regularity limits in certain countries. There is therefore a need to develop effective preservation systems that can inhibit bacterial growth without compromising on either formulation stability or efficacy of the active ingredient.

[0008] The present invention is thus based on the finding that the combination of specific biocides prevents bacterial contamination of suspoemulsion and suspension concentrate formulations comprising pydiflumetofen.

[0009] Thus, according to the present invention there is provided a composition comprising:

[0010] (a) pydiflumetofen; and

[0011] (b) a combination of biocides comprising:

[0012] (i) 2-bromo-2-nitro-1 ,3-propanediol; 111634-FF

[0013] 2

[0014] (ii) 1 ,2-benzisothiazol-3(2H)-one; and

[0015] (iii) A mixture of 5-chloro-2-methyl-1 ,2-thiazol-3-one and 2-methyl-1 ,2-thiazol-3- one.

[0016] Preferably, the composition according to the present invention is a suspoemulsion (SE) or suspension concentrate (SC). In one embodiment, the composition is a suspoemulsion (SE). In another embodiment, the composition is a suspension concentrate (SC).

[0017] Preferably, the composition according to the present invention comprises from 1 % w / v to 50% w / v pydiflumetofen, more preferably from 5 to 30 % w / v, even more preferably, from 10 to 30 % w / v, and more preferably still from 7.5 to 25 % w / v.

[0018] 2-bromo-2-nitro-1 ,3-propanediol, which is commonly referred to as ‘bronopol’, has the CAS registry number 52-51-7. Commercially available examples of 2-bromo-2-nitro-1 ,3-propanediol include, but are not limited to ACTICIDE® L30 and ACTICIDE® L10.

[0019] Preferably, in the composition according to the present invention, (i) 2-bromo-2-nitro-1 ,3- propanediol is present from 0.005% w / v to 0.05% w / v, more preferably, from 0.01 to 0.20% w / v, even more preferably from 0.01 to 0.18% w / v, more preferably still from 0.015 to 0.16% w / v, even more preferably still from 0.016 to 0.14% w / v.

[0020] 1 ,2-benzisothiazol-3(2H)-one, has the CAS registry number 2634-33-5. Commercially available examples of 1 ,2-benzisothiazol-3(2H)-one include, but are not limited to ACTICIDE® B20 and PROXEL® GXL.

[0021] Preferably, in the composition according to the present invention, (ii) 1 ,2-benzisothiazol-3(2H)- one is present from 0.001 % w / v to 0.5% w / v, more preferably from 0.05 to 0.5% w / v, even more preferably from 0.07 to 0.30% w / v, more preferably still from 0.09 to 0.30% w / v, even more preferably still from 0.10 to 0.27% w / v, and in a particularly preferred embodiment, from 0.11 to 0.26% w / v.

[0022] 5-chloro-2-methyl-1 ,2-thiazol-3-one has the CAS registry number 26172-55-4, and is commonly referred to as ‘CIT’. 2-methyl-1 ,2-thiazol-3-one has the CAS registry number 2682-20-4, and is commonly referred to as ‘MIT’.

[0023] Preferably, in the composition according to the present invention, (iii) 5-chloro-2-methyl-1 ,2- thiazol-3-one and 2-methyl-1 ,2-thiazol-3-one are present at a ratio of 3:1 . The combination of 5-chloro- 2-methyl-1 ,2-thiazol-3-one and 2-methyl-1 ,2-thiazol-3-one is commonly referred to as ‘CIT / MIT’ and the 3:1 mixture thereof has the CAS registry number 55965-84-9. Commercially available examples of ‘CIT / MIT’ include, but are not limited to ACTICIDE® CT, ACTICIDE® MV 14. 111634-FF

[0024] 3

[0025] Preferably, 5-chloro-2-methyl-1 ,2-thiazol-3-one and 2-methyl-1 ,2-thiazol-3-one are provided in an aqueous solution at a ratio of 3:1. In particular, the concentration of 5-chloro-2-methyl-1 ,2-thiazol-3- one and 2-methyl-1 ,2-thiazol-3-one (at a ratio of 3:1), in aqueous solution, is between 1.4% and 1.6%.

[0026] Preferably, in the composition according to the present invention, the aqueous solution of 5- chloro-2-methyl-1 ,2-thiazol-3-one and 2-methyl-1 ,2-thiazol-3-one, wherein 5-chloro-2-methyl-1 ,2- thiazol-3-one and 2-methyl-1 ,2-thiazol-3-one are present at a ratio of 3:1 , and at a concentration of from 1.4 to 1.6%, is present from 0.01 % w / v to 0.50% w / v, more preferably from 0.03 to 0.50% w / v, even more preferably from 0.07 to 0.3% w / v, more preferably still from 0.08 to 0.2% w / v, and even more preferably still from 0.08 to 0.15% w / v.

[0027] In a preferred embodiment according to the invention, the composition comprises: from 5% w / v to 30 % w / v pydiflumetofen; from 0.01 % w / v to 0.20% w / v 2-bromo-2-nitro-1 ,3-propanediol; from 0.09% w / v to 0.30% w / v 1 ,2-benzisothiazol-3(2H)-one; and from 0.03% w / v to 0.50% w / v of an aqueous mixture of 5-chloro-2-methyl-1 ,2-thiazol-3-one and 2-methyl-1 ,2-thiazol-3-one (at a ratio of 3:1) at a concentration of 1.4% and 1.6%.

[0028] In another preferred embodiment according to the invention, the composition comprises: from 7.5 to 25 % w / v pydiflumetofen; from 0.016% w / v to 0.14% w / v 2-bromo-2-nitro-1 ,3-propanediol; from 0.11 % w / v to 0.26% w / v 1 ,2-benzisothiazol-3(2H)-one; and

[0029] 0.08% w / v to 0.15% w / v of an aqueous mixture of 5-chloro-2-methyl-1 ,2-thiazol-3-one and 2- methyl-1 ,2-thiazol-3-one (at a ratio of 3:1) at a concentration of 1 .4% and 1 .6%.

[0030] Other examples of industrial biocides approved for agrochemical use include, but are not limited to, ACTICIDE® LA 1016 and ACTICIDE® LG.

[0031] ACTICIDE® L30 is an aqueous solution comprising 30% w / w 2-bromo-2-nitro-1 ,3-propanediol and 60% w / w 1 ,2-propanediol.

[0032] ACTICIDE® B20 is an aqueous solution comprising 20% w / w 1 ,2-benzisothiazol-3(2H)-one, 2.5% w / w sodium hydroxide, and a 59.2% w / w mixture of dipropylene glycol isomers.

[0033] ACTICIDE® LA 1016 is an aqueous solution comprising 7.6109% w / v ACTICIDE® MV 14 and 60.9427% w / v ACTICIDE® L30.

[0034] ACTICIDE® MV 14 is a 3:1 ratio of 5-chloro-2-methyl-1 ,2-thiazol-3-one and 2-methyl-1 ,2-thiazol- 3-one, wherein 5-chloro-2-methyl-1 ,2-thiazol-3-one is present at 1 .11 % w / v and 2-methyl-1 ,2-thiazol-3- one is present at 0.37% w / v.

[0035] The composition according to the present invention may further comprise one or more additional ingredients selected from an anti-freeze agent, an anti-foam agent, a thickening agent, a stabilizer, a 111634-FF

[0036] 4 pigment, a water-miscible solvent, a water-immiscible solvent and / or one or more additional non-ionic or ionic emulsifiers.

[0037] Still further according to the invention, there is provided a method of controlling or preventing infestation of a crop of a useful plant by phytopathogenic microorganisms, wherein a fungicidally effective amount of a composition according to the invention is applied to the plants, to parts thereof or the locus thereof.

[0038] The compositions according to the invention may comprise, in addition to pydiflumetofen, one or more further fungicides that are compatible with the SE or SC formulation. "Compatible" means in this context that the fungicide combination is chemically stable and physically stable in the SE or SC formulation.

[0039] The one or more further fungicides compatible with the SE and SC formulation of the present invention may be selected from, but not limited to, a sterol demethylation-inhibitor (DMI), quinone- outside-inhibitor (Qol) and a succinate dehydrogenase inhibitor (SDHI).

[0040] In particular, the composition may comprise as additional active ingredient(s), one or more of: benzovindiflupyr, isopyrazam, azoxystrobin, difenoconazole, prothioconazole, chlorothalonil, fenpropidin, acibenzolar-S-methyl, cyproconazole, cyprodinil, fenpropimorph, propiconazole, hexaconazole, penconazole, pyrifenox, fludioxonil, pyroquilon, tricyclazole, fluazinam, mandipropamid, metalaxyl, metalaxyl-M, oxadixyl, oxathiapiprolin, paclobutrazol, sulfur, thiabendazole, folpet, bixafen, boscalid, bromuconazole, captan, cyflufenamid, epoxiconazole, fluindapyr, fluopyram, fluoxytioconazole, fluquinconazole, fluxapyroxad, inpyrfluxam, ipconazole, isoflucypram, kresoxim- methyl, mancozeb, mefentrifluconazole, metconazole, metrafenone, metyltetraprole, penthiopyrad, picoxystrobin, prochloraz, proquinazid, pyraclostrobin, spiroxamine, tebuconazole, tetraconazole, trifloxystrobin, triticonazole, fluoxapiprolin, ipfentrifluconazole, sedaxane, cyclobutrifluram, flufenoxadiazam, quinofumelin, isotianil, mandestrobin, fenpyrazamine, ipflufenoquin, tebufloquin, tolprocarb, and dichlobentiazox.

[0041] More preferably, the composition according to the invention comprises one or more additional fungicidal active ingredients selected from benzovindiflupyr, azoxystrobin, difenoconazole, prothioconazole, chlorothalonil, cyproconazole, propiconazole, fludioxonil, fluazinam, metalaxyl, metalaxyl-M, captan, epoxiconazole, fluopyram, fluxapyroxad, isoflucypram, kresoxim-methyl, mancozeb, mefentrifluconazole, metconazole, metyltetraprole, picoxystrobin, prochloraz, pyraclostrobin, tebuconazole, trifloxystrobin, sedaxane, cyclobutrifluram, flufenoxadiazam, quinofumelin, isotianil, and mandestrobin.

[0042] Even more preferably, the composition according to the invention comprises one or more additional fungicidal active ingredients selected from azoxystrobin, difenoconazole, prothioconazole, propiconazole, epoxiconazole, prochloraz, and pyraclostrobin. 111634-FF

[0043] 5

[0044] More preferably still, the composition according to the invention comprises one or more additional fungicidal active ingredients selected from azoxystrobin, difenoconazole, prothioconazole, propiconazole, epoxiconazole, and pyraclostrobin.

[0045] In a particularly preferred embodiment, the composition according to the invention comprises one or more additional fungicidal active ingredients selected from azoxystrobin, difenoconazole, prothioconazole, and propiconazole.

[0046] In a still more preferred embodiment, the composition according to the invention comprises one or more additional fungicidal active ingredients selected from azoxystrobin, prothioconazole, and propiconazole.

[0047] Preferably, the additional fungicidal active ingredient is present in a weight ratio relative to pydiflumetofen of 10:1 to 1 :10, and preferably, a weight ratio of 5:1 to 1 :5, and more preferably from 1 :2 to 2:1.

[0048] EXAMPLES

[0049] Sample Formulations

[0050] Formulation A: Suspoemulsion (SE) formulation comprising pydiflumetofen suspended in water and propiconazole present as an oil-in-water emulsion. All the SE formulations were prepared using conventional processes familiar to those skilled in the art. 111634-FF

[0051] 6

[0052] Formulation B: Suspoemulsion (SE) formulation comprising pydiflumetofen suspended in water, propiconazole present as an oil-in-water emulsion. All the SE formulations were prepared using conventional processes familiar to those skilled in the art. Formulation C: Suspension concentrate (SC) formulation comprising pydiflumetofen and proth ioconazole suspended in water. All the SC formulations were prepared using conventional processes familiar to those skilled in the art. 111634-FF

[0053] 7

[0054] Example 1 : Bacterial Growth Testing

[0055] The samples were examined prior to inoculation to determine whether a microbiological population was present. The test samples were then inoculated on 3 occasions with a consortium comprising species of bacteria and fungi. The vulnerability of the test samples to microbial growth was determined by examining the samples for the presence of surviving microorganisms at 2, 5, and 12 days after inoculation and immediately prior to each re-inoculation.

[0056] ACTICIDE® L30 is an aqueous solution comprising 30% w / w 2-bromo-2-nitro-1 ,3-propanediol and 60% w / w 1 ,2-propanediol.

[0057] ACTICIDE® B20 is an aqueous solution comprising 20% w / w 1 ,2-benzisothiazol-3(2H)-one, 2.5% w / w sodium hydroxide, and a 59.2% w / w mixture of dipropylene glycol isomers.

[0058] ACTICIDE® LA 1016 is an aqueous solution comprising 7.6109% w / v ACTICIDE® MV 14 and 60.9427% w / v ACTICIDE® L30.

[0059] ACTICIDE® MV 14 is a 3:1 ratio of 5-chloro-2-methyl-1 ,2-thiazol-3-one and 2-methyl-1 ,2-thiazol-3-one.

[0060] Table 1 : Wet State Bacterial Resistance Test (Formulation A) cfu = colony forming units 111634-FF

[0061] 8

[0062] Bacterial Growth Key: 0 = no growth; 1 = very scant (1-10 colonies); 2 = scant (11-100 colonies); 3 = light (101-300 colonies);

[0063] 4 = moderate (301-400 colonies); 5 = heavy (401-500 colonies); 6 = dense (>500-blanket growth)

[0064] Growth Media: Nutrient agar was used for the detection and growth of aerobic bacteria

[0065] Table 1 above shows that neither the addition of 2-bromo-2-nitropropan-1 ,3-diol alone (see tests 2 & 3), nor the addition of a low level combination of 1 ,2-benzisothiazol-3(2H)-one and 2-bromo-2- nitropropan-1 ,3-diol (see test 4) was effective at controlling bacterial contamination.

[0066] Addition of a higher level combination of 1 ,2-benzisothiazol-3(2H)-one and 2-bromo-2-nitropropan-1 ,3- diol (see test 5), as well as the addition of ACTICIDE® LA 1016, an aqueous solution comprising 7.6109% w / v ACTICIDE® MV 14 & 60.9427% w / v ACTICIDE® L30 (see tests 6 & 7), did control the bacterial contamination.

[0067] Table 2: Wet State Bacterial Resistance Test cfu = colony forming units

[0068] Bacterial Growth Key: 0 = no growth; 1 = very scant (1-10 colonies); 2 = scant (11-100 colonies); 3 = light (101-300 colonies);

[0069] 4 = moderate (301-400 colonies); 5 = heavy (401-500 colonies); 6 = dense (>500-blanket growth)

[0070] Growth Media: Nutrient agar was used for the detection and growth of aerobic bacteria

[0071] Table 2 above shows that formulations comprising 1 ,2-benzisothiazol-3(2H)-one, bronopol, and 5- chloro-2-methyl-1 ,2-thiazol-3-one & 2-methyl-1 ,2-thiazol-3-one are more effective against bacterial growth than formulations comprising 1 ,2-benzisothiazol-3(2H)-one and bronopol alone.

Claims

111634-FF9CLAIMS1 . A fungicidal composition comprising:(a) pydiflumetofen; and(b) a combination of biocides comprising:(i) 2-bromo-2-nitro-1 ,3-propanediol;(ii) 1 ,2-benzisothiazol-3(2H)-one; and(iii) A mixture of 5-chloro-2-methyl-1 ,2-thiazol-3-one and 2-methyl-1 ,2-thiazol-3- one.

2. The composition according to claim 1 , which is a suspoemulsion or suspension concentrate.

3. The composition according to claim 1 or claim 2, which comprises from 10% to 30% w / v pydiflumetofen.

4. The composition according to any one of the previous claims, wherein (i) 2-bromo-2-nitro-1 ,3- propanediol is present at 0.005% w / v to 0.05% w / v.

5. The composition according to any one of the previous claims, wherein (ii) 1 ,2-benzisothiazol- 3(2H)-one is present at 0.001% w / v to 0.5% w / v6. The composition according to any one of the previous claims, wherein (iii) 5-chloro-2-methyl- 1 ,2-thiazol-3-one and 2-methyl-1 ,2-thiazol-3-one are present in an aqueous solution at a ratio of 3:1.

7. The composition according to claim 6, wherein (iii) the mixture of 5-chloro-2-methyl-1 ,2-thiazol- 3-one and 2-methyl-1 ,2-thiazol-3-one is present from 0.01% w / v to 0.50% w / v.

8. A fungicidal composition according to any one of the previous claims, wherein the composition comprises one or more additional fungicidal active ingredients selected from: benzovindiflupyr, isopyrazam, azoxystrobin, difenoconazole, prothioconazole, chlorothalonil, fenpropidin, acibenzolar-S-methyl, cyproconazole, cyprodinil, fenpropimorph, propiconazole, hexaconazole, penconazole, pyrifenox, fludioxonil, pyroquilon, tricyclazole, fluazinam, mandipropamid, metalaxyl, metalaxyl-M, oxadixyl, oxathiapiprolin, paclobutrazol, sulfur, thiabendazole, folpet, bixafen, boscalid, bromuconazole, captan, cyflufenamid, epoxiconazole, fluindapyr, fluopyram, fluoxytioconazole, fluquinconazole, fluxapyroxad, inpyrfluxam, ipconazole, isoflucypram, kresoxim-methyl, mancozeb, mefentrifluconazole, metconazole, metrafenone, metyltetraprole, penthiopyrad, picoxystrobin, prochloraz, proquinazid,111634-FF10 pyraclostrobin, spiroxamine, tebuconazole, tetraconazole, trifloxystrobin, triticonazole, fluoxapiprolin, ipfentrifluconazole, sedaxane, cyclobutrifluram, flufenoxadiazam, quinofumelin, isotianil, mandestrobin, fenpyrazamine, ipflufenoquin, tebufloquin, tolprocarb, and dichlobentiazox.

9. The composition according to claim 8, wherein the additional fungicidal active ingredient is selected from azoxystrobin, difenoconazole, prothioconazole, propiconazole, epoxiconazole, and pyraclostrobin.

10. The composition according to any one of claims 1 to 9, wherein the composition is in the form of a suspoemulsion.11 . The composition according to any one of claims 1 to 9, wherein the composition is in the form of a suspension concentrate.

12. The composition according to any one of claims 1 to 11 , further comprising one or more additional ingredients selected from: an anti-freeze agent, an anti-foam agent, a thickening agent, a stabilizer, a pigment, a water-miscible solvent, a water-immiscible solvent and one or more non-ionic or ionic emulsifiers.

13. A method of controlling or preventing infestation of a crop of a useful plant by phytopathogenic microorganisms, wherein a fungicidally effective amount of a composition according to any one of claims 1 to 12, is applied to the plants, to parts thereof or the locus thereof.

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