MXPA97006773A - Fungicide mixtures - Google Patents

Abstract

The present invention relates to a method of treating a site for controlling pathogens, which involves (1) preparing an agriculturally suitable emulsifiable formulation in water comprising (a) from 1 to 20% by weight of water. -methyl-5- (4-phenoxyphenyl) -3-phenylamino) -2,4-oxazolidinadinedione (ie OAD) non-crystalline and (b) a triazole fungicide (the triazole is present in a weight ratio to the OAD between 1: 9 and 9: 1, in which it is effective to inhibit the crystallization of the OAD in the formulation); (2) divide the formulation in a spray tank with water, to form an aqueous mixture containing a combination of OAD and triazole fungicide in an agriculturally effective amount, and (3) apply the aqueous mixture from the spray tank to the site. Also suitable are fungicidal compositions from the agricultural point of view, which involve OAD and fungicide triazoles

Description

FUNGICIDAL MIXTURES BACKGROUND OF THE INVENTION This invention relates to fungicidal mixtures and to the use thereof, and more particularly to fungicidal mixtures comprising 5-methyl-5- (4-phenoxyphenyl) -3- (phenylamino) -2, 4- oxazolidinedione (hereinafter referred to as OAD) and the use thereof to control plant diseases. Water-emulsifiable formulations of fungicides having limited solubility characteristics may suffer from unwanted crystallization of the fungicide during storage for prolonged periods of the formulations and are ulsifiable in water and / or after prolonged periods in admixture with water (for example in a spray tank). OAD is a known fungicide (see, for example, 'U.S. Patent No. 5,223,523). However, OAD has a limited solubility in water and in several non-aqueous solvents typically used to form emulsifiable formulations in water. OAD has proven to be particularly useful for the treatment of diseases in vines, potatoes and wheat. There is a need for emulsifiable OAD formulations that are stable to crystallization. REF: 25299 The application of the OAD in combination with at least one other fungicide having a different mode of action would be advantageous to provide more effective control of fungal diseases, and also to prevent the development of resistant pathogens, which can easily occur if used the OAD individually. Accordingly, there is interest in developing advantageous fungicidal combinations involving OAD and other fungicides, and especially combinations in which the undesired crystallization potential of the OAD is reduced. Fungicide triazoles are a known class of fungicides, and are recognized for their systemic activity in protecting plants from fungal pathogens. BRIEF DESCRIPTION OF THE INVENTION The present invention involves advantageous combinations of OAD with fungicidal triazoles. Agriculturally suitable fungicidal compositions comprising OAD and triazoles are provided by this invention, wherein the weight ratio of the OAD to the triazole is from about 1: 9 to 9: 1. This invention further provides a method of treating a site for controlling fungal pathogens, comprising: (1) preparing an emulsifiable formulation in water suitable from the agricultural point of view, comprising (a) from 1 to 20% by weight of non-crystalline OAD, and (b) a triazole fungicide; the triazole is present in a weight ratio to the OAD between 1: 9 and 9: 1, which is effective to inhibit the crystallization of the OAD in the formulation; (2) diluting the formulation in a spray tank with water, to form an aqueous mixture containing a combination of OAD and triazole fungicide in an effective amount from the fungicidal point of view; and (3) apply the aqueous mixture from the spray tank to the site. DETAILED DESCRIPTION OF THE INVENTION The crystalline OAD has a very low solubility in water, and in the normal dilution of the spray tank, it has been found that OAD particles remain substantially undissolved. In some circumstances, such as the treatment of wheat septoria, it has also been found that the application of an emulsified form of OAD provides a biological control substantially better than an equal amount of OAD in a particulate form. However, several attempts to make an emulsifiable formulation in commercially viable water, free from undesirable crystallization of the OAD have been unsuccessful. Surprisingly, it has been found that the presence of the triazole fungicide, in commercially desirable proportions relative to the OAD, inhibits the crystallization of the OAD in emulsifiable formulations. Because of the mode of action and the spectrum of controlled pathogens, the fungicidal triazoles are particularly useful mixing partners for OAD. On the other hand, the excellent curative and systemic activity of the triazole complements the strong preventive and residual activity of the OAD, so that in many circumstances, the mixture can provide a more effective control of the diseases than any individual component. The OAD can be prepared as described in U.S. Patent No. 5,223,523. Its structure is as follows: OAD The fungicidal triazoles are characterized by functionality: and include bromuconazole, cyproconazole, diclobutrazol, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, ipconazole, metconazole, myclobutanil, penconazole, probenazole, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, tricyclazole, uniconazole. Fungicidal triazoles are commercially available, or can be prepared by known methods. Normally, the weight ratio of the OAD to the triazole fungicide in the compositions of this invention is from 1: 9 to 9: 1, preferably is from 1: 9 to 3: 1, and more preferably is from 1: 3 to 3: 1. Of note to facilitate the preparation of emulsions in water are the compositions containing the OAD and the triazole fungicide wherein the OAD is non-crystalline. Typically, non-crystalline OAD is provided by mixing the crystalline OAD with suitable non-aqueous solvents and / or surfactants. The compositions containing OAD and triazole of this invention should be suitable from the agricultural point of view. An agriculturally suitable composition means a composition that can be used to treat agricultural crops itself, and / or to prepare a formulation for the treatment of agricultural crops. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and suspoemulsions) and similar liquids, which optionally can be thickened in gels. Useful formulations further include solids such as very fine powders, powders, granules, pellets, tablets, films and similar solids, which may be dispersible in water ("wettable") or water soluble. The active ingredients can be (micro) encapsulated and further formed into a suspension or solid formulations. Alternatively, the complete formulation of active ingredients can be encapsulated (or "coated"). The encapsulation can control or delay the release of the active ingredients. The formulations that can be applied by spraying can be extended in a suitable medium, and used in spray volumes from about one to several hundred liters per hectare. The high concentration compositions are used primarily as intermediates for their subsequent formulation. Of note are compositions consisting essentially of OAD and a triazole fungicide. Preferably, the compositions of this invention are in an emulsifiable form. By emulsifiable form it is proposed that when mixed with water, the composition it forms an emulsion. The term emulsion includes microemulsions. The emulsifiable compositions include the so-called emulsifiable concentrates (commonly abbreviated ECs), which are mixtures of OAD and triazole plus any formulation agents and solvents or diluents. Suitable compositions of this invention also include so-called concentrated emulsions (commonly abbreviated Ews) and micro-emulsion formulations, where an emulsifiable mixture of OAD and triazole is pre-emulsified with a small amount of water, so that a highly concentrated emulsion. Suitable compositions also include emulsifiable mixtures of OAD and triazole, which are adsorbed onto solid carriers. Suitable compositions also include emulsifiable mixtures of OAD and triazole which are microencapsulated. The composition of this invention is typically applied by adding it to a spray tank (where it is diluted when necessary with water to the desired concentration for spray), and spraying the contents of the tank onto the site to be treated. The compositions of the present invention which are in the form of an emulsifiable formulation in water typically they will comprise at least one surfactant. Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkylsulfosuccinates, alkyl sulphates, alkylbenzene sulfonates, organosilicones, N, N-dialkyltaurates, and polyoxyethylene / polyoxypropylene block copolymers. The surfactants to emulsify the mixture must be adapted to the particular composition; and methods for selecting suitable surfactants for this purpose are well known in the art. The compositions of the present invention, which are in the form of an emulsifiable formulation in water will typically comprise at least one non-aqueous solvent. Non-aqueous solvents include, for example, N, N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, propylene glycol, propylene carbonate, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, olive oils, castor oil, flaxseed. , tung (seeds of the tree of Aleuritis cordata - Stend), sesame, corn, peanut, cottonseed, soybean, rapeseed and coconut, esters of fatty acids, ketones (for example cyclohexanone, 2-heptanone, isoforone and 4-hydroxy- 4-methyl-2-pentanone) and alcohols (for example methanol, ethanol, propanol, isopropanol, cyclohexanol, decanol, benzyl alcohol and tetrahydrofurfuryl alcohol). OAD has a better solubility in more polar solvents such as propylene carbonate and N-alkylpyrrolidones. The solvent can be a mixture of two or more solvents. Of note they are a mixture that includes N-octylpyrrolidone and N-methylirrolidone; a mixture including N-octylpyrrolidone, N-methylpyrrolidone and methyl soyate; a mixture that includes methyl soyate and propylene glycol; a mixture that includes methyl soyate, propylene glycol and propylene carbonate; and a mixture that includes methyl soyate and glutamic acid dimethyl ester. Liquid emulsifiable formulations can usually be made by simply mixing the components with one another. To aid in the rate of dissolution, the mixture can be heated, subjected to a high shear stress, or both. Commercially useful emulsifiable formulations prepared in accordance with this invention typically are easily emulsified, and also remain emulsified by allowing them to stand for extended periods (more than about 12 hours) in a spray tank. These formulations are also preferably stable to chemical degradation and irreversible crystallization when subjected to storage. Particularly useful compositions of this invention include compositions in the form of emulsifiable formulations in water comprising from 1 to 20 weight percent non-crystalline OAD, at least one surfactant and at least one non-aqueous solvent; wherein the triazole fungicide is present in an amount effective to inhibit the crystallization of the OAD. Of note are the modalities that are essentially free of water. To control plant diseases, water-emulsifiable formulations of the present invention are typically diluted with water in a spray tank, to the desired OAD and triazole combination, effective from the fungicidal point of view, and the resulting mixture is applies by sprinkling on the crop that is going to be protected. The practice of the invention will become further apparent from the following non-limiting examples. EXAMPLES The emulsifiable concentrate formulations of Examples 1 through 7 and Comparative Examples A, B and C were prepared as summarized in Table I. The ingredients for the Examples are more fully identified in Table II.

Table I Percent by Weight of Ingredients Ingredients Ex. 1 Ex. To Ej. B Ex. 2 Ex. 3 OAD 10.2 - 10.2 10.2 10.2 Flusilazole 17.4 17.4 - 17.2 17.2 NOP 10 11.4 12.4 23.3 - NMP 5 5.7 6.2 11.7 - Methyl soyate 19.9 22.7 24.7 - 5 PluronicR L61 29.5 33.7 36.6 29.6 25.2 SoprophorTM 796P 8 9.1 9.9 8 25.2 Propiconazole - - - - - Propylene glycol - - - - 17.2 Stepan sprinkler test: material retained (mg) in the mesh +80 9.3 0.8 22.9 1.9 1.0 Table I (Continued) Percent by Weight of Ingredients Ingredients Ex. C Ex. 4 Ex. 5 Ex. 6 Ex. 7 OAD 10.2 10.2 13.8 9.5 9.7 Flusilazole - - 15.5 10.5 10.8 Methyl soyate 6.2 5 2.5 6 2.6 PluronicMR L61 31.16 25.2 30 30 31 SoprophorTM 796P 31.16 25.2 11 12.5 10 Propiconazole - 17.2 Propylene glycol 21.28 17.2 2.5 8.3 Dibasic Ester # 5 - - 28.4 Dilaurate of PEG 200 - - 7.5 Propylene carbonate 25 23.2 Stepan sprinkler test: retained material (mg) in the mesh +80 7.7 2.3 * 2.0 2.3 1.3 * This Stepan Test uses only half the normal sample size (5 rather than 10 mi) Table II Identity and Source of Ingredients Flusilazole: triazole fungicide (DuPont) Propiconazole: triazole fungicide (Chem Services, Inc.) Propylene carbonate: solvent (Huntsman Corp.) Methyl soyate: solvent (Herikel) Propylene glycol: solvent (Fisher ) Pluronic '* L61: EO / PO block copolymer surfactant (BASF) Soprophor'R 796P: EO / PO-tristyrylphenol (Rhone-Poulenc) NMP: N-methylpyrrolidone, solvent (ISP) NOP: N-octylpyrrolidone, solvent ( ISP) Dibasic Ester No. 5: Solvent, dimethyl ester of glutaric acid (D ^ μfont) PEG Dilaurate: polyethoxylated glycol surfactant (Henkel) Samples were prepared by mixing the ingredients with each other, typically in a glass bottle of 56.7 g (2 ounces), and homogenizing the mixture with a Polytron PT3000 disperser (10 mm probe at about 10,000 to 20,000 rpm) for 15 minutes, or until the mixture became clear. During mixing with the disperser, the temperature of the mixture typically rose, but not above about 80 ° C. The mixture was allowed to cool to room temperature. Examples from 1 to 7 remained clear and free of solids. Comparative Examples A and B relate directly to Example 1. Example A has the formulation of Example 1, wherein the OAD was omitted and replaced by additional formulation agents, in proportion to its concentration in Example 1. Example B has the formulation of Example 1, wherein flusilazole was omitted, and replaced by additional formulating agents, in proportion to its concentration in Example 1. Comparative Example C is directly related to Example 4. In Example C, Propiconazole was omitted, and replaced by formulating agents in proportion to its concentration in Example 4. When stored for about 6 months at room temperature in a closed vial, Examples 3 and 4 remained free of crystals, as judged by visual inspection of the vial. In contrast, Example C showed a large amount of crystals. When stored at -6 ° C for 48 hours, Examples 3 and 4 remained crystal free. Examples 1 and B were both free of crystals when stored for 6 months at room temperature; however, when stored at -6o C for 48 hours, Example B gave crystals, while Example 1 continued free of crystals. The crystals in Example B that were formed at -6 ° C were redissolved when heated again to room temperature. The crystallization behavior of the spray solutions was studied using a laboratory Stepan ™ Spray described in U.S. Patent No. 4,347,742, equipped with an integrated 80 mesh stainless steel screen (177 microns). A sample of 10 ml of formulation was mixed with 2 1 of tap water at 5 ° C in the sprinkler tank. The mixture was stirred in the tank for 30 minutes, by means of the recirculation pump, operated at 2.8 kg / cm2 (40 psi). The mixture was transferred after the deposit to a glass container, which was stored and sealed at room temperature for 24 hours. After remaining undisturbed for 24 hours, the mixture was returned to the spray tank tank, and recirculated again for 15 minutes at 5 ° C and a pump pressure of 2.8 kg / cm2 (40 psi). The content of the sprinkler was then applied by spraying, and in doing so all the mixture passed through the integrated sieve. The larger solids of the 80 mesh were captured by the integrated screen, which was subsequently removed from the sprinkler, air dried and weighed. The net weight of the waste was determined by the difference of a tare weight previously measured from the clean sieve. The residue on the screen, which is a crystalline solid, is considered to be entirely OAD. The results of the test are summarized in Table I. The results of the Stepan ™ Sprinkler Test in Table I illustrate that the non-triazole Cmparative Examples deposit substantially larger amounts of OAD crystals than the related triazole-containing examples. (Note: the material retained from Example 4 is double for comparison purposes, because only half of the normal amount of test sample was used in the sprinkler for that Example). The tests in the greenhouse illustrating the efficacy of the control of the compositions present on the diffuse dark spots of the wheat's glume (Septoria nodorum), one of many pathogens controlled by the compositions of this invention, are summarized in Table III. Formulation samples were mixed with purified water at the indicated concentrations, and the mixtures were applied by spray in the equivalent of 935 1 / ha on aerial leaves of wheat plants (Triticum aestivum? Fremont ') of six weeks of age. The evaluation of disease control was made at several points, as indicated.

Table III Percent Disease Control on Air Sheets (average of 2 tests) 1 Preventive Day with Proportion (g / ha) 1 Day Washing * 4 hours after * 8 Day * 2 Wave * Formulation (QAD) + fluailazole) Preventive1 of the application2 Residual3 Healing4 Example 5 150g + 160g 100 99.5 100 84 75g + 80g 100 95 98 84 Example 6 150g + 160g 100 100 100 85 75g + 80g 99.5 99 100 81 Example 7! 50g 160g 100 100 100 87"5g + 80g 99.5 98 98 86 Example Ds 150g 94 95 95 66 75g 89 84 84 59 captain *! IC4 160g 99.5 92 99 88 80g 100 90 93 83 Example D -i- 150S + 160g 100 99.5 100 88 captain "" EC 75g + 80g 100 99 99 83 (tank mix)% median disease in (51%) (44%) (64%) (48%) control * not treated * 1 Twenty-four hours after application, the plants were inoculated with a suspension of spores of Septoria nodorum, and placed in a saturated atmosphere at 22 ° C for 48 hours, then incubated in the greenhouse for 10 days, after which were the evaluations of the disease. : Four hours after the application, the plants were exposed to 3.8 cm (1.5 inches) of simulated rain. Twenty hours later, the plants were inoculated with a suspension of spores of Septoria nodorum, and were placed in a saturated atmosphere at 22 ° C for 48 hours, then incubated in the greenhouse for 10 days, after which the disease assessments were made. "After application, the plants were kept in the greenhouse for 8 days, then inoculated with a suspension of Septoria nodorum spores, and placed in a saturated atmosphere at 22 ° C for 48 hours. the greenhouse for 10 days, after which the disease assessments were made.4 Before application, the plants were inoculated with a suspension of Septoria nodorum spores, and placed in a saturated atmosphere at 22 ° C for 48 hours. After the application, the plants were incubated in the greenhouse for 8 days, after which the disease evaluations were done - Example D contains 20.4% OAD, 6.5% solvent SolvessoMR 150, 5% diisononyl phthalate, 5% acetophenone, 53.1% NOP, Soprophor'R 4D384 (POE (16) ammonium salt of tristyrylphenol sulfate from Rhone-Poulenc), and GafacMR RM 710 (ethoxylated nonylphenol phosphate ester of Rhone- Poulenc), and is prepared according to the procedure previously described for the other examples. Capitan® EC is a commercial formulation of flusilazole (250 g / 1). It will be recognized by those skilled in the art that even when the results illustrated using a combination of OAD and triazole are approximately comparable to the results illustrated using a similar total amount of one of these ingredients, the use of the combination provides a fungal control of a advantageous way, which provides both, the systemic action of the triazole and the residual activity of the OAD.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, property is claimed as contained in the following:

Claims (10)

1. CLAIMS 1. An agriculturally suitable fungicidal composition, characterized in that it comprises: (a) 5-methyl-5- (4-phenoxyphenyl) -3- (phenylamino) -2,4-oxazolidinedione; and (b) a triazole fungicide; wherein the weight ratio of 5-methyl-5- (4-phenoxyphenyl) -3- (phenylamino) -2,4-oxazolidinedione to the triazole fungicide is from about 1: 9 to 9: 1. The composition according to claim 1, characterized in that the triazole fungicide is selected from the group consisting of bromuconazole, cyproconazole, diclobutrazol, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, ipconazole, metconazole, myclobutanil, penconazole , probenazole, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, tricyclazole, uniconazole and mixtures thereof. 3. The composition according to claim 1, characterized in that it is in the form of an emulsifiable formulation in water, which includes from 1 to 20 weight percent of 5-methyl-5- (4-phenoxyphenyl) -3- ( non-crystalline phenylamino) -2,4-oxazolidinedione, at least one non-aqueous solvent and at least one surfactant; where the triazole fungicide is present in an amount effective to inhibit the crystallization of 5-methyl-5- (4-phenoxyphenyl) -3- (phenylamino) -2,4-oxazolidinedione. 4. The composition according to claim 3, characterized in that the non-aqueous solvent is selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, propylene glycol, propylene carbonate, polypropylene, n glycol, paraffins, alkylbenzenes, alkylnaphthalenes, olive oils, castor oil, linseed, tung (seeds of the tree of Aleuritis cordata - Stend), sesame, corn, peanut, cottonseed, soybean, rapeseed and coconut, esters of fatty acids, ketones, alcohols and mixtures thereof. The composition according to claim 3, characterized in that the surfactant is selected from the group consisting of polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkylsulfosuccinates, alkyl sulfates, alkylbenzene sulphonates, organosilicones, N, N -dialquiltaurates, polyoxyethylene / polyoxypropylene block copolymers, and mixtures thereof. 6. The composition according to claim 3, characterized in that it is essentially free of water. The composition according to claim 1, characterized in that it consists essentially of 5-methyl-5- (4-phenoxyphenyl) -3- (phenylamino) -2,4-oxazolidinedione, a triazole fungicide selected from the group consisting of bromuconazole , cyproconazole, diclobutrazol, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, ipconazole, metconazole, myclobutanil, penconazole, probenazole, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, tricyclazole, uniconazole and mixtures thereof, at least a non-aqueous solvent, and at least one surfactant. The composition according to claim 1, characterized in that the triazole fungicide is flusilazole. 9. A method to treat to control fungal pathogens, characterized because it comprises: (1) preparing an agriculturally suitable emulsifiable formulation in water, comprising (a) from 1 to 20% by weight of 5-methyl-5- (4-phenoxyphenyl) -3- (N-crystalline (phenylamino) -2,4-oxazolidinedione and (b) a triazole fungicide; the triazole is present in a weight ratio to 5-methyl-5- (4-phenoxyphenyl) -3- (phenylamino) -2,4-oxazoline-adenylate between 1: 9 and 9: 1, which is effective in inhibiting the crystallization of 5-methyl-5- (4-phenoxyphenyl) -3- (phenylamino) -2,4-oxazolidinedione in the formulation); (2) dilute the formulation in a spray tank with water, to form an aqueous mixture containing a combination of 5-methyl-5- (4-phenoxyphenyl) -3- (phenylamino) -2,4-oxazolidinedione and triazole fungicide in an amount effective from the fungicide point of view; and (3) apply the aqueous mixture from the spray tank to the site. The method according to claim 9, characterized in that the aqueous mixture of the spray tank is applied to wheat plants; and wherein the aqueous mixture contains a combination of 5-methyl-5- (4-phenoxyphenyl) -3- (phenylamino) -2,4-oxazolidinedione and triazole fungicide in an amount effective to control the wheat glume spot.