MXPA99010242A - Fungicidal mixtures - Google Patents

Abstract

The invention relates to a fungicidal mixture containing a synergistically active quantity of a1) a phenyl-benzyl ether derivative of formula (I.a), (I.b) or (I.c) or Ic, and/or a2) a carbamate of formula (I.d), in which X is CH and N, n is 0, 1 or 2 and R is a halogen, C1-C4 alkyl and C1-C4 halogen alkane, whereby the R radicals can be different if n equals 2, and one of its salts or adducts, as well as b) a dinitrophenol derivative of formula (II.a) or (II.b), in which n is 0, 1 or 2.

Description

FUNGICIDE MIXES The present invention relates to a fungicidal mixture which (lagoon) ai) a phenylbenzyl ether derivative of the formula I .a, I.b or I.c and / or a2) a carbamate of the formula Id where X is CH or N, n is 0, 1 or 2 and R is halogen, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl, it being possible for the radicals R to be different if n is 2, or one of its salts or adducts, and (sic) b) a dinitrophenol derivative of the formula II. or II. where n is 0, 1 or 2 in a synergistically effective amount. The invention also relates to methods for controlling harmful fungi by using mixtures of the compounds I (I. a, Ib or Ic) and II (II.a or II.b) and the use of the compound I and of the compound II for the preparation of such mixtures. The compounds of the formula Ia-c, their preparation and their activity against harmful fungi are known from the literature (EP-A 253 213, EP-A 254 426, EP-A 398 692). The compounds of the formula Id, their preparation and their activity are known from WO-A 93/15046, WO-A 96/01256 and WO-A 96/01258. The mixture of the compounds II (II.a and -II.b) (common name: Dinocap), their preparation and their activity against harmful fungi and arachnids (US-A 2,526,660, US-A 2,810,767) is also known. It is an object of the present invention to provide mixtures having an improved activity against harmful fungi together with a reduced total amount of applied active ingredients (synergistic mixtures), in order to reduce the application regimes and improve the spectrum of activity of the compounds known I and II. We have found that this object is achieved by the mixture defined at the beginning. Furthermore, we have found that, by applying compound I and compound II simultaneously, that is to say separately as well as jointly, or by applying compound I and compound II in succession, a better control of the harmful fungi is obtained than in the case in which the compounds are used individually. The formula Id in particular represents carbamates where the combination of substituents corresponds to a row of the following table: No. X Rn 1. 1 N 2-F 1. 2 N 3-F 1. 3 N 4-F 1. 4 N 2-Cl 1. 5 N 3-Cl 1. 6 N 4-Cl 1. 7 N 2-Br 1. 8 N 3-Br 1. 9 N 4-Br 1. 10 N 2-CH3 1. 11 N 3-CH3 1. 12 N 4-CH3 1.14 N 3-CH2CH3 1. 15 N 4-CH22CH3 1. 16 N 2 -CH (CH 3) 2 1. 17 N 3-CH (CH 3) 2 1. 18 N 4-CH (CH 3) 2 1. 19 N 2-CF3. 1. 20 N 3-CF3 1. 21 N 4-CF3 1. 22 N 2,4-F2 1. 23 N 2,4-Cl2 1. 24 N 3,4-Cl 2 1.25 N 2-Cl, 4-CH3 1.26 N 3-Cl, 4-CH3 1.27 CH 2-F 1.28 CH 3-F 1.29 CH 4-F 1.30 CH 2-Cl 1.31 CH 3-Cl 1.32 CH 4-Cl 1.33 CH 2-Br _ ~ 1.34 CH 3-Br 1.35 CH 4-Br 1.36 'CH 2 -CH 3 1.37 CH 3-CH 3 1.38 CH 4-CH 3 1.39 CH 2 -CH 2 CH 3 1.40 CH 3-CH 2 CH 3 _ 1.41 CH 4-CH 2 CH 3 1.42 CH 2-CH (CH 3) 2 1.43 CH 3-CH (CH 3) 2 1.44 CH 4-CH (CH 3) 2 1.46 CH 3-CF 3 1.48 CH 2,4-F 2 1.49 CH 2,4-Cl 2 1.50 CH 3.4-Cl2 1.51 CH 2-Cl, 4-CH3 1.52 CH 3-Cl, 4-CH3 Particular reference is made to compounds 1.12, 1.23, 1.32 and 1.38. When the They are especially suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mold) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, Rhizocjonia species in cotton , rice and lawns, Ustilago species in cereals and sugarcane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis ciñera (sic) (gray mold) in strawberries, vegetables, plants decoration and vines, Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticola in vines, Pseudocercosporella species in hops and cucumbers, Alternarla species in vegetables and fruits, species of Mycosphaerella in banana, and Fusarium and Verticillium species. In addition, they can be used for the protection of materials (for example, the protection of wood), for example against Paecilomyces variotii. The compounds I and II can be applied simultaneously, i.e. either jointly or separately, or in succession, the sequence in the case of a separate application generally has no effect on the result of the control measures.

The compounds I and II are generally in a weight ratio of from 10: 1 to 0.01: 1, preferably from 5: 1 to 0.05: 1, particularly from 1: 1 to 0.05: 1. Depending on the nature of the desired effect, the application rates of the mixtures according to the present invention are, in particular, agricultural seeds, from 0.01 to 8 kg / ha, preferably from 0.1 to 5 kg / ha, particularly from 0.5 to 3.0. kg / ha. The application regimes are, in the case of compounds I, from 0.01 to 2.5 kg / ha, preferably from 0.05 to 2.5 kg / ha, particularly from 0.05 to 1.0 kg / ha. In the case of the compounds II, the application regimes are from 0.01 to 10 kg / ha, preferably from 0.05 to 5 kg / ha, particularly from 0.1 to 2.0 kg / ha. For the treatment of seeds, the rates of application of the mixture are generally from 0.001 to 250 g / kg of seed, preferably from 0.01 to 100 g / kg, particularly from 0.01 to 50 g / kg. If the object is to control harmful phytopathogenic fungi, the separate or combined application of the compounds I and II or mixtures of the compounds I and II is achieved by spraying or spraying the seeds, plants or soils before or after the sowing of the plants, either before or after the emergence of the plants. The synergistic fungicidal mixtures according to the present invention or compounds I and II can be formulated, for example, in the form of ready-to-spray solutions, powders and suspensions, or in the form of aqueous, oil or other suspensions. Highly concentrated, dispersions, emulsions, dispersions in oil, pastes, powders, materials for application or granules and are applied by spraying, atomization, volley, or emptying. The form of use depends on the intended purpose; in any case, it must guarantee the finest and uniform distribution possible of the mixture according to the invention. The formulations are prepared in a manner known per se, for example by the addition of solvents and / or vehicles. It is usual to mix inert additives such as emulsifiers or dispersants, to the formulations. Suitable surfactants are alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acid such as, for example, ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and sulfates of fatty alcohols, and salts of sulfated hexa-, hepta- and octadecanoles, or of glycol ethers of fatty alcohols, condensates of sulfonated naphthalene and their derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene sctylphenol ethers, isooctyl-, octyl- or nonylphenol ethoxylates, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene (lagoon), lauryl alcohol polyglycol ether acetate, sorbitol ester s, lignosulfite residue liquors or methylcellulose. Powders, spraying materials can be prepared by mixing or co-grinding the compounds I and II or the mixture of the compounds I and II with a solid carrier. Granules, (for example coated granules, impregnated granules or homogeneous granules) are usually prepared by binding the active ingredient, or the active ingredients, to a solid carrier. Fillers or solid carriers are, for example, mineral earths, such as silica gel, silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, clayey earth, loess, clay, dolomite, earth diatomaceous, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, and fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal flours , particles of tree bark, wood particles, and particles of walnut shells, cellulose powders or other solid vehicles. The formulations generally comprise from 0.1 to 95% by weight, preferably from 0.5 to 90%, of one of the compounds I or II or "either of the mixture of the compounds I and II." The active ingredients are used in a purity from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum or HPLC (sic)). Compounds I and II, or the mixtures, or the corresponding formulations, are applied by treating the harmful fungi, their habitat, or the plants, seeds, soils, areas, materials or spaces that must be kept free of them with a fungicidally effective amount, or else of the compounds I and II in the case of separate application. The application can be made before or after infection by harmful fungi. Example of use The synergistic action of the mixtures according to the present invention was demonstrated by the following experiments: The active ingredients, separately or together, were formulated as a 10% emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil® LN (Lutensol® AP6, wetting agent having an emulsification and dispersion action, based on ethoxylated alkylphenols) and 10% by weight of Emulphor® EL (Emulan® EL, emulsifier based on fatty alcohols) ethoxylated) and diluted with water to provide the desired concentration. Example 1 Activity against dusty mildew of wheat Leaves of small wheat plants of the variety "Frühgold" that had been planted in pots were sprayed to the point of runoff with an aqueous preparation of the active ingredient made from a stock solution containing 10% of active compound, 63% of cyclohexanone and 27% of emulsifier, and, 24 hours after drying of the sprayed application, they were sprinkled with spores of the powdery mildew of wheat (Erysiphe graminis forma specialis tritici). The test plants were subsequently placed in a greenhouse at a temperature between 20 and 24 ° C and a relative atmospheric humidity of 70 to 90%. After 7 days, the magnitude of mold development was visually determined as percentage of infection of the total area of the leaf. An evaluation was carried out by determining the infected leaf areas as a percentage. These percentages were converted into degrees of action. The efficacy (E) was calculated in the following way using the formula of Abbot: E = (1 - alpha) 100 / ß alpha corresponds to the fungal infection of the treated plants in percentage and beta corresponds to the fungal infection of the plants not treated (controls) in percentages. A degree of action of 0 means that the level of infection of the treated plants corresponds to the level of infection of the untreated control plants; a degree of action of 100 indicates that the treated plants were not infected. The expected degrees of action of the mixtures of the active ingredients were determined using the formula of Colby (R.S. Colby, Weeds 15, (1967) 20-22) and compared with the observed degrees of action. Colby's formula: E = x + y - xy / 100 E is the expected degree of action, expressed as a percentage - of the untreated control, when the mixture of the active ingredients A and B in concentrations a and bx is used is the degree of action, expressed as a percentage of the untreated control, when the active ingredient A is used at a concentration of a and is the degree of action, expressed as a percentage of the untreated control, when the active ingredient B is used at a concentration of b.

The results of the activity against dusty mildew of wheat appear in the following tables. Ex Ingredient concentration of efficacy in% of Active ingredient active control untreated in the spray liquor in ppm IV control (100% infection) (untreated) 2V la 0.6 0 0.3 0 3V Ib 0.6 15 0.3 15 4V compound 0.63 75 1.32 (Id) 0.31 40 5V lia 12.5 10 6.3 0 3.1 0 Table 3 Ex. Conformance mixture Effectiveness efficiency with the present observed calculated *) invention 6 0.6 ppm the 40 10 + 12.5 ppm bundle 7 0.3 ppm the 40 10 + 12.5 ppm lia 8 0.6 ppm Ib 85 23.5 + 12.5 ppm lia 9 0.3 ppm Ib 80 23.5 + 12.5 ppm lia 10 0.63 ppm Id 95 75 + 6.3 ppm lia 11 _ 0.31 ppm Id 80 40 + 3.1 ppm lia *) calculated using Colby's formula The results of the test show that the efficiency observed in all mixing proportions is greater than the efficiency calculated in advance using Colby's formula.

Claims (1)

1. CLAIMS A fungicidal mixture comprising ai) a phenylbenzyl ether derivative of the formula I. a, I.b or I.c and / or a2) a carbamate of the formula Id where X is CH or N, n is 0, either 2 and R is halogen, C?-C4 alkyl or C?-C4 haloalkyl, it being possible for the radicals R to be different if n is 2, or one of its salts or adducts, and b) a dinitrophenol derivative of the formula II. a or II.b where n is 0, 1 or 2 in a synergistically effective amount. A fungicidal mixture according to claim 1, wherein the weight ratio between compound I and compound II is within a range of 10: 1 to 0.01: 1. A method for controlling harmful fungi, comprising the treatment of the harmful fungi, their habitat, or the plants, seeds, soils, areas, materials or spaces that should be kept free of them with a compound of the formula I as proposed in claim 1 and a compound of formula II as set forth in claim 1. A method according to claim 3, wherein a compound I in accordance with that set forth in claim 1 and a compound II in accordance with the raised in claim 1 they are applied simultaneously, i.e. separately or together, or successively. A method according to claim 3 or 4, wherein the compound I in accordance with that set forth in claim 1 is applied in an amount of 0.01 to 2.5 kg / ha. A method according to any of claims 3 to 5, wherein the compound II as set forth in claim 1 is applied in an amount of 0.01 to 10 kg / ha. The use of a compound I in accordance with the provisions of claim 1 to prepare a synergistic fungicidally effective mixture as claimed in claim 1. The use of a compound II according to claim 1 to prepare a synergistic fungicidally effective mixture according to as claimed in claim 1. A composition according to claim 1 which is conditioned in two parts, a part comprising a compound of the formula I as set forth in claim 1 in a solid or liquid carrier and the other part that comprises a compound of formula II as set forth in claim 1 in a solid or liquid carrier, SUMMARY OF THE INVENTION A fungicidal mixture comprising ai) a phenylbenzyl ether derivative of the formula I.a, I.b or I.c. and / or a2) a carbamate of the formula Id where X is CH or N, n is 0, 1 or 2 and R is halogen, C?-C4 alkyl or C halo-C4 haloalkyl, it being possible for the radicals R to be different if n is 2, or one of its salts or adducts, and b) a dinitrophenol derivative of the formula II. a or II.b where n is 0, 1 or 2 in an amount, synergistically effective,