MXPA98008777A - Fungicide mixtures - Google Patents

Abstract

The present invention relates to: fungicidal mixtures containing (a) a carbamate of the formula I, in which T stands for CHN, n is 0, 1 and 2 and R means halogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl, the radicals R being different when n is 2, and / or (b) an oxymer of the formula II, in which the substituents have the following meanings: X oxygen or amino (NH); Y CH or N; Z oxygen , sulfur, amino (NH) or C1-C4-alkylamino (N-C1-C4-alkyl); RIC1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl, C2-C6-haloalkenyl, C3- C6-alkynyl, C3-haloalkynyl, C3-C6-cycloalkyl-methyl, obenzyx which may be partially or completely halogenated and / or carry from one to three of the following radicals: cyano, C1-C4-alkyl, C1-C4-haloalkyl , C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy and C 1 -C 4 -alkylthio; and (c) a dinitroaniline of the formula III, in an active synergistic amount.

Description

FUNGICIDE MIXES. Description The present invention relates to a fungicidal mixture containing a) a carbamate of the formula I, wherein T means CH or N, n is 0, 1 or 2 and R means halogen, C? -C4-alkyl or C? -C4-haloalkyl, the radicals R being different when n is 2, and / ob) an oxim ether of the formula II, wherein the substituents have the following meanings: X oxygen or amino (NH); And CH or N; Z oxygen, sulfur, amino (NH) or C? -C4-alkylamino (N-C? -C4-alkyl), - R 'Ci-Ce-alkyl, C? -C6-haloalkyl, C3-C6-alkenyl, C2-C6-haloalkenyl, C3-C6-alkynyl, C3-C6 ~ halogeno-alkynyl, C3-C6-cycloalkyl-methyl, obencil which may be partially or completely halogenated and / or carry from one to three of the following radicals: cyano, C? -C4-alkyl, C? -C4-haloalkyl, C? -C4-alkoxy, C? -C4- halogenoalkoxy and C? -C4-alkylthio; and c) a dinitroaniline of formula III, in an active synergetic quantity.

Furthermore, the invention relates to processes for controlling harmful fungi with the mixtures from the compounds I and / or II and III and to the use of the compounds I and II and III for obtaining such mixtures. The compounds of the formula I, their preparation and action against harmful fungi are known from the literature (WO-A 96 / 01,256 and WO-A 96 / 01,258). The compounds of formula II, their preparation and their action against fungi are described in WO-A 95 / 21,153, WO-A 95 / 21,154, DE-A 195 28 651.0.

Compound III, its preparation and its use are also known (CAS RN 79622-59-6, common ñame: Fluazinam). In order to reduce the amounts of aliquot and improve the spectrum of action of the known compounds, the present invention was aimed at finding mixtures which, with the application of a lower total content of the active substances, had a better effect against harmful fungi (synergistic mixtures). ).

Therefore, the mixtures defined above were found. In addition, it was found that by simultaneously applying compounds I and / or II and compound III in a joint or separate form, or by applying compounds I and / or II and compound III succesively more harmful fungi are achieved, than by Apply the compounds alone.

The present invention relates both to binary mixtures from compounds I and III or II and III, as well as to ternary mixtures from I, II and III. The "general formula I" represents especially carbamates, in which the combination of the substituents corresponds to a line in the following table.

Table 1: Compounds 1.12, 1.23, 1.32 are especially preferred. 1. 38 General formula II is especially representative for oxymethylether, wherein X means oxygen and Y means CH or X is amino and Y is N. Furthermore, compounds II are preferred, wherein Z means oxygen. Also preferred are compounds II, wherein R 'signifies alkyl or benzyl. With respect to their use in the synergistic mixtures of the invention, the compounds II listed in the following tables are preferred: Table 2. Compounds of the formula IIA, in which ZR 'means a compound of one line respectively of Table A Table 3. Compounds of formula IIB, wherein ZR 'means a compound of one line respectively of Table A Table A: The compounds of the formula II can be present with respect to the C = Y double bond in the E or Z configuration (with respect to the carboxylic acid functional group). Thus, in the mixtures of the invention, they can be used as a pure E or Z isomer or as an E / Z isomer mixture. The E / Z isomer mixture or the E-isomer is preferred, especially the E-isomer for compound II being preferred. The C = N double bonds of the oxymer groups in the lateral chain of the compounds II can be present as pure E or Z isomers or as E / Z isomeric mixtures. The compounds I can be used in the mixtures according to the invention, both in the form of pure isomers, and also in the form of isomeric mixtures. With respect to their use, compounds I are preferred, in which the terminal oxy-terminal group of the side chain is present in the cis configuration (group OCH3 with respect to ZR ').

Thanks to their basic character, compounds I and II are able to form salts with inorganic or organic acids or adducts or with metal ions. Examples of inorganic acids are the hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, sulfuric acid, phosphoric acid and nitric acid. Suitable organic acids are, for example, formic acid, carbonic acid and the alkanoic acids, such as acetic acid, trifluoroacetic acid and propionic acid, as well as glycolic acid, thiocyanuric acid, lactic acid, succinic acid, citric acid, benzoic acid, acid cinnamic, oxalic acid, alkylsulfonic acids (sulfonic acids with linear or branched alkyl radicals having 1 to 20 carbon atoms), arylsulfonic or aryldisulfonic acids (aromatic radicals, such as phenyl and naphthyl carrying one or two sulphonic acid groups), alkylphosphonic acids (phosphonic acids with linear or branched alkyl radicals with 1 to 20 carbon atoms), arylphosphonic or aryl-disulfonic acids (aromatic radicals, such as phenyl and naphthyl carrying one or two phosphoric acid radicals), whose alkyl or aryl radicals can carry other substituents, eg p-toluenesulfon acid ico, salicylic acid, p-amino-salicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic etc. Suitable metal ions are, in particular, the ions of the elements of the second main group, especially calcium and magnesium, of the third and fourth main groups, especially aluminum, tin and lead, as well as of the eighth secondary group, especially chromium, manganese, iron, cobalt, nickel, copper, zinc, etc. Especially preferred are the metal ions of the elements of the secondary groups of the fourth period. The metals can be present in the different valences that correspond to them.

In the preparation of mixtures of pure active substances I, II and III, to which, if appropriate, other active substances are added against harmful fungi or other parasites, such as insects, arachnids or nematodes, or also active regulatory substances. of growth or fertilizers. The mixtures of compounds I and / or II and III or the combined or separate use of compounds I and / or II and III provide an excellent effect against a broad spectrum of phytopathogenic fungi, especially of the class of ascomycetes, deute- romicetos, fitomycetes and basidiomycetes. In part they have systemic action, so they can also be used as foliar and soil fungicides.

They are especially important for combating a myriad of fungi in different crop plants, such as cotton, legumes (eg cucumbers, beans and cucurbits), barley, turf, oats, coffee, corn, rice, rye, soy, vine, barley, ornamental plants, sugar cane and countless seeds.

They are especially suitable for combating the following phytopathogenic fungi: Erysiphe graminis (mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbitaces, Podosphaera leucotricha in apples, Uncinula necator in the vine, Puccinia species in cereals, Rhizoctonia species in cotton, rice and turf, Ustilago species in cereals and sugarcane, Venturia inaequalis in apples, Helmin-thosporium species in cereals, Septoria nodorum in wheat, Botrytis ciñera (gray rot) in strawberries, legumes, ornamental plants and vine, Cercospora arachidicola peanuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Pseudope-ronospora species in cucurbitas and hops, Plasmopara viticulture in the vine, Alternate species in legumes and fruits, as well as Fusarium and Verticillium species. In addition, they can be used in the protection of materials (eg wood preservation), for example against Paecilomyces variotii. The compounds I and / or II and III can be applied simultaneously together or separately or successively; in the separate application, generally, the order in which the compounds are applied has no effect on the success of the treatment.

The compounds I and / or II and III are usually applied in a weight ratio of 200: 1 to 0.1: 1, preferably 100: 1 to 1: 1, especially 50: 1 to 5: 1 (III: I and / or II) . The application rates of the mixtures according to the invention vary according to the desired effect in the case of compounds I and / or II from 0.005 to 0.5 kg / ha, preferably 0.01 to 0.5 kg / ha, in particular 0 , 01 to 0.3 kg / ha.

The application rates of the compounds III vary correspondingly from 0.1 to 10 kg / ha, preferably 0.5 to 5 kg / ha, especially 1 to 4 kg / ha.

In the treatment of the seeds, the mixtures are applied in amounts of 0.001 to 100 g / kg of seeds, preferably 0.01 to 50 g / kg, especially 0.01 to 10 g / kg. Provided that the plants are to combat phytopathogenic fungi, the separate or combined application of the compounds I and / or II and III or of the mixtures is carried out from the compounds I and / or II and III by spraying or spraying of seeds, plants or soils before or after planting of plants, or before or after plant emergence.

The synergistic fungicidal mixtures of the invention or the compounds I and / or II and III can be used in the form of solutions, powders, suspensions or dispersions, emulsions, oil dispersions, spraying agents, spraying agents, directly sprayable granules. , by spraying nebulization, atomization, spraying or watering. The forms of application depend entirely on the respective application purposes; in all cases, the finest possible distribution of the mixtures of the invention should be ensured. The formulations are prepared in known manner, eg by the addition of solvents and / or support substances. The formulations are usually added inert additives, such as emulsifiers or dispersants. Suitable surfactants are: alkali metal, alkaline earth metal, ammonium salts of lignin sulphonic acid, naphthalenesulfonic acid, phenylsulfonic acid and dibutylnaphthalene sulfonic acid, alkylaryl sulphonates, alkyl sulfates, alkyl sulphonates, fatty alcohol sulfates, and acids fatty acids, alkaline and alkaline earth metal salts, sulfated fatty alcohol glycol ethers, naphthalene condensates and naphthalene derivatives with formaldehyde, naphthalene condensates or naph alkylsulfonic acid with phenol and formaldehyde, polyoxyethylethylphenol ethers, isooctylphenol, octylphenol or nonylphenol ethoxylates, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, condensates of fatty alcohol-ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ethers, polyoxypropylene, polyglycol ether acetal d lauryl alcohol, the esters of sorbitol, sulphite residual liquors and methylcellulose.

The powders, spraying and spraying agents can be obtained by mixing or grinding together the compounds I and / or II and III or the mixture from the compounds I and / or II and III with a solid support. Granules (eg coated, impregnated or homogenous granules) are usually prepared by binding the active substance 0 the active substances with a solid support. As solids or solid supports, for example, mineral earths, such as silica gel, silicic acid, silica gel, silicates, talc, kaolin, limestone, lime, bolus, loess, clay, dolomite, diatomaceous earth, sulphate calcium and magnesium sulfate, magnesium oxide, ground plastics, as well as fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and mineral products, such as ce-real flour, bark powder, wood and of nut shells, cellulose powders or other solid supports. The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight, of one of the compounds I and / or II and III, or of the mixture of the compounds posts 1 and / or II and III. The active substances are used here in a purity of 95 to 100%, preferably 95 to 100% (according to NMR / HPLC spectrum). The compounds I and / or II and III, or the mixtures or the corresponding formulations are used, treating the noxious fungi, the plants, the seeds, the floors, the surfaces, the materials or the enclosures to keep free of them, with an active fungicidal quantity of the mixture, or of the compounds I and / or II and III in the separate application. The application can be made before or after the infestation by the harmful fungi. The fungicidal action of the compounds and mixtures can be checked by means of the following tests: The active substances are prepared separately or together as a 20% emulsion in a mixture from 70% by weight of cyclohexanone, 20% by weight of Nekanil® LN (Lutensol® AP6, hu-mectant with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight of Emulphor® (Emulan® EL, emulsifier based on ethoxylated fatty alcohols), and diluted with water according to the desired concentration. The evaluation is carried out, determining the area of the leaves in-festedas in percent. These percentage values are converted into degrees of action. The expected degrees of action of the mixtures of active substances are determined by the formula of Colby [R.S. Colby, Weeds 15., 20-22 (1967)] and compared with the observed degrees of action. Colby's formula: E = x + y + - x-y / 100 E means the expected degree of action, translated in% of the untreated control, when using the mixture from the active substances A and B in the concentrations a and b; x is the degree of action, translated in% of untreated control, by using active substance A in concentration a; and it is the degree of action, translated in% of the untreated control, by using the active substance B in the concentration b. The degree of action (W) is calculated on the basis of the Ab-bot formula as follows: W = (1 - a) «100 / ß a equals the fungal infection of the plants treated in% and ß equals the infection fungus from untreated (control) plants in%.

Given a degree of action equal to O, the infestation of the treated plants is equivalent to that of the untreated control plants; in the case of a 100% action grade, the treated plants do not show any infestation.

Claims (1)

Claims

1. Fungicidal mixture containing a) a carbamate of the formula I, where T denotes CH or N, n is 0, 1 or 2 and R is halogen, C? -C4-alkyl or C? -C4-haloalkyl, the radicals R being different when n is 2, and / or) an oxim ether of the formula II, wherein the substituents have the following meanings: X oxygen or amino (NH); And CH or N; Z oxygen, sulfur, amino (NH) or C? -C4-alkylamino (N-C? -C4-alkyl); R 'Ci-Cβ-alkyl, C? -C6-haloalkyl, C3-C6-alkenyl, C-C6-haloalkenyl, C3-C6-alkynyl, C3-C6-haloalkynyl, C3-C? -cycloalkyl-methyl, obencil which may be partially or completely halogenated and / or carry from one to three of the following radicals: cyano, C? -C4-alkyl, C? -C4-halogenoalkyl, C? -C4-alkoxy, C? -C4- haloalkoxy and C? -C4-alkylthio; and c) a dinitroaniline of formula III, in an active synergetic quantity. Fungicide mixture according to claim 1, characterized in that the weight ratio between compound III and compounds I and / or II is 200: 1 to 0.1: 1. Process for controlling harmful fungi, characterized in that the harmful fungi, their environment or the plants, seeds, soils, surfaces or enclosures to be kept free of them are treated with a compound of the formula I and / or a compound of the Formula II according to claim 1 and compound III according to claim 1. Method according to claim 3, characterized in that a compound I and / or II according to claim 1 and compound III according to claim 1 is applied simultaneously in joint or separate form or successively. Process according to claim 3, characterized in that the harmful fungi, their environment or the plants, seeds, soils, surfaces or enclosures to be kept free thereof are treated with 0.005 to 0.5 kg / ha of a compound I and / or II according to claim 1. Method according to claim 3, characterized in that the harmful fungi, their environment or the plants, seeds, soils, surfaces or enclosures are treated to be exempt thereof with 0.1 to 10 kg / ha of the compound or according to claim 1. use of the compounds I and / or II according to claim 1 for the preparation of active synergistic fungicidal mixtures according to claim 1. Use of a compound III according to claim 1 for the preparation of active, synergetic fungicidal mixtures according to claim 1. Summary of the Invention Fungicide mixtures containing a) a carbamate of the formula I, wherein T means CH or N, n is 0, 1 or 2 and R means halogen, C 1 -C 4 -alkyl or C?-C4-haloalkyl, the radicals R being able to be different when n is 2, and / or b) an oxim ether of the formula II, wherein the substituents have the following meanings: X oxygen or amino (NH); And CH or N; Z oxygen, sulfur, amino (NH) or C? -C4-alkylamino (N-C? -C4-alkyl); R 'Ci-Cβ-alkyl, Ci-Cβ-halogenoalkyl, C3-C6-alkenyl, c2-C6-haloalkenyl, C3-C6-alkynyl, C3-C6-halogenoalkynyl, C3-C6-cycloalkyl-methyl, obencilo can be partially or completely halogenated and / or carry from one to three of the following radicals: cyano, C? -C4-alkyl, C? -C4-halogenoalkyl, C? -C4-alkoxy, C? -C4-halogen - noalkoxy and C? -C4-alkylthio; and c) a dinitroaniline of formula III, in an active synergetic quantity. 0 5 0 5 0 5 0 5