MXPA98008781A - Fungicide mixtures - Google Patents

Abstract

The present invention relates to: fungicidal mixtures containing (a) a carbamate of the formula I, wherein X means CH or N, 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 able to be different when n is 2, and (b) a dithiocarbamate (II) selected from the group consisting of manganese-manganese (zinc dithiocarbamate) ethylenebis (dithiocarbamate) (IIa), manganese-ethylenebis (dithiocarbamate) ( IIb), - zinc ammonium (IIc) and zinc (IId) ethylenebis (dithiocarbamate), and / or (c) 1- (2-cyano-2-methoxyiminoacetyl) -3-ethylurea (III) H3CCH2-NHCONH-C (CN) = NOCH3 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 X means CH or N, n is 0, 1 or 2 and R means halogen, C? -C -al uilo or C? -C4-haloalkyl, the radicals R being different when n is 2, Y b) a dithiocarbamate (II) selected from the group consisting of manganese (zinc complex) (lia) ethylenebis (dithiocarbamate) manganese (Ilb) ethylenebis (dithiocarbamate) zinc ammonium (lye) and ethylenebis (dithiocarbamate) ethylene bis (dithiocarbamate) zinc (lid)), and / or c) 1- (2-cyano-2-methoxyiminoacetyl) -3-ethylurea (III) H3CCH2-NHCONH-C (CN) = NOCH3 III in an active synergistic amount.

In addition, the invention relates to processes for controlling harmful fungi with mixtures of compounds I, II and / or III and the use of compounds I, II and / or 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 dithiocarbamates II (lia: common yam: Mancozeb, US-A 3,379,610; llb: common yam: Maneb, US-A 2,504,404; lie: common ame anterior: Metiram, US-A 3,248,400; l d: common yam: Zineb, US-A 2,457,674), its preparation and its action against harmful fungi are also known. Also known are compound III (US-A 3,957,847; common ame: Cymoxanil), its preparation and its use against harmful fungi.

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, II and / or III jointly or separately, or by applying compounds I, II and / or III successively, it is better to combat harmful fungi than by applying the compounds by themselves. For this purpose, mixtures from I and II or I and III are suitable, but also mixtures containing 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 and Thanks to their basic character, compounds I and III 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 production of mixtures of pure active substances I and II and / or III, to which are added, if necessary, other active substances against harmful fungi or other parasites, such as insects, arachnids or nematodes, or else substances active growth regulators or fertilizers. The mixtures of compounds I and II and / or III or the combined or separate use of compounds I and II and / or 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,? Rysiphe cichoracearum and Sphaerotheca fuliginea in cucurbitáces, Podosphaera leucotricha in apples, Uncinula ñecator in the vine, Puccinia species in cereals, Rhizoctonia species in cotton, rice and turf, Ustilago species in cereals and sugar cane, 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 in peanuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, species of Pseudope-ronospora in cucurbitáces and hops, Plasmopara viticola in the vine, species of Alternaria 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 II and / or 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.

Compounds I and II 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 (11: 1).

Compounds I and III are usually applied in a weight ratio of 10: 1 to 0.1: 1, preferably 5: 1 to 0.2: 1, especially 3: 1 to 1: 3 (III: I).

The application rates of the mixtures according to the invention vary according to the desired effect in the case of compounds I of 0.005 to 0.5 kg / ha, preferably 0.01 to 0.5 kg / ha, especially 0.01 to 0. , 3 kg / ha.

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

The application rates of the compounds III vary, generally, from 0.005 to 0.8 kg / ha, preferably 0.01 to 0.5 kg / ha, especially 0.05 to 0.3 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.

Whenever the plants are to combat phytopathogenic fungi, the separate or combined application of compounds I, II and / or III or mixtures of compounds I, II and / or 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, II and / or III can be used in the form of solutions, powders, suspensions or dispersions, emulsions, oil dispersions, spraying agents, sprays, directly sprayable granules, atomization spray, atomization, spray 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 sulfonic acid, naphthalene sulphonic acid, phenylsulfonic acid and dibutylnaphthalene sulfonic acid, alkylaryl sulphonates, alkyl sulfates, alkyl sulphonates, fatty alcohol sulfates, and fatty acids , as well as their alkali metal and alkaline earth metal salts, the sulphated fatty alcohol glycol ethers, the naphthalene condensates and naphthalene derivatives with formaldehyde. condensates of naphthalene or naphthalene sulphonic acid with phenol and formaldehyde, polyoxyethylenectylphenol ethers, isooctylphenol, octylphenol or nonylphenol ethoxylates, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol-oxide condensates of ethylene, ethoxylated castor oil, polyoxyethylene alkyl ethers, polyoxypropylene, acetal polyglycol ether lauryl alcohol, sorbitol esters, sulphite residual liquors and methylcellulose. The powders, spraying and spraying agents can be obtained by mixing or co-mingling compounds I, II and / or III or mixing them from compounds I, II and / or III with a solid support. Granules (eg coated, impregnated or homogeneous granules) are usually prepared by joining the active substance or 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 cereal 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, II and / or III, or of the mixture of the compounds. posts I, II and / or III. The active substances are used here in a purity of 90 to 100%, preferably 95 to 100% (according to NMR / HPLC spectrum).

The compounds I, II and / or III, or the mixtures or the corresponding formulations are used, treating the harmful 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, II and / or III in the separate application. The application can be made before or after the infestation by the fungi no-civos.

Examples of the synergistic action of the mixtures according to the invention against 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 action and dispersant based on ethoxylated alkyl phenols) 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 done, determining the area of the leaves infested 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 compare them with the observed degrees of action.

Colby's formula: E = x + y + - x-y-z / 100 E signifies the expected degree of action, translated in% of the untreated control, by using the mixture from active substances A and B at concentrations a, b and c; x is the degree of action, translated in% of the untreated control, by using the active substance A in the concentration a; and it is the degree of action, translated in% of the untreated control, by using active substance B in the concentration b; z is the degree of action, translated in% of the untreated control, by using active substance C in the concentration c.

The degree of action (W) is calculated based on the Ab-bot formula as follows: W = (1 - a) «100 / ß a is equivalent to the fungal infection of the plants treated in% and ß is equivalent to the fungal infection of the 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.

Examples 1 - 6 Curative action against Plasmopara viticola Vine leaves grown in "Müller-Thur-gau" pots are inoculated with an aqueous suspension of the Plasmopara 'viticultural zoo-spores. The plants are then stored for 48 hours at 2-24 ° C in a chamber saturated with steam. Then they are removed from the chamber and once dry, the plants are sprayed until they drip with an aqueous preparation of active substances prepared with a stock solution from 10% of active substance, 63% of cyclohexanone and 27% of emulsifier. After the sprayed layer has dried, the plants are grown for 5 days in the greenhouse at temperatures between 20 and 30 ° C. After this time the plants are again placed for 16 hours in a humid chamber in order to accelerate the development of the sporangia. The extent of the development of the infection on the reverse sides of the leaves is then visually assessed. * calculated according to Colby's formula From the results obtained in the examples, it is found that the degree of action observed is with all the mixing ratios higher than the degree of action previously calculated according to the Colby formula.

Examples 7-19 Efficiency against Plasmopara viticola The vine leaves grown in pots of the "Müller-Thurgau" variety are sprayed until they drip with an aqueous preparation of active substances prepared with a stock solution from 10% active substance, 63% cyclohexanone and 27% emulsifier. In order to evaluate the lasting effect of the substances, the plants are placed after the sprayed layer has been dried for 7 days in the greenhouse. Only now are the plants inoculated with an aqueous suspension of zoospores of Plasmopara viticola. The plants are then stored for 48 hours at 24 ° C in a chamber saturated with water vapor and then for 5 days in the greenhouse at temperatures between 20 and 30 ° C. After this time the plants are again placed for 16 hours in a humid chamber in order to accelerate the development of the sporangia support. The extension of the development of the enfastación in the reverse sides of the leaves is then visually evaluated.

The visually determined values for the percentage of the infected leaf surface are converted to degrees of action as% of the untreated control. A degree of action equal to O means the same infection as in the untreated control, a degree of action of 100 means 0% infection. The expected action levels for the combination of active substance are determined according to Colby's formula (Colby, SR (Calculating synergistic and antagonistic responses of herbicide Combinations ", Weeds, 15, pp. 20 to 22, 1967) and compared with the degrees of observed action. * calculated according to the formula of Colby From the results obtained in the examples it is found that the observed degree of action is with all the mixing ratios higher than the degree of action previously calculated according to Colby's formula.

Claims (6)

1. Claims 1. Fungicidal mixture containing a) a carbamate of the formula I, wherein X 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 able to be different when n is 2, and / or ) a dithiocarbamate (II) selected from the group consisting of manganese (zinc complex) (lia) ethylenebis (dithiocarbamate) manganese (Ilb) ethylenebis (dithiocarbamate) zinc ammonium (lye) and ethylenebis (dithiocarbamate) ethylenebis (dithiocarbamate) zinc (lid)), and / or c) 1- (2-cyano-2-methoxyiminoacetyl) -3-ethylurea (III) H3CCH2-NHCONH-C (CN) = NOCH3 III in an active synergetic quantity.
2. 2. Fungicidal mixture according to claim 1, characterized in that it contains manganese ethylenebis (dithiocarbamate) (zinc complex) (bundle).
3. 3. Fungicidal mixture according to claim 1, characterized in that it contains manganese ethylenebis (dithiocarbamate) (Ilb).
4. 4. Fungicidal mixture according to claim 1, characterized in that it contains zinc ammonium ethylenebis (dithiocarbamate) (zinc).
5. 5. Fungicidal mixture according to claim 1, characterized in that it contains zinc ethylenebis (dithiocarbamate) (lid).
6. 6. Fungicide mixture according to claim 1, characterized in that the weight ratio between compound II and compound I 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 exempted thereof are treated with a compound of the formula I according to claim 1 and the compound II and / or III according to claim 1.