MXPA99010160A - Fungicidal mixtures - Google Patents

Abstract

The invention relates to a fungicidal mixture containing a synergistically active quantity of a) a carbamate of formula (I) in which T is CH or N, n is 0, 1 or 2 and R is a halogen, C1-C4-alkyl or C1-C4 halogen alkyl, where the R radicals can be different if n equals 2;and b) an active ingredient of the formula (II) in which the substituents have the following meanings:Y is hydrogen, a metal from main groups I to III of the periodic table of elements or an NR3R4R5R6 group;R2 is hydrogen, a C1-C18 alkyl group which can be substituted with halogen or a nitro-group, a C2-C8-alkenyl or C2-C8-alkynyl group which can be substituted with halogen or a nitro-group, a C1-C8-alkoxy-C1-C8-alkyl or a C2-C8-alkenyl-C1-C8-alkyl group, an optionally substituted aryl group with between 6 and 14 C-atoms, a C3-C7-cycloalkyl group, aC1-C4-alkyl aryl group or a heterocyclic group with 5 or 6 ring atoms and a heteroatom from the group N, O or S, whereby the heterocyclic group is linked to the oxygen atom directly or via an aliphatic chain;R3-R6 independently of each other are a C1-C4-alkyl group or a C1-C4 hydroxy alkyl group.

Description

FUNGICIDE MIXES.

Description The present invention relates to fungicidal 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? -C4-alkyl or Ci-C ^ -halogenoalkyl, the radicals R being able to be different when n is 2, and b) an active substance of formula II, H R2-0-P-OY (ID wherein the substituents have the following meanings: And hydrogen, a metal atom from the Ier up to the IIIrd main group of the periodic system of elements or a group NR3RR5R6; R2 hydrogen, a C? -C? 8-alkyl group, which may be substituted by halogen or a nitro group, a Ca-C? -alkenyl group, or C2-C8-alkynyl which may be substituted by halogen or a nitro group, a Ci-Cβ alkoxy-Ci-Cs-alkyl group or a C2-C-8-alkenyl-C? -8-alkyl group, an alkyl group optionally substituted by 6 to 14 carbon atoms, a group C3-C-cycloalkyl, a C? -C-4-alkylaryl group or a heterocyclic group with 5-6 ring atoms and a heteroatom of the group N, O or S, the heterocyclic group being linked directly or via an aliphatic chain to the oxygen atom, and R3-R6 each independently of the other, a Ci-Ca-alkyl group or a C-C-4-hydroxyalkyl group in an active synergetic quantity.

In addition, the invention relates to a process for controlling harmful fungi with mixtures of compounds I and II and to the use of compounds I and II for the preparation of 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 96 / 01,258).

Compounds II are described in the literature as fungicides and insecticides (eg DE 24 63 046 and the literature cited therein, a known representative of this class of active substances is commercially available under the common name: Fosetyl or Fo -setyl-Al The processes for obtaining the compounds of the formula II are known per se to the expert, so it is not necessary to detail them here.

In order to be able to reduce the amounts of aliquot and improve the action spectrum 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. Furthermore, it was found that by simultaneously applying the compound I and the compound II together or separately, or by applying the compounds I and the compounds II successively, it is better to fight off harmful fungi than by applying the compounds alone.

Formula I represents, in particular, carbamates, in which the combination of substituents is equivalent to one of the lines in the following table: Table 1: 0 , compounds 1.12, 1.23, 1.32 and 1.38 are especially preferred. the general formula II is especially representative for the compounds in which R2 means hydrogen or an alkyl group with 1 to 4 carbon atoms, and, especially, an ethyl group (-CH2CH3) and Y means a metal of the IIIrd main group of the Peridiodic system of elements. Also suitable are the first and second secondary group metals, such as Li, K, Na, Cs, Mg or Ca, to denote a few as examples. But basically compounds II are also suitable, in which R2 and R3_R6 have the meanings indicated above.

Especially preferred as compound II is the active substance 0 known under the name Fosetyl or its aluminum salt, Fosetyl-Al. The compounds of the formula I can be present with respect to the double bonds C = Y- or C = CH or the double bonds C = N in the E or Z configuration (in relation to the carboxylic acid function) Therefore, they can be used in the mixture according to the invention as pure E or Z isomers, or else as E / Z isomeric mixtures.

E / Z or the Z-isomer, with the Z-isomer being particularly preferred. The C = N double bonds of the oxymer ether groups in the side chain of compounds I may be present in the form of pure E or Z isomers, or as mixtures isomers E / Z. The compounds I can be used as isomeric mixtures or as pure isomers ^ - > in the mixtures according to the invention. With respect to their use, compounds I are especially preferred, in which the terminal oxymer ether of the side chain is in the cis configuration (OCH3 with respect to ZR ').

Thanks to their basic character, the compounds I are capable of forming 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 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, cinnamic acid, oxalic acid, alkylsulfonic acids (sulphonic 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 sulfonic acid groups) , alkylphosphonic acids (phosphonic acids with linear or branched alkyl radicals with 1 to 20 carbon atoms), arylphosphonic or aryl-sulphonic acids (aromatic radicals, such as phenyl and naphthyl carrying one or two phosphoric acid radicals), whose alkyl radicals or aryl can carry other substituents, eg p-toluenesulf acid nico, salicylic acid, p-amino- salicylic, 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 the mixtures of pure active substances I and II, to which, if appropriate, other active substances are added against harmful fungi or other parasites, such as insects, arachnids or nematodes, or also regulatory active substances. of growth or fertilizers.

The mixtures of compounds I and II or the combined or separate use of compounds I and II provide an excellent effect against a broad spectrum of phytopathogenic fungi, especially of the class of ascomycetes, deuteromycetes, phyco-mycetes 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 countless fungi in different crop plants, such as cotton, legumes (eg cucumbers, beans and cucurbits), barley, turf, oats, coffee, corn, rice, rye, soybeans, 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 cucurbitáces, Podosphaera leucotricha in apples, Uncinula ñécator in the vine, Puccinia species in cereals, Rhizoctonia species in al-godón , rice and grass, Ustilago species in cereals and sugarcane, Venturia inaequalis in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis ciñera (gray rot) in strawberries, legumes, ornamental plants and grapes, Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Pseudoperonospora species in cucurbitas and hops, Plasmopara viticola in the vine, Alternate species in legumes and fruits, as well as species of Fusarium and Verticilli? M.

In addition-- they can be used in the protection of materials (eg wood preservation), for example against Paecilomyces variotii.

The compounds I and II 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 0.05: 1 to 20: 2, preferably 0.1: 1 to 10: 1, especially 0.2: 1 to 5: 1 (11: 1).

The application rates of the mixtures according to the invention vary according to the desired effect, in case of compounds I, from 0.005 to 0.5 kg / ha, preferably 0.05 to 0.5 kg / ha, especially from 0.05 to 0.2 kg / ha.

The amounts of application of the compounds II vary, correspondingly, generally, from 0.01 to 2 kg / ha, preferably 0.05 to 1 kg / ha, especially 0.1 to 0.8 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 and II or mixtures from compounds I and II is carried out by spraying or spraying the seeds, plants or soils. before or after the planting of the plants, or before or after the emergence of the plants.

The synergistic fungicidal mixtures of the invention or compounds I and II can be used in the form of solutions, powders, suspensions or dispersions, emulsions, oil dispersions, spraying agents, sprays, directly sprayable granules, by spraying nebulization, atomization , sprayed or watered. 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 dibutyl naphthalene 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, sulfated fatty alcohol glycol ethers, naphthalene condensates and naphthalene derivatives with formaldehyde, those containing naphthalene or naphthalene sulphonic acid with phenol and formaldehyde, polyoxyethylene-ethylphenol ethers, Isooctylphenol, octylphenol or nonylphenol ethoxylates. alkylphenol polyglycol ethers, tributyl phenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, condensates of fatty alcohol-ethylene oxide, castor-ethoxylated oil, polyoxyethylene alkyl ethers, polyoxypropylene, polyglycol ether acetal of lauryl alcohol, esters of sorbitol, sulphite residual liquors and methylcellulose.

The powders, spraying and spraying agents can be obtained by mixing or milling together the compounds I or II and / or the mixture from the compounds I and II with a solid support.

Granules (eg coated, impregnated or homogenous granules) are usually prepared by joining the active substance or active substances with a solid support.

As solids or solid carriers, for example, mineral earths, such as silica gel, silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, bolus, loess, clay, dolomite, diatomaceous earth, sulfate, can be used. of 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 nut shells, powders, cellulose 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 or II, or of the mixture of the compounds I and II. 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 or II, 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 be kept free of them, with a active fungicidal amount of the mixture, or of the compounds I and II in the separate application. The application can be made before or after the infestation by the harmful fungi.

Application example 1 - Effect against Plasmopara vi tícola Vine leaves grown in pots of the "Müller-Thurgau" variety are sprayed until they drip with aqueous preparation of active substance with a stock solution prepared from 63% cyclohexanone and 27% emulsifier. In order to evaluate the lasting effect of the substances, the plants are placed after drying the sprayed layer for 7 days in the greenhouse. Only then are the leaves inoculated with an aqueous suspension of zoo-spores of Plasmopara viticola. Next, the plants are placed, first, for 48 h in a chamber saturated with air vapor at 2 ° C, and then for 5 days in the greenhouse at temperatures between 20 and 30 ° C. After this time the plants are placed again, to accelerate the eruption of the sporangiophores, for 16 h in a humid chamber. The development of the extent of the disease on the lower sides of the leaves is then visually determined.

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 1-5, 20-22 (1967)] and compare-two with the observed degrees of action.

Colby's formula: E = x + y - x-y.z / 100 E means the expected degree of action, translated in% of the untreated control, by 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 the untreated control, by using the active substance A in the concentration a; is the degree of action, translated in% of the untreated control, by using active substance B in the concentration b; 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 determined by means of the formula of Abbot in the following way: W = (l - a) -100 / ß a equals the fungal infection of the plants treated in% and ß equals 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.

Table 2 Table 3 *) calculated according to Colby's formula From the results of the test it can be deduced that the degree of action observed is with all the mixtures higher than the degree of action precalculated according to the Colby formula.

Claims (1)

Claims

1. Fungicide 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, Ci-Gi-alkyl or C? -C4-haloalkyl, the radicals R being able to be different when n is 2, and b) an active substance of formula II, H R2-0-P-OY (11) wherein the substituents have the following meanings: And 'hydrogen, a metal atom of the Ier up to IIIrd main group of the periodic system of elements or a group NR3R4R5R6; R2 hydrogen, a Ci-Cia-alkyl group, which may be substituted by halogen or a nitro group, a C2-C8-alkenyl group, or C2_C8-alkynyl which may be substituted by halogen or a nitro group, a Ci- Cß alkoxy-Ci-Cß-alkyl or a C 2 -C 8 -alkenyl-C?-C 8 -alkyl group, an alkyl group optionally substituted by 6 to 14 carbon atoms, a C 3 -C -cycloalkyl group, a group C? -C4-alkylaryl or a heterocyclic group with 5 or 6 ring atoms and a heteroatom of the group N, O or S, the heterocyclic group being linked directly or via an aliphatic chain to the oxygen atom, and R3-R6 each independently of the other, a C?-C 4 alkyl group or a C C-hydroxyalkyl group in an active synergetic quantity. The fungicidal mixture according to claim 1, which contains a compound of the formula II, wherein Y is a metal of the IIIrd main group. Fungicide mixture according to claim 2, wherein the metal of the III major group is Al. Fungicidal mixture according to one of claims 1 to 3, which contains a compound II in which R 2 is hydrogen or an alkyl group having 1 to 4 carbon atoms. Fungicidal mixture according to claim 1, which contains a compound of the formula II, wherein Y means Al and R2 means CH2-CH3. Procedure to control harmful fungi, characterized in that harmful fungi are treated, their. living space or the plants, seeds, soils, surfaces or enclosures to be exempted therefrom with a compound of the formula I according to claim 1 and a compound of the formula II according to claim 1. Process according to claim 6, characterized in that the harmful fungi, their living space or the plans are treated. seeds, soils, surfaces or enclosures to be exempt from them with 0.005 to 0.5 kg / ha of a compound I claim 1. Process according to claim 6, characterized in that the harmful fungi, their living space or the plants, seeds, floors, surfaces or enclosures to be kept free thereof with 0.01 to 2 kg / ha of a compound II are treated. .