MXPA00005666A - Fungicide mixtures based on pyridine amides and chlorothalonil - Google Patents

Abstract

The invention relates to fungicide mixtures containing, as active components, a) an amide compound of formula (I) A-CO-NR1R2, wherein A represents an aryl group or an aromatic or non-aromatic, 5- or 6-structured heterocyclic compound having 1 to 3 heteroatoms selected from O, N, S;whereby the aryl group or the heterocyclic compound can optionally comprise 1, 2 or 3 substituents selected independently of one another from alkyl, halogen, CHF2, CF3, alkoxyl, haloalkoxyl, alkylthio, alkyl sulfinyl and alkyl sulfonyl;R1 represents a hydrogen atom;R2 represents a phenyl group or cycloalkyl group optionally containing 1, 2 or 3 substituents selected independently of one another from alkyl, alkenyl, alkynyl, alkoxyl, alkenyloxyl, alkynyloxyl, cycloalkyl, cycloalkenyl, cycolalkyloxyl, cycloalkenyloxyl, phenyl and halogen, whereby the aliphatic and cycloaliphatic radicals can be partially or completely halogenated and/or the cycloaliphatic radicals can be substituted by 1 to 3 alkyl groups, whereby the phenyl group can contain 1 to 5 halogen atoms and/or 1 to 3 substituents selected independently of one another from alkyl, haloalkyl, alkoxyl, haloxyl, alkylthio and haloalkylthio, and whereby the amidic phenyl group is optionally condensed with a saturated 5-structured ring which is optionally substituted by one or more alkyl groups and/or can comprise a heteroatom selected from O and S, and b) tetrachloisophthalonitrile (II). The active components are provided in a synergistically effective quantity.

Description

OF AMIDA AND TETRACLOROISOFTALONITRILO Description The present invention relates to fungicidal mixtures for controlling harmful fungi, as well as methods for controlling harmful fungi using these mixtures.

WO 97/08952 describes mixtures of amide compounds of the formula I A-CO-NRiR2 (I) wherein A means an aryl group or an aromatic or non-aromatic heterocycle with 5 or 6 members, having 1 to 3 heteroatoms selected from O, N and;; The aryl group or the heterocycle may optionally have 1, 2 or 3 substituents, each of which can be selected independently from the other, from alkyl, halogen, C? F2, CF3, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl and alkylsulfonyl; R1 means a hydrogen atom; R2 means a phenyl or cycloalkyl group, optionally having 1, 2 or 3 substituents, which are selected from alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloalkenyloxy, phenyl and halogen, whose aliphatic and cycloaliphatic radicals can be partially or completely halogenated and / or the cylcoaliphatic radicals can be substituted by 1 to 3 alkyl groups, and whose phenyl group can have from 1 to 5 halogen atoms and / or 1 to 3 substituents, which are independently selected from alkylaryl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, and whose amidic phenyl group can be fused with a saturated 5-membered ring, which is optionally substituted by one or more alkyl groups and / or a heteroatom selected from O, and S, and as acaricide the active substance known as Fenazaquin.

These mixtures are described as being especially effective against botrytis.

Collection and its action against harmful fungi are known (see "Pesticide Manual", page 193).

From EP-A 741 970 mixtures are known from representatives of the class of strobilorins and chlorothalonil.

The present invention has for its object to provide other additional products for controlling harmful fungi and especially for de-terminated indications, which contain as an active substance chlorothalonil.

Surprisingly, it has been found that this object is achieved with a mixture, which contains as active substances amide compounds of the formula I defined above and as another component of fungicidal action a fungicidal active substance tetrachloro-isophthalonityl II.

The mixtures according to the invention have synergetic action, so they are suitable for controlling harmful fungi and especially for controlling powdery mildew fungus in legumes and vines.

In the sense of the present invention, halogen means fluorine, chlorine, bromine and iodine, and especially fluorine, chlorine and bromine.

The term "alkyl" embraces linear or branched alkyl groups. Preferably, they are linear or branched alkyl groups of 1 to 12 and especially 1 to 6 carbon atoms. Examples of alkyl groups are alkyl, such as, especially methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl , 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2 -dimethylbuyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1-trimethylpropyl, 1,2,2-trimethylpropyl , 1-ethylbutyl, 2-ethylbutyl, l-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, decyl, dodecyl. which is partially or completely halogenated with one or more halogen atoms, especially fluorine and chlorine. Preferably it will contain from 1 to 3 halogen atoms, with preference being given to the difluoromethane group or the trifluoromethyl group.

The explanations given above with respect to the alkyl and haloalkyl group are analogously valid for the alkyl and haloalkyl groups in alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl and alkylsulfonyl.

The alkenyl group comprises linear and branched alkenyl groups. Preferably, they are linear or branched alkenyl groups with 3 to 12 and especially 3 to 6 carbon atoms. Examples of alkenyl groups are 2-propenyl, 2-butenyl, 3-bute-nyl, l-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, l-methyl -2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, l-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1 -dimethyl-2-propenyl, 1, 2-dimethyl-2-propenyl, l-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexe-nyl, l-methyl-2-pentenyl , 2-methyl-2-pentenyl, 3-methyl-2-pente-nyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-pente-nyl, 3-methyl-3 -pentenyl, 4-methyl-3-pentenyl, l-methyl-4-pente-nyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pente-nile, 1, dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, , 3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2, 2-dimethyl-3-bu-tenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl , 1-ethyl-2-butenyl, l-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-bute-nile, 1, 1, 2-trimethyl-2-pro penyl, l-ethyl-l-methyl-2-propenyl and l-ethyl-2-methyl-2-propenyl, especially 2-propenyl, 2-bute-nyl, 3-methyl-2-butenyl and 3-methyl-2 -pentenyl.

The alkenyl group can be partially or completely halofenode with one or more halogen atoms, especially fluoro and chloro. Preferably, it will have from 1 to 3 halogen atoms.

The alkynyl group comprises linear or branched alkynyl groups. Preferably, these are linear or branched alkynyl groups having 3 to 12 carbon atoms and especially 3 to 6 carbon atoms. Examples of alkynyl groups are 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2- methyl-3-butynyl, l-methyl-2-butynyl, 1, l-dimethyl-2-propynyl, l-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-alkynyl, 5-hexynyl, l- methyl-2-penti-nyl, l-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentyl-3-butynyl, 2,2-dimethyl-3-butynyl, l-ethyl-2-butynyl, l-ethyl-3-butynyl, 2-ethyl-3-butynyl and l- ethyl-l-methyl-2-propy-nyl.

The explanations given above with respect to the alkenyl group and its halogen substituents, as well as for the alkynyl group, are analogously valid for f-alkenyloxy and alkynyloxy.

In the cycloalkyl group, it is preferably a C3-C6-cycloalkyl group, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. When the cycloalkyl group is substituted, then it will preferably have 1 to 3 C? -C4-alkyl radicals as substituents.

Cycloalkenyl represents, preferably a C-C6-cycloalkenyl group, such as, for example, cyclobutenyl, cyclopentenyl or cyclohexenyl. When the cycloalkenyl group is substituted, then, it will preferably have 1 to 3 C? -Calkyl radicals as substituents.

A cycloalkoxy group is preferably a C5-C6-cycloalkoxy group, such as, for example, cyclopentyloxy or cyclohexyloxy. When the cycloalkoxy group is substituted, then it will preferably have 1 to 3 C-C4-alkyl radicals as substituents. The cycloalkenyloxy group is preferably a C5-C6-cycloalkenyloxy group, such as, for example, cyclopentyloxy or cyclohexyloxy. When the cycloalkenyloxy group is substituted, then, it preferably has 1 to 3 alkyl radicals with 1 to 4 carbon atoms as substituents.

Aryl preferably represents phenyl.

When A means a phenyl group, it may contain one, two or three of the abovementioned substituents in an arbitrary position. Preferably, these substituents will be selected, independently, from alkyl, difluoromethyl, trifluoromethyl and halogen, especially chlorine, bromine and iodine. The fe-nyl group very preferably has a substituent at position 2.

When A means a 5-membered heterocycle, it is, in particular, a furyl, thiazolyl, pyrazolyl, a radical or a tetra or a corresponding radical. A thiazolyl or pyrazolyl radical is preferred.

When A represents a 6-membered heterocycle, then it is a pyridyl radical or a radical of the formula: where one of the radicals X and Y means O, S or NR23, meaning R23 H or alkyl and the other radical representing X and Y CH, S, SO, S02 or NR23. The dotted line means that a double bond is eventually present.

Most preferably, the 6-membered aromatic heterocycle is a pyridyl radical, especially a 3-pyridyl radical, or a radical of the formula (A3; where X is CH2, S, SO or S02.

The aforementioned heterocyclic radicals can optionally have 1, 2 or 3 of the abovementioned substituents, the substituents being preferably selected, each independently of the other, from alkyl, halogen, difluoromethyl or trifluoromethyl.

Most preferably, A means a radical of the formulas: (Al) (A2) (A5) (A7) CH3 of another, r eneno, a quo, espec a men e o, halogen, especially chloro, CHF2 or CF3.

The radical R 1 in formula I preferably represents a hydrogen atom.

The radical R2 in the formula I preferably means a phenyl radical. Preferably, R 2 has a substituent, which is found especially at position 2. The (or substituents) are preferably selected from alkyl, cycloalkyl, cycloalkenyl, halogen or phenyl.

The substituents of the radical R.sup.2 may in turn be replaced again. The aliphatic or aromatic substituents may be partially or completely halogenated, especially fluorinated or chlorinated. Preferably, they will have 1, 2 or 3 fluorine or chlorine atoms. When the substituent of the radical R2 is a phenyl group, then it can be substituted, preferably, by 1 to 3 halogen atoms, especially chlorine atoms, and / or by a radical, which is selected, preferably, from alkyl and alkoxy. Especially preferred is the phenyl group with a halogen atom in the p-position, that is, the especially preferred substituent of the radical R2 is a phenyl radical substituted by halogen in p. The radical R2 can also be condensed with a five-membered ring, the ring itself being able to have from 1 to 3 alkyl substituents.

R2 represents, then, for example, indanyl, thiaindanyl and oxaindanyl. Preferred are indanyl and 2-oxaindanyl, which are linked, especially via the 4-position with the nitrogen atom.

In a preferred variant, the product according to the invention contains, as the amide compound, a compound of the formula I, wherein A has the following meanings: phenyl, pyridyl, dihydropyranyl, dihydrooxathiinyl, dihydro-oxathiinyl oxide, dihydrooxathiinyl dioxide, furyl, thiazole. lyl, pyrazolyl or oxazolyl, the groups may have 1, 2 or 3 substituents, independently selected from alkyl, halogen, difluoromethyl and trifluoromethyl.

According to another preferred variant A means: pyridin-3-yl, which optionally is stabilized in position 2 by halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl or methylsulfonyl; methyl, trifluoromethyl, chlorine, bromine or iodine; 2-methyl-5,6-dihydropyran-3-yl; 2-methyl-5,6-dihydro-l, 4-oxatiin-3-yl or the 4-oxide or 4,4-dioxide; 2-methyl-furan-3-yl, which is optionally substituted in the 4-position and / or 5 by methyl; thiazol-5-yl, which is optionally substituted in the 2-position and / or 4 by methyl, chloro, difluoromethyl or trifluoromethyl; thiazol-4-yl, which is optionally substituted in the 2-position and / or 5 by methyl, chloro, difluoromethyl or trifluoromethyl; l-methylpyrazol-4-yl, which is optionally substituted in the 3-position and / or 5 by methyl, chloro, difluoromethyl or trifluoromethyl; or oxazol-5-yl, which, optionally, is substituted in the 2-position and / or 4 by methyl or chloro.

According to another preferred variant, the products according to the invention contain as the amide compound a compound of the formula I, wherein R 2 represents a phenyl group, which is optionally substituted by 1, 2 or 3 of the aforementioned substituents.

According to another preferred variant, the products according to the invention contain as the amide compound a compound of the formula I, wherein R 2 represents a phenyl group, which in the 2-position has one of the following substituents: C 3 -C 6 -alkyl, Cs-C 6- cycloalkenyl, C5-C6-cycloalkyloxy, cycloalkenryloxy, the groups of which may be substituted by 1, 2 or 3 alkyl groups with 1 to 4 carbon atoms, phenel, which is substituted by 1 to 5 halogen atoms and / or 1 to 3 groups, independently selected from C? -C4-alkyl, C? -C4-haloalkyl, C? -C-alkoxy, C? C4-halogen-alkoxy, C? -C4-alkylthio and C1-C4-haloalkylthio, indanyl or oxaindanyl, which, optionally, is substituted by 1, 2 or 3 alkyl groups with 1 to 4 carbon atoms.

According to another preferred variant, the products according to the invention contain, as the amide compound, a compound of the formula la, where A means (Al) (A2 (A3) (A7) (A8.

X means methylene, sulfur, sulfinyl or sulfonyl (S0), R3 signifies methyl, difluoromethyl, trifluoromethyl, chloro, bromo or iodo, R4 signifies trifluoromethyl or chloro, R5 signifies hydrogen or methyl, R6 signifies methyl, difluoromethyl, trifluoromethyl or chloro, R7 means hydrogen or, methyl or chloro, R8 signifies methyl, difluoromethyl or trifluoromethyl, R9 signifies hydrogen or, methyl, difluoromethyl, trifluoromethyl or chloro, R10 signifies C? -C-alkyl, C-alkoxy, C? -C4-alkylthio or halogen.

According to an especially preferred variant, the products contain as the amide compound a compound of the formula Ib where R 4 is halogen and R 11 is phenyl, which is substituted by halogen.

Suitable amide compounds of formula I are those, of EP-A-545 099 and 589 301, which are incorporated herein by reference in their entirety.

The preparation of the amide compounds of the formula I is known, for example, from EP-A-545 099 or 589 301 or can be carried out according to analogous processes.

To develop the synergistic effect, a small proportion of the amide compound of formula 1 is sufficient. Preferably, the amide compound and the tetrachloroisophthalonitrile are used in a quantitative ratio of 20: 1 to 1:20, especially 10: 1 to 1. : 10 Thanks to the basic character of the nitrogen atoms contained in them, the compounds I are capable of forming salts or adducts with inorganic or organic acids or with salts of metal ions.

Examples of inorganic acids are the halogenated hydroxides, such as, for example, 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, trichloroacetic acid and propionic acid, as well as glycolic acid, thiocyanic 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 and aryldi sulphonic acids (aromatic radicals, such as phenyl and naphthyl) , carrying one or two sulfonic acid groups), alkyl branched acids with 1 to 20 carbon atoms), aryl phosphonic or aryl diphosphonic acids (aromatic radicals, such as phenyl and naphthyl, bearing one or two phosphoric acid radicals) ), whose alkyl or aryl radicals can carry additional substituents, such as, for example, p-toluenesulfonic acid, icílico, p-aminosalicyclic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

As metal ions, especially the ions of the first to eighth secondary group elements, especially chromium, manganese, iron, cobalt, nickel, copper, zinc and, in addition, of the second main group, especially calcium, are especially suitable. and magnesium, from the third and fourth main group, especially alu-ni, tin and lead. Metals may even be present in their corresponding valences.

Preferably, pure substances I and II are used in the preparation of the mixtures, to which other active substances can be added against harmful fungi or against other parasites, such as insects, arachnids, nematodes or also herbicidal or regulating active substances. of growth or fertilizers.

The mixtures of the compounds I and II or the combined or separate use of the compounds I and II provide an excellent effect against a broad spectrum of phytopathogenic fungi, especially of the class of the ascomycetes, basidiomycetes, ficomycetes and deuteromycetes. 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, bananas, 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 (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbitáces, Podosphaera leucotricha in apples, Uncinula necator in the vine, Puccinia species in cereals, Rhizoctonia species in cotton, rice and grass, Ustilago species in cereals and sugar cane, Venturia inaequalis in apples, Helminthos-porium 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, ronospora in cucurbitáces and hops, Plasmopara viticola in the vine, Alternate species in legumes and fruits, as well as Fusarium and Verticillium species.

The mixtures according to the invention are most preferably used to control powdery mildew in vine and vegetable crops, as well as ornamental plants.

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.

The application rates of the mixtures according to the invention vary, especially in agricultural growing areas, according to the desired effect of 0.01 to 8 kg / ha, preferably 0.1 to 5 kg / ha, especially 0.2 to 3.0 kg / ha.

The application rates of compounds I vary from 0.01 to 2.5 kg / ha, preferably 0.05 to 2.5 kg / ha, especially 0.1 to 1.0 kg / ha.

The application rates of compounds II vary, correspondingly, from 0.01 to 10 kg / ha, preferably 0.05 to 5 kg / ha, especially 0.05 to 2.0 kg / ha.

In the treatment of the seeds, the mixtures are applied in amounts of 0.001 to 250 g / kg of seeds, preferably 0.01 to 100 g / kg, especially 0.01 to 50 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 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 directly pulverisable solutions, powders and suspensions or in the form of aqueous, oleic or other highly concentrated suspensions, dispersions, emulsions, oil dispersions. , spraying agents, spraying agents, directly sprayable granules, by spraying, spraying, spraying or spraying. The forms of application depend entirely on the ends of the finest possible distribution of the mixes.

The formulations are prepared in a known manner, for example by mixing the active substance with solvents and / or support substances, if desired, using emulsifiers and dispersants, it being necessary, that in the case of using water as a diluent, they can also use other organic solvents as auxiliary solvents. Suitable acyloid substances are essentially: solvents, such as aromatics (eg xylenes), chlorinated aromatics (eg chlorobenzenes), paraffins (eg petroleum fractions), alcohols (e.g. methanol, butanol), ketones (eg cyclohexanone), amines (eg ethanolamine, dimethylformamide) and water; carrier substances, such as natural stone pilings (eg kaolins, clays, talcum) and synthetic stone powders (eg highly disperse silicic acid, silicates); emulsifiers, such as non-ionogenic and anionic emulsifiers (eg polyoxyethylene fatty alcohol, alkyl and aryl sulfonates) and dispersants, such as sulphite residual liquors and methylcellulose.

Suitable surface-active substances are the alkaline earth metal and ammonium salts of lignin sulphonic acid, naphthalamine acid, phenolsulfonic acid, dibutyl naphthalene sulphonic acid, fatty acids, alkyl and alkylaryl sulphonates, alkyl sulfates, lauryl ether sulphates and alcohol sulfates. fatty acids, and the salts of sulphonated hexa, hepta and octadecanols, sulphonated naphthalene condensates and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene-noctilphenol ethers, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol condensates, ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ether, polyoxypropylene ethoxylated, polyglycol ether-ketal of lauryl alcohol, sorbitol ester, lignin sulphide residual liquors cas and methylcellulose.

The powders, spraying and spreading agents can be obtained by mixing or co-grinding the compounds I or II or the mixture from the compounds I and II with a solid support.

Granules, eg coated granules, impregnated granules and homogeneous granules can be prepared by joining active substances with solid supports. minerals, such as silicagel, siliceous acids, silicates, aleo, kaolin, attaclay, limestone, chalk, bolus, loess, dolomite, diatomaceous earth, magnesium sulfate and calcium sulfate, magnesium oxide, ground plastics, fertilizers, as p ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flours, tree bark powders, wood and nut shell powders, cellulose powders and other solid supports.

The formulations generally contain between 0.1 and 95% by weight, preferably between 0.5 to 90% by weight, of one of the compounds I or II or of the mixture of the compounds I or II. The active substances are used here in a purity of 90% up to 100%, preferably 95% up to 100% (according to HPLC spectrum).

The compounds I or II or of the mixtures or the corresponding formulations are applied, treating the harmful fungi, their living space or the plants, seeds, floors, areas, materials or enclosures to be kept free of them, with an active quantity fungicide of compounds I and II in the separate application.

The application can be made before or after infection by harmful fungi.

Examples of formulations of this type, which contain the active substances, are: I. a solution from 90 parts by weight of the active substances and 10 parts by weight of N-methylpyrrolidone, suitable for use in the form of tiny drops; II. a mixture from 20 parts by weight of the active substances, 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 5 parts by weight of the addition product of 40 moles of ethylene oxide to 1 moles of castor oil; by distributing the solution finely in water a dispersion is obtained; III. an aqueous dispersion from 20 parts by weight of the active substances, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 40 moles of ethylene oxide to 1 mole of oil of castor active substances, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction from boiling point 210 to 280 ° C and 10 parts by weight of the addition product of 40 moles of ethylene oxide to 1 mole of Castor oil; V. a milled mixture in a hammer mill from 80 parts by weight of the active substances, 3 parts by weight of the sodium salt of diisobutylnaphthalene-1-sulphonic acid, 10 parts by weight of the sodium salt of a lignin sulphonic acid of a sulphite residual liquor and 7 parts by weight of powdery silicagel; by distributing the mixture finely in water, a spray mixture is obtained; SAW. an intimate mixture from 3 parts by weight of the active substances and 97 parts by weight of finely particulate kaolin; this spray agent contains 3% by weight of active substance; VII. an intimate mixture is 30 parts by weight of the active substances, 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil applied on the surface of this silica gel; this preparation gives an active substance with good adhesion; VIII. a stable aqueous dispersion from 40 parts by weight of the active substances, 10 parts by weight of the sodium salt of a condensate of phenolsulfonic acid, urea-formaldehyde, 2 parts by weight of silica gel and 48 parts by weight of water, which can be be further diluted; IX. a stable olefin dispersion from 20 parts by weight of the active substances, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of the fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of an acid condensate phenylsulphonic-urea-formaldehyde and 88 parts by weight of a paraffinic mineral oil.

Application example The synergistic effect of the mixtures according to the invention can be demonstrated by the following tests: The active substances, used separately or together, are formulated as a 10% emulsion in a mixture from 63% by weight of cyclohexanone and 27% by weight of an emulsifier, and are diluted in water to the desired concentration. festadas in by c in. These percentage values are converted into degrees of action. The degree of action (W) is determined by means of the formula of Abbot in the following way: = (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.

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 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 the active substance B in the concentration b.

Application example 1 - Efficiency against Botryis cinerea in peppers Slices of green peppers are pulverized until they drip with an aqueous preparation of active substance prepared from a wood solution composed of 10% active substance, 63% cyclohexanone and 27% emulsifier. 2 hours after drying the sprayed layer the fruit slices are inoculated with a spore suspension of Botrytis cinerea, which contains 1.7 x 106 spores per ml of a 2% aqueous solution of malt. The inoculated slices are incubated, then, in humid chambers for 4 days to ro a as to ru as n e as.

As compounds of the formula I the following components are used: The results are shown in the following tables 1 and 2, Table 1 Table 2 From the results of the test it can be deduced that the degree of action observed is with all the mixing ratios higher than the degree of action calculated according to the Colby formula.

Application example 2 - Efficiency against Phytophthora infestans in tomatoes Leaves of tomato plants of the variety "Grobe Fleichto-mate" grown in pots are sprayed until dripping with an aqueous suspension prepared from a stock solution comprising 10% active ingredient, 63% cyclohexanone and 27% of emulsifier The next day the leaves are infected with an aqueous suspension of zoospores of Phytophthora infestans. Next, the plants are placed in a chamber saturated with water vapor at temperatures between 16 and 18 ° C. After 6 days the infection has developed so strongly in the sintered but infected control plants, that the infection can be evaluated visually in%.

The results are shown in tables 3 and 4 below.

Table 3 Table 4 *) calculated according to the formula of Colby From the results of the test it is clear that the degree of action observed is with all the mixing ratios higher than the degree of action calculated according to Colby's formula.

Claims (7)

1. A fungicide mixture containing as active components: a) an amide compound of the formula I A-CO-NR1-} 2 wherein A is one of the following groups: pyridyl, thiazolyl, or pyrazolyl, wherein these group may have 1, 2 or 3 substituents which are selected, independent of each other, from alkyl, halogen, difluoromethyl, and difluoromethyl; R is a hydrogen atom; R is a phenyl group having 1, 2 or 3 substituents which are selected from alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloalkenyloxy, phenyl and halogen, independent of each other, wherein the aliphatic and Cycloaliphatics can be partially or completely halogenated and / or the cycloaliphatic radicals can be substituted by from 1 to 3 alkyl groups and where the phenyl group can have from 1 to 5 halogen atoms and / or 1 to 3 substituents which are selected, independently of one another, from alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, and wherein the amide phenyl group may or may not be fused with a 5-membered, saturated ring, which may or may not be substituted by one or more alkyl groups and / or may have a heteroatom selected from O and S, or is a cycloalkyl group which may have one of the aforementioned substituents, and tetrachloro talonitrile [sic] II CN in an effective amount for a synergistic effect. The fungicide mixture, as mentioned in claim 1, wherein in the formula I, the radical A is one of the following groups: pyridin-3-yl, which may or may not be substituted in the 2-position by halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, methylthito, methylsulfinyl, methylsulfonyl; thiazol-5-yl, which may or may not be substituted at the 2-position and / or 4 by methyl, difluoromethyl, trifluoromethyl; thiazol-5-yl, which may or may not be substituted in the 2-position and / or 5 by methyl, chloro, difluoromethyl, or trifluoromethyl; l-methylpyrazol-4-yl, which may or may not be substituted in the 3-position and / or 5 by methyl, chloro, difluoromethyl or trifluoromethyl.

The fungicide mixture, as mentioned in one of the preceding claims, which contains a compound of the formula I in which R2 is a phenyl group which may or may not be substituted by 1, 2 or 3 of the substituents mentioned in claim 1 .

Four . The fungicide mixture, as mentioned in claim 3, wherein R * "is a phenyl group having one of the following substituents at position 2:

C-C5 alkyl, Cs-C¿ cycloalkenyl, Cs-Ce cycloalkyloxy, cycloalkenyloxy, wherein these groups may be substituted by 1, 2 or 3 C1-C4 alkyl groups, phenyl substituted by from 1 to 5 halogen atoms and / or from 1 to 3 groups which are selected, independent of each other, of C 1 -C alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy C4, C 1 -C 4 alkylthio C 1 -C 4 haloalkylthio, or wherein R 2 is indanyl or oxaindanyl which may or may not be substituted by 1, 2 or 3 C 1 -C 4 alkyl groups.

5. The fungicidal mixture, as mentioned in any of claims 1 to 4, which contains an amide compound of the formula as follows: R? O in which A is (A7) R4 is trifluoromethyl or chloro, R6 is methyl, difluromethyl, trifluoromethyl o.chloro, R7 is hydrogen, methyl or chloro, R8 is methyl, difluoromethyl or trifluoromethyl, R9 is hydrogen, methyl, difluoromethyl, trifluoromethyl or chloro, R 10. is C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio or halogen.

6. The fungicidal mixture, as mentioned in any of claims 1 to 5, which contains as compound amide a compound of the following formula Ib: wherein R 4 is halogen, and R 11 is phenyl which is substituted by halogen.

7. The fungicidal mixture, as mentioned in claim 1, which contains as compound amide a compound of the following formulas: The fungicide mixture, as mentioned in any of the preceding claims, which is conditioned in two parts, one part containing the amide compound I in a solid or liquid carrier and the other part containing the compound of the formula II in a solid or liquid carrier. A method to control harmful fungi, which consists of treating the fungi, their habitat or the materials, plants, seeds, soils, areas or spaces that are going to be protected against fungal attack, with a fungicide mixture as mentioned in any of the claims 1 to 9 [sic], wherein the application of the active ingredients, the amide compound I and the compound of the formula II can be carried out simultaneously, together or separately or in succession. SUMMARY OF THE INVENTION Fungicidal mixtures containing as active components a) an amide compound of the formula i A-CO-NRiR2 (I) wherein A is an aryl group or an aromatic or non-aromatic heterocycle with 5 or 6 members, having 1 to 3 heteroatoms selected from O, N and S; the aryl group or the heterocycle may optionally have 1, 2 or 3 substituents, each of which can be independently selected from alkyl, halogen, CHF 2, CF 3, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl and alkylsulfonyl; R1 means a hydrogen atom; R2 means a phenyl or cycloalkyl group, optionally having 1, 2 or 3 substituents, which are selected from alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloalkenyloxy, phenyl and halogen, whose aliphatic and cycloaliphatic radicals can be partially or completely halogenated and / or the cylcoaliphatic radicals can be substituted by 1 to 3 alkyl groups, and whose phenyl group can have from 1 to 5 halogen atoms and / or 1 to 3 substituents , which are independently selected from alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, and whose amidic phenyl group can be fused with a saturated 5-membered ring, which is optionally substituted by one or more alkyl groups and / or a heteroatom selected from O, and S, and in an active synergetic quantity. 10 fifteen twenty 25 30 35 40 Four. Five