MXPA00005384A - Fungicide mixtures based on amide compounds and pyridine derivatives - 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, R1 and R2 have the meanings given in the description, and b) compounds of formula (II), the N-oxide thereof or one of the salts thereof, whereby the substituents R12 to R18 have the meanings given in the description;and/or c) compounds of formula (III), whereby the substituents X1 to X5 and R19 to R22 have the meanings given in the description. The active components are provided in a synergistically effective quantity.

Description

AND DERIVATIVES OF PYRIDINE Description The present invention relates to fungicidal mixtures for controlling harmful fungi, containing amide compounds of the formula I A-CO-NR1! * 2 (I) where A denotes 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 can optionally have 1, 2 or 3 solvents, which can be selected, independently of one another, 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 amide phenidic 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 compounds of formula II, their N-oxide or one of their salts R15 wherein the substituents have the following meanings: R12, R13, R1, R15 each independently of the other: hydrogen, hydroxy, nitro, halogen, C? -C4-alkyl, C? -C -halogenoalkyl, C? -C-alkoxy, C! -C4-halogeno-alkoxy , C! -C-alkylthio, C? -C4-haloalkylthio; R16, R17, R18 each independently of the other: hydrogen, hydroxy, cyano, nitro, halogen, C? -C -alkyl, C? -C7-halogenoalkyl, C? -C7-alkoxy, C? -C7-halogeno-alkoxy , C? -C7-alkylthio, Ci-C-7-haloalkylthio, C? -C7-hydroxyalkyl, C2-C-acyl, aryl, aryloxy, the groups with aryl being capable of carrying from one to three of the following groups : cyano, nitro, halogen, C? -C4-alkyl, C? -C -haloalkyl, C? -C4-alkoxy, C? -C -haloalkoxy, C? -C4-alkylthio and C? -C4-haloalkylthio and / or compounds of formula III wherein the substituents X1 through X5 and R19 through R22 have the following meanings: X1 to X5 each independently of the other, hydrogen, halogen, C1-C4-alkyl, C? -C4-haloalkyl, C? -C4-alkoxy, C? -C4-haloalkoxy, C? -C-alkylthio, am no, NC? _C4-Carbox lam no, N-? - 4-a quam no; l9 C? -C4-alkyl / C2-C4-alkenyl, C2-C4-alkynyl, C? -C4-aiqiyl-C3-G-cycloalkyl, these radicals being able to carry substituents selected from the group halogen, cyano, and C? ~ C4 -alkoxy R20 a phenyl radical or a saturated or unsaturated heterocyclyl radical of 5 or 6 members with at least one heteroatom selected from the group N, O and S, the cyclic radicals being able to present from one to three drei substituents selected from the group comprising halogen, C?-C4-alkyl, C?-C4-alkoxy, C?-C4-haloalkyl, C?-C4-halo-alkoxy, C?-C4-C2-C4-alkenyl alkoxy, C?-C - C4-alkynyl alkoxy, * and R22 each independently of the other, hydrogen, Ci-CTi-alkyl, C1-C4-alkoxy, C? -C4-alkynyl, N-? -C4-alky1ru.no, C? -C4-haloalkyl or cl-C4 - haloalcoxy in an active synergetic quantity.

The amide compounds of the formula I are known per se and are described in the literature (EP-A 545 099).

In WO 97/08952, fungicidal mixtures containing, together with the neben compounds of the formula I, Fenazaquin, are described as another additional component. These compounds are described as very effective against botrytis.

The compounds of formula II are known per se and are described, for example, in US-A 5,240,940. Also known are fungicidal mixtures, which contain compounds of the formula II together with other compounds with fungicidal action and these are described in the German patent application O.Z. 45483.

Die compounds of formula III, as well as processes for their preparation are described in WO-A 96/19442 beschrieben.

In order to be able to reduce the amounts of application and improve the action spectrum of the known compounds, the present invention has for its object to provide mixtures, which make it possible to obtain better totals of its ancestones, mixed mixtures.

Therefore, the mixtures defined above were found. In addition, it was found that by simultaneously applying, separately or jointly, the compounds I and compounds II to III or by applying the compounds I and compounds II to III successively, the harmful fungi are better controlled than with the compounds I or II to III by themselves.

The mixtures according to the invention have a synergetic effect, so they are suitable for combating harmful fungi and especially powdery mildew in legumes, grapes and cereals.

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-dimethylbuyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-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.

Halogenoalkyl represents an alkyl group defined above, 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-3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-met l-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-nyl, 1, l-dimethyl-2-butenyl, 1, l-dimethyl-3-butenyl, 1,1 dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, , 2-dimethy1-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, l-ethyl-2-butenyl, l-ethyl-3-butenyl, 2-ethyl-2 -butenyl, 2-ethyl-3-butenyl, 1, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl and 1-ethyl-2-methyl-2-propenyl, and especially 2-propenyl, 2-butenyl, 3-methyl-2-butenyl and 3-methyl-2-pente-nyl.

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. Preferablyit is linear or branched alkynyl groups having from 3 to 12 carbon atoms and especially from 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, 1-methyl-2-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-alkynyl, 5-hexynyl, 1-methyl- 2-penti-nyl, l-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-roethyl-4-pentynyl, 3-methyl-4-pentynyl, 4- methyl-2-pentynyl, 1,2-dimethyl-2-butynyl, 1, 1-dimethyl-3-butynyl, 1,2-dimethyl-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-propynyl.

The explanations given above with respect to the alkenyl group and its halogen substituents, as well as 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-C? -C4-a or as its listeners.

Cycloalkenyl represents, preferably a C4-C6-cycloalkenyl group, such as, for example, cyclobutenyl, cyclopentenyl or cyclohexyl. 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 Cs-Ce-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 arbitrary position. Preferably, these substituents will be selected, independently, from alkyl, difluoromethyl, trifluorome-txlo and halogen, especially chlorine, bromine and iodine. The phenyl group very preferably has a substituent at the 2-position.

When A is a 5-membered heterocycle, it is in particular a furyl, thiazolyl, pyrazolyl, imidazolyl, oxazolyl, thienyl, triazolyl or thiadiazolyl radical or a corresponding dihydro or tetrahydro derivative. 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 R H or C and C represent another branch 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: (Ai; (A2) (A5) (A7) CH3 where R3, R4, R6, R ?, R8 and R9 signify, each independently of the other, hydrogen, alkyl, especially methyl, halogen, especially chloro, CHF2 or CF3. hydrogen atom.

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

The substituents of the radical R 2 can themselves 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 to say the especially preferred substituent of the radical R 2 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, dihydroxyatinyl oxide, dihydrooxathiinyl dioxide, furyl, thiazolyl, 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 the 2-position by halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl or methylsulfonyl; phenyl, which is optionally substituted in the 2-position by methyl, trifluoromethyl, chloro, bromo or iodo; 2-methyl-5,6-dihydro-l, 4-oxatiin-3-yls or the 4-oxide or 4,4-dioxide; 2-methyl-furan-3-yl, which, optionally, is substituted at 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; thia2; ol-4-yl, which is optionally substituted in the 2 and / or 5 position 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, C 5 -C 6- cycloalkenyl, C5-C6-cycloalkyloxy, cycloalkenyloxy, whose groups may be substituted by 1, 2 or 3 alkyl groups with 1 to 4 carbon atoms, phenyl, which is substituted by 1 to 5 halogen atoms and / or 1 to 3 groups, selected, independently, from C? -C4-alkyl, C? -C4-haloalkyl, C? -C-alkoxy;, C? -C4-halogeno-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, R 10 where it 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 or methyl, 6 means methyl, difluoromethyl, trifluoromethyl or chloro,? means hydrogen or, methyl or chloro, R8 means methyl, difluoromethyl or trifluoromethyl, R9 means hydrogen or, methyl, difluoromethyl, trifluoromethyl or chloro, halogen.

According to a particularly preferred variant, the products contain as compound of amide uri 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.

As component b), the compounds lia according to Table 1 below are especially preferred.

Especially preferred are the compounds lia according to Table 2, as well as the hydrochloride and the N-oxide of compound 2.78 mentioned therein.

Table 2 The compounds of formula Ia mentioned in Tables 1 and 2 are known from US-A 5 240 940 and / or from ACS Sympos. Ser. 443, page 538 to page 552 (1991).

Among the compounds of the formula III, those in which X 1 means a C?-C4-haloalkyl group, especially a trifluoromethyl group, and X 2 and X 3 are a hydrogen atom or a halogen group, especially a hydrogen atom, are especially preferred. hydrogen. X 4 and X 5 are preferably hydrogen, halogen (especially Cl or F), C 1 -C 4 -alkoxy (especially methoxy or ethoxy), C 4 -C alkylthio (especially methylthio or ethylthio), C 4 -Chaloalkyl (especially trifluoromethyl) or C? -C4-haloalkoxy (especially trifluoromethoxy).

Preferred substituents R19 are C?-C4-alkyl (methyl, ethyl, n- and i-propyl and t-butyl), C 1 -C 4 -alkylene-C 3 -C 7 -cycloalkyl, C?-C 4 -alkenyl (especially ethenyl, propenyl and butenyl, which may be substituted, in particular, by halogen (preferably Cl), propynyl, cyanomethyl and methoxymethyl bevorzug, are especially composed of methylenecyclopropyl, methylenecyclopentyl, methylenecyclohexyl and methylenecyclohexenyl. rings in these substituents may be substituted, preferably, by halogen.

As R 20 substituents, it is also possible to mention phenyl (optionally substituted) especially thienyl, pyrazolyl, pyrrolyl, imidazolyl, thiazolyl, furyl, pyridazinyl and pyrimidinyl. Preferred substituents in these ring systems are halogen (especially F and Cl), C? -C4-alkoxy (especially methoxy) and C? -C4-alkyl (especially methyl, ethyl). The number of the ring substituents can be from 1 to 3, in particular 1 to 2. Phenyl or substituted phenyl are especially preferred.

Preferred substituents R21 and R22 are hydrogen, F, Cl, methyl, ethyl, methoxy, thiomethyl and N-methylamino. R3 and R4 can also together form a group = 0.

Preferred compounds of formula III can be derived from the tables of WO 96/019442 already mentioned. Of these, especially preferred are the compounds indicated in the following Table 3 (R21 and R22 in each case mean hydrogen).

Table 3: In the Table above cpr means cyclopropyl, cHxe-n means unsaturated cyclohexenyl in the n-position, c-Hex means cyclohexyl and Ph means phenyl.

Especially preferred are compounds III, in which R19 represents a CH2-cPr radical and R20 represents an optionally substituted phenyl radical. Among these, the compounds are preferred, in which X 4 and X 5 mean halogen, preferably F.

The physical data of these compounds, as well as the methods for obtaining them, are described in the aforementioned WO 96/19442.

To develop the synergistic effect, a small proportion of the amide compound is already sufficient. Formula I. Preferably, the amide compound is reacted with the active substance of formula II and / or III in a weight ratio of 50: 1 to 1: 50, especially 10: 1 to 1:10. Here it is also possible to use ternary mixtures, which together with the amide compound I also contain compounds II as well as the compounds III. In such mixtures, the mixing ratio between compounds II and III is increased from one another to 50: 1 to 1:50, preferably 10: 1 to 1:10.

Thanks to the basic character of the nitrogen atoms contained in them, the compounds II are capable of forming salts or adducts with inorganic or organic acids or with salts of metal ions. such as, for example, hydrofluoric acid, hydrochloric acid, hydrochloric 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 with 1 to 20 carbon atoms), arylsulfonic and aryldi-sulphonic acids (aromatic radicals, such as phenyl and naphthyl, which carry one or two sulfonic acid groups), alkyl phosphonic acids (phosphonic acids with linear or branched alkyl radicals having 1 to 20 carbon atoms), aryl phosphonic or aryl diphosphonic acids (aromatic radicals, such as phenyl and naphthyl, which have one or two phosphoric acid radicals), whose alkyl or aryl radicals can carry additional substituents, such as, for example, p-toluenesulfonic acid, slicic acid, p-aminosalicyclic acid, 2-phenoxybenzoic acid, zoic 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 aluminum, 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 may 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 and / or III or the combined use or separate of the compounds I and II and / or III provide an excellent effect against a broad spectrum of phytopathogenic fungi, especially of the class of Ascomycetes. , basidiomycites, phycomycetes and deuteromycetes. In part they have systemic action, so they can also be used as fungicides fo-lil and soil. in different cultivation plants, such as cotton, legumes (eg cucumbers, beans and cucurbits), barley, turf, oats, coffee, corn, rice, rye, soy, vine, barley, ornamental plants, cane of sugar 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 nesator in the vine, Puccinia species in cereals, Rhizoctonia species in cotton, rice and grass, Ustilago species in cereals and sugarcane, 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, Phytophthora infestans in potatoes and tomatoes, Pseudoperonospora species in cucurbitas and hops, Plasmopara viticulture in the vine, Alternaria species in legumes and fruits, as well as Fusarium species and of Verticillium.

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

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.

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 the compounds II and / or II vary, correspondingly, from 0.001 to 5 kg / ha, preferably 0.005 to 2 kg / ha, especially 0.01 to 1.0 kg / ha. t a is e, up to 250 g g e se, emen e e e e, up to 100 g / kg, especially 0.01 up to 50 g / kg.

Whenever the plants are to combat phytopathogenic fungi, the separate or combined application of compounds I and II and / or III or mixtures from compounds I and II and / or III is carried out by spray or spray. of seeds, plants or soils before or after planting of plants, or before or after the emergence of plants.

The synergistic fungicidal mixtures of the invention or compounds I and II and / or III can be used in the form of directly sprayable solutions, powders and suspensions or in the form of aqueous, oleic or other highly concentrated suspensions, dispersions, emulsions. , oil dispersions, spraying, spraying agents, directly pulverized granules, by spraying, atomization, spraying or re-gating. 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 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 acyl 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, as well as the salts of hexa, hepta and octadecanoles sulpholine with formaldehyde, condensates of naphthalene or of naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene-noctilphenol ether, isooctylphenol ethoxylate, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenylpolyglycol ether, alkylaryl polyether alcohols , isotridecyl alcohol, fatty alcohol condensates, ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether-ketal, sorbitol ester lignin sulphite residual liquors and methyl cellulose.

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

Granules, eg coated granules, impregnated granules and homogeneous granules can be prepared by bonding active substances with solid supports.

Suitable solid fillers or carriers are, for example, mineral earths, such as silica gel, siliceous acids, silicates, aleo, kaolin, attaclay, limestone, chalk, bolus, loess, dolomite, diatomaceous earth, magnesium sulfate and sulphate. calcium, magnesium oxide, ground plastics, fertilizers, such as eg ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flours, bark powders of trees, wood and nut shell, cellulose powder 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 and / or III or of the mixture of the compounds I or II. II and / or III. 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 and / or III 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 fungicidal amount of the compounds I or II and / or III in the separate application.

The application can be made before or after infection by harmful fungi. active companies, 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 IV. an aqueous dispersion from 20 parts by weight of the active substances, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral acid fraction from the boiling point of 210 to 280 ° C and 10 parts by weight of the product of addition 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 sulfite residual lye and 7 parts by weight of pulverulent 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 divided kaolin; This spray agent contains 3% in. 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; 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 a phenylsulphonic acid-urea-formadehyde condensate 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.

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 degree of action (W) is determined by means of the formula of Abbot in the following way: W = (1 - a) -l ?? / ß equivalent to 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.

The expected degrees of action of the mixtures of active substances are determined by the formula of Colby [R.S. Colby, Weeds JL5, 20-22 (1967)] and compared with the observed degrees of action.

Colby's formula: E = x + y - x-y / 100 E signifies 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; l use 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.

Efficiency against wheat powdery mildew The leaves of wheat seedlings of the variety "Frühgold" are plurved until they are squirted with aqueous preparations of active substance prepared from a stock solution composed of 10% of the active substance, 63% of cyclohexanone and 27% of emulsifier, and 24 hours after drying the sprayed layer is sprayed with spores of wheat powdery mildew (Erysiphe graminis forma specialis tritici). The test plants are then placed in the greenhouse at temperatures between 20 and 24 ° C and 60 to 90% relative humidity of the air. After 7 days the extent of powdery mildew development in% of the total leaf area is visually determined ..

As a compound of formula I, the following components are used: The results can be derived from the following tables 4 and 5.

Table 5 *) 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 mixing ratios higher than the degree of action calculated according to the Colby formula.

Claims (2)

Claims

1. Fungicidal mixtures containing as active components a) an amide compound of the formula I A-CO-NRiR2 I where A denotes 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 independently of the other, 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, 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, optionally substituted by one or more alkyl groups and / or a heteroatom selected from O, and S, And b) compounds of formula II, their N-oxide or one of their salts Rl5 wherein the substituents have the following meanings: R 12, R 13, R 14, R 15 each independently of the other: hydrogen, hydroxy, nitro, halogen, C! -C 4 -alkyl, C? -C 4 -haloalkyl, C? -C 4 -alkoxy, C? -C 4 -haloalkoxy , C? -C4-alkylthio, C? -C4-haloalkylthio; R16, R17, R18 each independently of the other: hydrogen, hydroxy, cyano, nitro, halogen, C? -C7-alkyl, C? -C -haloalkyl, C? -C-7-alkoxy, C? -C -halogenoalkoxy, C? -C7-alkylthio, C? -C7-haloalkylthio, C? -C7-hydroxyalkyl, C2-C4-acyl, aryl, aryloxy, the groups with aryl can in turn carry from one to three of the groups following: cyano, nitro, halogen, C? -C4-alkyl, C1-C4-haloalkyl, C? -C -alkoxy, C? -C -haloalkoxy, C? -C4-alkylthio and C? -C4-haloalkylthio I c) compounds of formula III wherein the substituents X1 through X5 and R19 through R22 have the following meanings: hydrogen, halogen, C? -C4-alkyl, C? -C -haloalkyl, C? -C4-alkoxy, C? -C4-halogenoalkoxy, C! -C 4 -alkylthio, C 1 -C -thioalkoxy, C 1 -C 4 -sulfonylalkyl, nitro, amino, N-C 1 -C 4 -carboxylamino, NC?-C 4 -alkylamino; R19 C? -C4-alkyl, C2-C-alkenyl, C2-C4-alkynyl, C? -C4-C3-C7-alkyl-cycloalkyl, these radicals being able to carry substituents selected from the group halogen, cyano, and C? -C4 -alcoxi R20 a phenyl radical or a saturated or unsaturated heterocyclyl radical of 5 or 6 members with at least one heteroatom selected from the group N, O and S, the cyclic radicals having one to three drei substituents selected from the group comprising halogen, C -? - C4-alkyl, C? -C4-alkoxy, C? -C4-halogenoalkyl, C? -C4-halogenoalkoxy, C? -C4-C2-C-alkenyl-alkenyl, C? -C4-alkoxy- C -C4-alkynyl, R21 and R22 each independently of the other, hydrogen, C? -C4-alkyl, C? -C4-alkoxy, C? -C4-alkylthio, NC? -C -alkylamino, C1-C-haloalkyl or C? -C4-halogenoalkoxy in an active synergetic quantity. Fungicidal mixture according to claim 1, wherein in the formula I the radical A means one of the following groups: phenyl, pyridyl, dihydropyranyl, dihydrooxathiinyl, dihydrooxathiinyl oxide, dihydrooxathiinyl dioxide, furyl, thiazolyl, pyrazolyl or oxazolyl, which groups may have 1, 2 or 3 substituents selected, independently, from alkyl, halogen, difluoromethyl and trifluoromethyl. Fungicidal mixture according to claim 1, wherein in the formula I the radical A means one of the following groups: 2 by halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl or methylsulfonyl; phenyl, which is optionally substituted in the 2-position by methyl, trifluoromethyl, chloro, bromo or iodo;

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 thereof; 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 is optionally substituted in the 2-position and / or 4 by methyl or chloro. Fungicidal mixture according to one of the preceding claims, which contains a compound of the formula I, wherein R 2 represents a phenyl group, which is optionally substituted by 1, 2 or 3 of the substituents indicated in claim 1. Fungicidal mixture according to claim 4, wherein R2 means a phenyl group, which has in the 2-position one of the following substituents: C3-C6-alkyl, C5-C6-cycloalkenyl, C5-C6-cycloalkyloxy, cycloalkenyloxy, whose groups may be substituted by 1, 2 or 3 alkyl groups with 1 to 4 carbon atoms, phenyl, which may be substituted by 1 to 5 halogen atoms and / or 1 to 3 groups, independently selected from C? -C-alkyl, C C4-haloalkyl, Ci-Cj-alkoxy, C? -C4-halogenoalkoxy, C? -C4-alkylthio and C? -C-haloalkyl-thio, is defined by 1, groups with or with atoms of carbon. Fungicidal mixture according to one of claims 1 to 5, which contains an amide compound of the formula as follows: where it means X means methylene, sulfur, sulfinyl or sulfonyl (S02), R3 means 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 signifies hydrogen, methyl or chloro, R8 signifies methyl, difluoromethyl or trifluoromethyl, lime or chlorine, R10 means C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C -alkylthio or halogen. Fungicidal mixture according to one of claims 1 to 5, which contain as compounds of amide a compound of the following formula Ib: (Ib) where R 4 is halogen and R 11 is phenyl, which is substituted by halogen. Fungicidal mixture according to claim 1, which contain as compound of amide a compound of the following formulas: Fungicidal mixture according to one of the preceding claims, which is conditioned in two parts, the first containing the amide compound I in a solid or liquid support and the second part the compounds II and / or III in a solid or liquid support. because the fungi, their living space or the materials, plants, seeds, soils, areas or enclosures to be kept free from fungal infestation are treated with a fungicidal mixture according to one of claims 1 to 9, the active substances being able to be applied , amide compounds, I and compounds II and / or III simultaneously, namely, in a joint or separate manner, and successively.