MXPA00009122A - Fungicide mixtures based on triple oxime ether derivatives and resistance inductors - Google Patents

Abstract

The invention relates to fungicide mixtures comprised as active components a) phenylacetic acid derivatives of formula (I) in which the substituents and the index have the meanings cited in the description, and the salts thereof, and b) at least one compound of formulas (II) to (III) in a synergistically effective quantity.

Description

FUNGICIDAL MIXTURES BASED ON TRIS DERIVATIVES (OXIMA ETER) AND RESISTANCE INDUCERS The present invention relates to fungicidal mixtures for controlling harmful fungi, which consist of: a) fe-ylacetic acid derivatives of the formula I wherein the substituents and the Index have the following meanings: X is NOCH3, CHOCH3, CHCH3; And it is 0, NR; R1, R independently of one another are each hydrogen and C1-C4 alkyl; C is cyano, nitro, trifluoromethyl, halogen, C 1 -C 4 alkyl and C 1 -C 4 alkoxy; 2 is 0, 1 or 2, where the radicals R can be different if it is 2; R ~ is hydrogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl; R \ Rc independent from each other are each hydrogen, are C? -C? Alkyl, C3-C6 cycloalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C10 alkylcarbonyl, C2-C alkenylcarbonyl C3-C10 alkynylcarbonyl or C1-C10 alkylsulfonyl, wherein these radicals may be partially or completely halogenated or may carry from one to three of the following groups: cyano, nitro, hydroxyl, ercapto, amino, carboxyl, aminocarbonyl, to ín -thiocarbonyl, halogen, C?-Cd alkyl, haloalkyl of C-C6, alkylsulfonyl of C? -Ce, alkylsulfoxyl of C3.-C6, alkoxy of C? -C $, haloalkoxy of C? -C6, alkoxycarbonyl of C? -C6, alkylthio of C-C6, alkylamino of Ci-Ce, di-C 1 -C β alkylamino, Ci-Cβ alkylaminocarbonyl, C?-C6 di-alkylaminocarbonyl, Ci-Cß inothiocarbonyl alky, C?-C6 di-alkylaminothiocarbonyl, C 2 -C 6 alkenyl, C2-C6 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkyloxy, heterocyclyl, heterocyclyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio wherein the cyclic groups on the other hand may be partially or completely halogenated or can carry from one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C? -Cg alkyl, C? -Cd haloalkyl, C? -C6 alkylsulfonyl , C? -C6 alkylsulfoxyl, C3-C6 cycloalkyl, C? -C6 alkoxy, C? -C6 haloalkoxy, C? -C? alkyloxycarbonyl, C? -C6 alkylthio, alkylaryl C6-C6-dialkylamino, C? -C6 dialkylamino, C? -Cg alkylaminocarbonyl, C? -Cg di-alkylaminocarbonyl, C? -C6 alkylaminthiocarbonyl, C? -C6 di-alkylaminthiocarbonyl, C2-alkenyl C6, C2-C6 alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio or C (= NOR7) -An-R8; they are aryl, arylcarbonyl, arylsulfonyl, hetaryl, hetarylcarbonyl or hetarylsulfonyl, where these radicals may be partially or completely halogenated or may carry from one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C? -C6 alkyl, C? -C6 haloalkyl, C-C6 alkylcarbonyl, C? -C6 alkylsulfonyl, C? -Ce alkylsulfoxyl, C3-C6 cycloalkyl, C? -C6 alkoxy, haloalkoxy of C? -C6, Cx-Cs alkyloxycarbonyl, C-C6 alkylthio, C? -Cg alkylamino, C? -C6 dialkylamino, C? -C6 alkylaminocarbonyl, C? -C6 di-alkylaminocarbonyl, alkylaminthiocarbonyl C? -C6, C? -C6 di-alkylaminthiocarbonyl, C2-C6 alkenyl, C2-C6 alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy or C (= NOR) -An-R; it's hydrogen is C? -C6 alkyl, C2-C6 alkenyl, C2-C? alkynyl where the hydrocarbon radicals of these groups may be partially or completely halogenated or may carry from one to three of the following radicals: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C?-Cd alkylaminocarbonyl, C?-Cg di-alkylaminocarbonyl, C?-C6 alkylaminothiocarbonyl, C-C6 di-alkylaminothiocarbonyl, C alqu ~ alkylsulfonyl CQ, C -C6 alkylsulfoxyl, C? -Cal alkoxy, C? -Cd haloalkoxy, C? -Cd alkoxycarbonyl, C? -C6 alkylthio, C? -C6 alkylamino, C? C6C 3 -C 6 alkenyloxy, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, C 1 -C arylalkoxy, arylthio, C 1 -C 4 arylalkylthio, hetaryl, hetaryloxy, hexylalkyl C? -C4, hetarylthio, hetarylalkylthio of C? -C4, where the cyclic radicals on the other hand can be partially or completely halogenated and / or can carry from one to three of the following groups: cyano, nitro, hydroxyl, mercapto amino, carboxyl, aminocarbonyl, aminothiocarbonyl, C? -Cg alkyl, C? -Cg haloalkyl, C? -Cg alkylsulfonyl, C? -Cg alkylsulfoxyl, C3? Cg cycloalkyl, C? alkoxy? -Cg, haloalkoxy of C? -Cg, alkoxycarbonyl of C? -Cg, alkylthio of C? -Cg, alkylamino of C? -Cg, dialkylamino of C? _Cg, alkylaminocarbonyl of C? -Cg, di-alkylaminocarbonyl of C? -Cg, alkylaminothiocarbonyl of C? -Cg, di-alkylaminothiocarbonyl of C? -Cg, alkenyl of C2-Cg, alkenyloxy of C2-Cg, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetaryl dude and C (= NOR7) -An-R8; is C3-Cg cycloalkyl, C3-Cg cycloalkenyl, heterocyclyl, aryl, hetaryl, wherein the cyclic radicals may be partially or completely halogenated or may carry from one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C? -Cg alkyl, C? -Cg haloalkyl, C? -Cg alkylsulfonyl, C? -Cg alkylsulfoxyl, C3-Cg cycloalkyl, C? -Cg alkoxy, C? -Cg haloalkoxy, C? -Cg alkoxycarbonyl, C? -Cg alkylthio, C? -Cg alkylamino, C? -Cg di-alkylamino, C? -Cd alkylaminocarbonyl, C-di-alkylaminocarbonyl? -Cg, alkylaminothiocarbonyl of C? -Cg, di-alkylaminothiocarbonyl of C? -Cg, alkenyl of C2-Cg, alkenyloxy of C2-C6, benzyl, benzyloxy, aryl, aryloxy, hetaryl and hetaryloxy; where A is oxygen, sulfur or nitrogen and where the nitrogen carries hydrogen or C? -Cg alkyl; n is 0 or 1; R is hydrogen or C? -Cg alkyl, and R is hydrogen or C? -Cg alkyl, and salts thereof, and b) at least one fungicide selected from the fungicides of formulas II to III An object of the present invention is to provide fungicidal mixtures having good fungal activity, in particular against fungal diseases in rice, which exceed the efficacy of the individual blend components. We have found that this objective is achieved according to the invention by the mixtures as claimed in claim 1. The compounds of the formula I are known per se and are described in the literature (WO 97/15552). The fungicides of formulas II to III are also known and described in the literature. In addition, they are available commercially under the trademarks given below in brackets: II: EP 313,512, proposed common name: acibenzolar (registered trademark: Bion®, Novartis) III: common name: probenazole (registered trademark) Oryzamate®, from Meiji Sei a) Due to its double bonds C = C and C = N, the preparation of the compounds I can produce mixtures of E / Z isomers which can be separated into individual compounds in a customary manner, for example by crystallization or chromatography. However, if the synthesis produces mixtures of isomers, a separation is generally not necessary since in some cases the individual isomers can be converted in the other during preparation for use or in use (for example under the action of light, acids). or bases). Similar conditions can also occur after use, for example in the treatment of plants in the treated plants or in harmful fungi or animal pests to be controlled. With respect to the double bond C = X, preference is given to the E isomers of the compounds I (configuration based on X the group -OCH3 or -CH3 in relation to the group -C02R) with respect to its activity. With respect to the double bond -C (R) = NOCH2-, preference is given to the cis isomers of the compounds I (configuration based on the radical R with respect to the group -OCH2-) with respect to its activity. In the definitions of the compounds I given at the beginning, collective terms were used that generally represent the following groups: Halogen: fluorine, chlorine, bromine and iodine; Alkyl: straight or branched chain alkyl groups having from 4, β or 10 carbon atoms, for example C alquilo-Cg alkyl, such as: methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, -methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-di-methylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3-3- dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,2-trimethylpropyl 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and l-ethyl-2-methylpropyl; Haloalkyl: straight or branched chain alkyl groups having from 1 to 6 carbon atoms, it being possible that some or all of the hydrogen atoms in these groups are substituted by halogen atoms, as already mentioned, for example: haloalkyl of C? -C2, such as chloromethyl, dichlorometiu, trichloromethyl, fluoromethyl, difluoro ethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoroethyl, chlorodifluoromethyl, l-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethylene, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, , 2-dichloro-2-fluoroethyl, 2, 2, 2-trichloroethyl and pentafluoroethyl; Cycloalkyl: monocyclic alkyl groups having from 3 to 6 carbons as ring members, for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; Alkenyl: straight or branched chain alkenyl groups having from 2 to 6 or 10 carbon atoms and a double bond in one position, for example: C2-Cg alkenyl, such as: ethenyl, 1-propenyl, 2-propenyl , 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, -pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl -2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1, 2 dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, -hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl , 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4 -methyl-3-pentenyl, l-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, l-dimethyl-2-butenyl, 1 , 1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2, 3-dimethyl-3-butenyl, 3, 3-dimethyl-l-butenyl, 3, 3-dimethyl-2-butenyl, 1-ethyl-l-butenyl, l-ethyl-2-butenyl, l-ethyl-3- butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-aethyl-2-propenyl; Alkynyl: straight or branched chain alkynyl groups having from 2 to 10 carbon atoms and a triple bond at any position, for example: C2 ~ C alkynyl, such as ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, l-methyl-2-propinyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 1,1-dimethyl- 2-propinyl, l-ethyl-2-propinyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, 1-methyl-3-pentynyl, l-methyl-4 pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1, 1-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 1- ethyl-l-methyl-2-propinyl; Heterocyclyl or heterocyclyloxy, heterocyclylthio and heterocyclylamino: three saturated or partially unsaturated monocyclic or polycyclic heterocycles of three to six members containing from one to three heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur and which are directly attached to the backbone or ( heterocyclyloxy) for an oxygen atom or (heterocyclicthio) for a sulfur atom or (heterocyclylamino) for a nitrogen atom, such as, for example, 2-tetrahydrofuranyl, oxiranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl , 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazoldinyl [sic], 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-urazolidinyl, 2 -oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1, 2,4-oxadiazolidin -5- ilo 1, 2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl, 1 , 3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,3-dihydrofur-4 -yl, 2, 3-dihydrofur-5-yl, 2,5-dihydrofur-2-yl, 2,5-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3 -yl, 2,3-dihydrothien-4-yl, 2,3-dihydrothien-5-yl, 2, 5-dihydrothien-2-yl, 2,5-dihydrothien-3-yl, 2,3-dihydropyrrol-2-yl, 2,3-dihydropyrrol-3-yl, 2,3-dihydropyrrol-4-yl , 2,3-dihydropyrrol-5-yl, 2,5-dihydropyrrol-2-yl, 2,5-dihydropyrrol-3-yl, 2,3-dihydro-isoxazol-3-yl, 2,3-dihydroisoxazol-4-yl 5-dihydroisoxazol-5-yl-2,5-dihydroisothiazol-3-yl, 2,3-dihydroisoxazol-5-, 4, 5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl, 4, , 2, 5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol yl 5-yl 3-dihidroisopirazol-3-yl-3-dihidroisopirazol-5-, 2, 2, 3-dihidroisopirazol-4-yl, 2, , 4,5-dihidroisopirazol-3-yl, 4, 5-dihidroisopirazol-4-yl, 5-dihidroisopirazol-3-yl 2,5-dihidroisopirazol-4-yl-4,5-5-dihidroisopirazol, 2, , 2, 5-yl-5-dihidroisopirazol, 2,3-dihydrooxazol-3-yl, 2, 3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl-4, 5-dihydrooxazol-3-yl , 4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-3-yl, 2,5-dihydrooxazol-4-yl, 2,5-dihydrooxazol-5-yl , 2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl, 2,3-dihydrothiazol-5-yl, 4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazol-4-yl, 4,5-dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl, 2,3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4-yl 4,5-dihydro-4, 4, 5-dihydro-5-yl, 5-dihydroimidazole-2-yl-2,5-dihydroimidazole-2-yl-2, 5-dihydroimidazole-4-yl, 2,5-dihydro-5-yl-2-morpholinyl, 3-morpholinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-tetrahydropyridazinyl, 4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetrahydropyrazinyl, 1,3,5-tetrahydrotriazin-2-yl, 1, 2, 4-tetrahydrotriazin-3-yl, 1,3-dihydrooxazin-2-yl, 1,3-dithiane-2-yl, 2- tetrahydropyranyl, 1,3-dioxplan-2-yl, 3,4,5,6-tetrahydropyridin-2-yl, 4H-1,3-thiazin-2-yl, 4H-3, 5-benzothiazin-2-yl, 1, 1-dioxo-2, 3, 4, 5-tetrahydrothien-2-yl, 2H-1,4-benzothiazin-3-yl, 2H-1,4-benzoxazin-3-yl, 1,3-dihydrate rooxazin-2-yl, 1,3-dithian-a-yl; Aryl or aryloxy, arylthio, arylcarbonyl and arylsulfonyl: mono- or polycyclic, aromatic hydrocarbon radicals which are attached to the skeleton directly or (aryloxy) through an oxygen atom (-0-) or (arylthio) a sulfur atom (- S-), (arylcarbonyl) through a carbonyl group (-C0-) or (arylsulfonyl) through a sulfonyl group (-S02-), for example phenyl, naphthyl and phenanthrenyl or phenyloxy, naphthyloxy and phenanthrenyloxy and the corresponding carbonyl and sulfonyl radicals; Hetaryl or hetaryloxy, hetarylthio, hetarylcarbonyl and hetarylsulfonyl: mono- or polycyclic aromatic radicals which, in addition to the carbon ring members, may also contain from 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and the oxygen atom or of sulfur or an oxygen atom or one of sulfur and which are attached to the skeleton directly or (hetaryloxy) through an oxygen atom (-0-) or (hetarylthio) a sulfur atom (-S-), ( hetarylcarbonyl) through a carbonyl group (-C0-) or (hearylsulfonyl) through a sulfonyl group (-SO2-), for example: -membered heteroaryl, containing from 1 to 3 nitrogen atoms: 5-membered heteroaryl groups which, in addition to the carbon atoms, may contain from 1 to 3 nitrogen atoms as ring members, for example: 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2, 4-triazol-3-yl and 1, 3, 4-triazol-2-yl; - 5-membered heteroaryl, containing from 1 to 4 nitrogen atoms or from 1 to 3 nitrogen atoms and a sulfur or oxygen atom or an oxygen atom or a sulfur atom: 5-membered heteroaryl groups which, in addition, of the carbon atoms, may contain from 1 to 4 nitrogen atoms or from 1 to 3 nitrogen atoms and a sulfur atom or oxygen atom or an oxygen or sulfur atom as ring members, for example: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3- pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2, 4-oxadiazole- 3-yl, 1,2,4-oxadiazol-5-yl, 1, 2,4-thiadiazol-3-yl, 1, 2,4-thiadiazol-5-yl, 1, 2,4-triazole-3- ilo, 1, 3, 4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3-triazol-2-yl; - 5-membered benzofused heteroaryl containing from 1 to 3 nitrogen atoms or a nitrogen atom and / or an oxygen or sulfur atom: 5-membered heteroaryl groups which, in addition to IQS carbon atoms, may contain 1 to 4 nitrogen atoms or from 1 to 3 nitrogen atoms and a sulfur or oxygen atom or an oxygen atom or a sulfur atom as ring members, in which two adjacent carbon ring members or a nitrogen and one of the adjacent carbon ring members may be bridged by a buta-1,3-dien-l, 4-diyl group; - 5-membered heteroaryl bonded through nitrogen and containing 1 to 4 nitrogen atoms, or 5-membered benzofused heteroaryl, bonded by nitrogen and containing from 1 to 3 nitrogen atoms: 5-membered heteroaryl groups which, furthermore, of the carbon atoms, may contain from 1 to 4 nitrogen atoms and from 1 to 3 nitrogen atoms, respectively, as ring members, and in which two adjacent carbon ring members or a nitrogen and a ring member adjacent carbon may be bridging by a buta-1,3-die-1,4-diyl group, these rings being attached to the backbone through one of the ring members nitrogen; - 6-membered heteroaryl containing from 1 to 3 and from 1 to 4 nitrogen atoms, respectively: 6-membered heteroaryl groups which, in addition to the carbon atoms, may contain 3 and 4 nitrogen atoms, respectively, as ring members, for example: 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1, 3, 5 triazin-2-yl, 1,2,4-trazin-3-yl and 1, 2, 4, 5-tetrazin-3-yl; - benzofused 6-membered heteroaryl containing from 1 to 4 nitrogen atoms: 6-membered heteroaryl groups in which two adjacent carbon ring members can be bridged by a 1,3-dien-1,4-diyl group, for example quinoline, isoquinoline, quinazoline and quinoxaline, and the corresponding oxy, thio, carbonyl sulfonyl groups.

Hetarylamino: mono- or polycyclic, aromatic radicals which, in addition to the carbon ring members, may also contain from 1 to 4 nitrogen atoms or from 1 to 3 nitrogen atoms and one oxygen atom or one sulfur atom and which are attached to the skeleton through a nitrogen atom. The specification "partially or completely halogenated" means that it expresses that some or all of the hydrogen atoms in the groups thus characterized can be replaced by identical or different halogen atoms as already mentioned. With respect to its biological activity, preference is given to the compounds of the formula I in which m is 0. Similarly, preference is given to the compounds of the formula I in which R is methyl. In addition, preference is given to compounds I in which R is hydrogen, cyano, cyclopropyl, methyl, ethyl, 1-methylethyl or CF3. In addition, preference is given to compounds I in which R is methyl. In addition, preference is given to compounds I in the 3 which R is cyano. In addition, preference is given to compounds I in the 3, R is cyclopropyl. Additionally, preference is given to compounds I in which R is CF3. In addition, preference is given to compounds I in which R is unsubstituted or substituted hydrogen, cyclopropyl, methyl, ethyl, isopropyl, aryl or hetaryl. In addition, preference is given to compounds I in which R is methyl. Moreover, preference is given to compounds I in the which R is ethyl. Also, preference is given to compounds I in which R is isopropyl. Preference is also given to compounds I in which R is cyclopropyl. Also, preference is given to compounds I in which R is CF3. Likewise, preference is given to compounds I in which R is aryl or substituted or unsubstituted hetaryl. In the same way, preference is given to compounds I in which R is unsubstituted or substituted pyridyl, pyrimidyl, pyrazinyl, pyridazinyl or triazinyl. Likewise, preference is given to compounds I in which R is substituted or unsubstituted furyl, thienyl or pyrrolyl. In addition, preference is given to compounds I in which R is substituted or unsubstituted oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl or imidazolyl.

Likewise, preference is given to compounds I in which R is unsubstituted or substituted oxyazolyl [sic], thiadiazolyl or triazolyl. Preference is also given to compounds I in which R is phenyl which is unsubstituted or carries from one to two of the following groups: nitro, cyano, hydroxyl, amino, aminocarbonyl, aminothiocarbonyl, halogen, C? -C alkyl , haloalkyl of C-C4, alkoxy of C-C4, haloalkoxy of C? -C4, alkylamino of C-C4, di-C1-C4 alkylamino, alkylsulfonyl of C-C4, alkoxycarbonyl of CC, alkylaminocarbonyl of C-C4 or di-C3-alkylaminocarbonyl. In addition, preference is given to compounds I in which R is hydrogen, C? -Cg alkyl, C2-Cg alkenyl, C2-Cg alkynyl, allyl, arylalkyl, hetarylalkyl, aryloxyalkyl, hetaryloxyalkyl, aryl or hetaryl. Preference is also given to compounds I in which R is C? -Cg alkyl. Other preferred compounds I are described in WO 97/15552. The compounds I that are contained in the mixtures according to the invention have outstanding activity against a wide variety of phytopathogenic fungi, in particular against fungi of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes classes.

These are especially important for controlling a large amount of fungi in a variety of crop plants such as cotton, plant species (for example cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grasses, oats, bananas, coffee, corn, fruit species, rice, rye, soybeans, vines, wheat, ornamental plants, sugar cane and variety of seeds. These are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mold) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, Rhizoctonia species in cotton, rice and turf, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals and rice, Septoria nodorum in wheat, Botrytis ciñera [sic] (gray mold) in strawberries, vegetables, ornamental plants and -vides , Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice and turf, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticulture in vines, Pseudoperonospora species in hops and cucumbers, Alternating species in vegetables and fruits, Mycosphaerella species in bananas and Fusarium and Verticillium species.

Compound II is commercially available as an inducer of resistance (ie, an additive ingredient that immunizes against disease attack), ie II has no direct fungal activity, but induces resistance against harmful fungi in the plant treated. The compound III is known as a fungicide. When preparing the mixtures, it is preferred to use the pure active ingredients I and II to III, with which other active ingredients can be mixed against harmful fungi or other pests, such as insects, arachnids or nematodes, or even herbicidal or regulatory active ingredients. of growth or fertilizers. The mixtures of the compounds I and at least one compound II to III can be applied simultaneously, i.e. together or separately, and have outstanding activity against a wide variety of phytopathogenic fungi, in particular of the class of Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes. Some of these act in a systematic way and therefore they are also suitable for use as fungicides of action in leaves and soils. They are also especially important for controlling a large amount of fungi in a variety of crop plants, such as cotton, plant species (eg, cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grasses, oats, bananas, coffee, corn , fruit species, rice, rye, soybeans, vines, wheat, ornamentals, sugarcane and a variety of seeds. These are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mold) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula necator in vines, Puccinia species in cereals, Rhizoctonia species in cotton, rice and turf, Ustilago species in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals and rice, Septoria nodorum in wheat, Botrytis ciñera [sic] (gray mold) in strawberries, vegetables, ornamental plants and vines, Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyrícularia oryzae in rice and turf, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticulture in vines, Pseudoperonospora species in hops and cucumbers, Alternate species in vegetables and fruits, Mycosphaerella species in bananas and Fusarium and Verticillium species. The mixtures according to the invention are particularly preferably used to control Pyricularia oryzae. The compounds I and at least one of the compounds II to III can be applied simultaneously, together or separately, or in succession, the sequence in the case of separate application, generally having no effect on the results of the control. Depending on the nature of the desired effect, the application rates of the mixtures according to the invention are, in particular, in agricultural crops, from 0. 01 to 8 kg / ha, preferably from 0.1 to 5 kg / ha, in particular from 0.5 to 3.0 kg / ha. In the case of the compounds I, the application rates are from 0.01 to 2.5 kg / ha, preferably from 0.05 to 2.5 kg / ha, in particular from 0.1 to 1.0 kg / ha. Correspondingly, in the case of compounds II to III, application rates are from 0.001 to 5 kg / ha, preferably from 0.005 to 2 kg / ha, in particular from 0.01 to 1.0 kg / ha. For the treatment of the seeds, the application rates of the mixture are generally from 0.001 to 250 g / kg of seeds, preferably from 0.01 to 100 g / kg, in particular from 0.01 to 50 g / kg. If harmful phytopathogenic fungi are to be controlled, the separate or combined application of the compounds I and at least one of the compounds II to III is carried out by spraying or sprinkling the seeds, plants or soils before or after planting the plants or before or after the germination of the plant.

The mycotic synergistic mixtures according to the invention can be formulated, for example, in the form of solutions prepared for sprinkling, powders and suspensions or in the form of aqueous, oily or other highly concentrated suspensions, dispersions, emulsions, oily dispersions, pastes, powders. , materials for broadcast sowing or granules, and can be applied by spraying, atomization, dusting, broadcast sowing or irrigation. The form of use depends on the proposed purpose; in any case, a distribution as fine and uniform as possible of the mixture according to the invention must be ensured. The formulations are prepared in a known manner, for example by expanding the active ingredient with solvents and / or carriers, if desired by the use of emulsifiers and dispersants. If the diluent used is water, it is also possible to use other organic solvents as auxiliary solvents. Suitable auxiliaries are mainly: solvents such as aromatics (for example xylene), chlorinated aromatics (for example chlorobenzenes), paraffins (for example fractions of mineral oils), alcohols (for example methanol, butanol), ketones (for example cyclohexanone), amines (for example ethanolamine, dimethylformamide) and water; carriers such as crushed natural minerals (e.g. kaolins, clays, talc, gypsum) and crushed synthetic minerals (e.g. finely divided silica gel, silicates); emulsifiers as non-ionic and anionic emulsifiers (for example ethers of polyoxyethylene fatty alcohols, alkylsulfonates and arylsulfonates), and dispersants as residual liquors of lignosulfite and methylcellulose. Suitable surfactants are alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, for example ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and fatty acids, alkyl- and alkylarylsulfonates, alkyl , lauryl ether and sulfates of fatty alcohols, and salts of sulfated hexa-, hepta- and octadecanols or of glycol ethers of fatty alcohols, condensates of sulfonated naphthalene and their derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde , polyoxyethylene octylphenol ether, isooctyl-, octyl- or nonylphenol ethoxylate, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, condensates of fatty alcohol ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene [sic] , lauryl alcohol polyglycol ether acetate, sorbitol esters, residual liquors d e lignosulfite or methylcellulose. The powders, volatile materials and powders can be prepared by mixing or commingling the compounds I and at least one of the compounds II to III or the mixture of the compounds I and at least one compound II or III to the solid carrier. Granules (for example coated granules, impregnated granules or homogeneous granules) are usually prepared by agglomerating the active ingredient, or active ingredients, to a solid carrier. Solid carriers or carriers are, for example, mineral earths such as silica gel, silica, silica gels [silica], silicates, talc, kaolin, limestone, quicklime, gypsum, ferrous clay, loess, clay , dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, crushed synthetic minerals and fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of plant origin such as cereal flour, flour tree bark, wood flour and nut shell flour, cellulose powder or other solid carriers. The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight of one of the compounds I and at least one of the compounds II to III or of the mixture of the compounds I and at least one of the compounds II to III. The active ingredients are used in a purity from 90% to 100%, preferably from 95% to 100% (according to NMR or the HPLC spectrum [sic]). The corresponding formulations are applied by treating the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces that have to be kept free of these, with an effective amount as a fungicide of the mixture, or of the compounds I and at least one of the compounds II or III in the case of separate application. The application can be made before or after the infection by the harmful fungus. Examples of such preparations containing the active ingredients are: I, A solution of 90 'parts by weight of the active ingredients and 10 parts by weight of N-methylpyrrolidone; This solution is suitable for use in the form of microdroplets; II. A mixture of 20 parts by weight of the active ingredients, 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonate, 5 parts by weight of the addition product of 40 moles of ethylene oxide and 1 mole of castor oil; a dispersion is obtained by finely distributing the solution in water; III. An aqueous dispersion of 20 parts by weight of the active ingredients, 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 and 1 mole of castor oil; IV. An aqueous dispersion of 20 parts by weight of the active ingredients, 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 and 1 mole of castor oil; V. A mixture, crushed in a martini mill, of 80 parts by weight of the active ingredients, 3 parts by weight of the sodium salt of diisobutylnaphthalene-1-halophonic acid, 10 parts by weight of the sodium salt of an acid lignosulfonic acid sulphite residual liquor and 7 parts by weight powdered silica gel; a spray mixture is obtained by finely distributing the mixture in water; SAW. An intimate mixture of 3 parts by weight of the active ingredients and 97 parts by weight of finely divided kaolin; this powder contains 3% by weight of the active ingredient; VII. An intimate mixture of 30 parts by weight of the active ingredients, 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel; this formulation imparts good adhesion to the active ingredient; VIII. A stable dispersion of 40 parts by weight of the active ingredients, 10 parts by weight of the sodium salt of a phenolsulfonic acid / urea / formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water; this dispersion can also be diluted. IX. An oily, stable dispersion of 20 parts by weight of the active ingredients, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of polyglycol ether of fatty alcohols, 20 parts by weight of the sodium salt of a Feholsulfonic acid / urea / formaldehyde condensate and 88 parts by weight of paraffinic mineral oil.

The synergistic activity of the mixtures according to the invention can be demonstrated by the following experiments: The active ingredients, together or separately, are formulated as a 10% emulsion in a mixture of 63% by weight of cyclohexanone and 27% by weight of the emulsifier, and diluted correspondingly with water to the desired concentration. The evaluation is done by determining the areas of infected leaves in percent. These percentages become efficiencies. The efficiency () is calculated as follows using the Abbot formula: W = (1 - a) -100 / ß a corresponds to the fungal infection of the plants treated in%, and ß corresponds to the fungal infection of the treated plants (control) in%.

An efficacy of 0 means that the level of infection of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected. The expected efficacies of the mixtures of the active ingredients were determined using the formula of Colby [R. S. Colby, Weeds 15, 20-22 (1967)] and compared with the observed efficiencies.

Colby's formula: E = x + y - xy / 100 E expected efficacy, expressed in% of the untreated control, when using the mixture of the active ingredients A and B in concentrations a and bx efficacy, expressed in% of the untreated control, when the active ingredient A is used at the concentration a and efficacy, expressed in% of the untreated control, when the active ingredient B is used at the concentrationb Example of use 1 - Activity against Pyricularia oryzae (protection) The leaves of potted rice seedlings c.v. "Tai-Nong 67" were sprayed to the point of condensation with an aqueous preparation of the active ingredient that had been prepared from a standard solution containing 10% of the active ingredient, 63% cyclohexanone and 27% emulsifier. The next day, the plants were inoculated with an aqueous suspension of spores of Pyricularia oryzae. The test plants were subsequently placed in chambers with climate at 22-24 ° C and 95-99% relative atmospheric humidity for 6 days. The degree of development of the disease on the leaves was then determined visually. The visually determined values for the percentage of diseased leaf areas were converted into efficiencies as a percentage of the untreated control. An efficacy of 0 means the same level of disease as in the untreated control, an efficacy of 100 means 0% of disease. The expected efficacies for the combinations of active ingredients were determined using the Colby formula (Colby, SR "Calculating synergistic and antagonistic responses of herbicide combinations", Weed, 15, pp. 20-22, 1967) and compared with the observed efficacies . The following compound I was used as component a): The results of the tests are shown in the following Tables 1 and 2: Table 1: Table 2: calculated using Colby's formula The results of the tests show that for all mixing ratios the observed efficiency is greater than the efficiency that had been calculated using the Colby formula.

Claims (1)

1. CLAIMS A mixture for crop protection contains, as active components: a) phenylacetic acid derivatives of the formula I wherein the substituents and the index have the following meanings: X is NOCH3, CHOCH3, CHCH3; And it is 0, NR; R independently from each other are each hydrogen and C? -C4 alkyl; R? is cyano, nitro, trifluoromethyl, halogen, C 1 -C 4 alkyl and C 1 -C 4 alkoxy; m is 0, 1 6 2, where the radicals R can be different if m is 2; R ~ is hydrogen, cyano, C? -C alkyl, C? -C4 haloalkyl, C3? C cycloalkyl; R, R independent from each other are each hydrogen, are C? -C? Alkyl, C3-C6 cycloalkyl, C2-C? Alkenyl, C2-C? Alkynyl, C? -C? Alkylcarbonyl. or, C2-C3 alkenylcarbphenyl, C3-CX0 alkynylcarbonyl or C? -C? alkylsulfonyl, wherein these radicals may be partially or completely halogenated or may carry from one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, 10 C? -Cg alkyl, haloalkyl of C? -Cg, alkylsulfonyl of C? -Cg, alkylsulfoxyl of C-C6, alkoxy of C-C6, haloalkoxy of C? -Cg, alkoxycarbonyl of C? -Cg, Alkylthio of C? -Cg, C? -Cg alkylamino, C? -C6 dialkylamino, they are C? -Cg alkylaminocarbonyl, C? -Cg di-alkylaminocarbonyl, Alkylaminothiocarbonyl of C? -Cg, di-alkylaminothiocarbonyl of C? -Cg, alkenyl of C2-Cg, alkenyloxy of C2-C6, cycloalkyl of C3 ~ Cg, cycloalkyloxy of C3 ~ Cg, heterocyclyl, heterocyclyloxy, benzyl, benzyloxy, aryl , Aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio where the cyclic groups on the other hand can be partially or completely halogenated or can carry from one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl , halogen, i-Cg alkyl, C?-Cg haloalkyl, C?-Cg alkylsulfonyl, C?-Cg alkylsulfoxyl, C3-C cycloalkyl, C-C6 alkoxy, C?-Cg haloalkoxy, alkyloxycarbonyl of C? -Cg, alkylthio 10 C? -Cg, C? -Cg alkylamino, C? -Cg di-alkylamino, C? -Cg alkylaminocarbonyl, C? -Cg di-alkylaminocarbonyl, C? -Cg alkylaminthiocarbonyl, C-di-alkylaminothiocarbonyl Cg, C2-15 alkenyl, C2-Cg alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio or C (= N0R7) -An-R8; They are. aryl, arylcarbonyl, arylsulfonyl, hetaryl, Heteroylcarbonyl or hetaryl sulfonyl, wherein these radicals may be partially or completely halogenated or may carry from one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, Aminothiocarbonyl, halogen, C? -Cg alkyl, C? -Cg haloalkyl, C? -Cg alkylcarbonyl, C? -Cg alkylsulfonyl, C? -Cg alkylsulfoxyl, C3-Cg cycloalkyl, C-alkoxy? -Cg, haloalkoxy of C? -Cg, alkyloxycarbonyl of C? -Cg, alkylthio of C? -Cg, alkylamino of C? -Cg, di-alkylamino of C? ~ Cg, alkylaminocarbonyl of C? -Cg, di-alkylaminocarbonyl of C? -Cg, C? -Cg alkylaminthiocarbonyl, C? -Cg di-alkylaminothiocarbonyl, C-10 Cg alkenyl, C2-Cg alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy or C (= N0R7) -An- R is hydrogen, is C? -Cg alkyl, C2-Cg alkenyl, C2-Cg alkynyl, where the hydrocarbon radicals of these groups may be partially or completely halogenated or may carry from one to three of the The following radicals are cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C 1 -Cg alkylaminocarbonyl, C 1 -Cg-di-alkylaminocarbonyl, C 1 -Cg alkylaminothiocarbonyl, di-alkylaminothiocarbonyl C? -Cg, C? -Cg alkylsulfonyl, C? -Cg alkylsulfoxyl, C? -Cg alkoxy, C? -Cg haloalkoxy, C? -Cg alkoxycarbonyl, C? -Cg alkylthio, C? ? -Cg, dialkylamino of C? -Cg, alkenyloxy of C2 ~ Cg, cycloalkyl of C3 ~ Cg, cycloalkyloxy of C3 ~ C, heterocyclyl, heterocyclyloxy, aryl, aryloxy, arylalkoxy of CC, arylthio, arylalkylthio of C? ~ C4, hetaryl, hetaryloxy, hetarylalkoxy of CC, hetarylthio, hetarylalkylthio of C-C4, where Ten cyclic radicals can be partly or completely halogenated and / or can contain from one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, C? -Cg alkyl, C? -Cg haloalkyl, C? -C6 alkylsulfonyl, C? -Cg alkylsulfoxyl, C3? C cycloalkyl, C? -Cg alkoxy, C? Haloalkoxy? Cg, C? -Cg alkoxycarbonyl, C? -Cg alkylthio, C? -Cg alkylamino, di¬ 20 C? -Cg alkylamino, C? -Cg alkylaminocarbonyl, C? -Cg di-alkylaminocarbonyl, C? -Cg alkylaminthiocarbonyl, C? -Cg di-alkylaminothiocarbonyl, C2-Cg alkenyl, C2 aicynyloxy. Cg, benzyl, benzyloxy, 25 aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio and C (= NOR) -An-R it is C3 ~ C cycloalkyl, C3 ~ C cycloalkenyl, heterocyclyl, aryl, hetaryl, where the cyclic radicals may be partially or completely halogenated or may carry from one to three of the following groups: cyano, nitro, hydroxyl, mercapto, amino carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C? -Cg alkyl, C? -Cg haloalkyl, C? -Cg alkylsulfonyl, C? -Cg alkylsulfoxyl, C3? C cycloalkyl, C? -Cg alkoxy, C? -Cg haloalkoxy, C? -Cg alkoxycarbonyl, C? -C6 alkylthio, C? -Cg alkylamino, C? -Cg di-alkylamino, C? -Cg alkylaminocarbonyl, C-di-alkylaminocarbonyl? -Cg, alkylaminothiocarbonyl of C? -Cg, di-alkylaminothiocarbonyl of C? -Cg, alkenyl of C2-Cg, alkenyloxy of C2-Cg, benzyl, benzyloxy, aryl, aryloxy, hetaryl and hetaryloxy; where A is oxygen, sulfur or nitrogen and where the nitrogen carries hydrogen or C? -Cg alkyl; n is 0 or 1; R is hydrogen or C? -Cg alkyl, and R is hydrogen or C? -Cg alkyl, and its salts, and b) at least one fungicide selected from the fungicides of formulas II to III in an effective amount for a synergistic effect. The fungicidal mixture as claimed in claim 1, which is conditioned in two parts, one part contains the compound I in a solid or liquid carrier and the other part contains at least one of the compounds I or III in a solid carrier or liquid. A method to control harmful fungi, which consists in treating the fungi, their habitat or the materials, plants, seeds, soils, areas or spaces that have to be protected against the attack of fungi, with a fungicide mixture as claimed in any of claims 1 to 2, wherein the application of the compound I and at least one of the compounds II to III can be carried out simultaneously, together or separately, or in succession. The method as claimed in claim 3, wherein the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces that have to be kept free of these, are treated with 0.005 to 1 kg / ha of a compound I as set forth in claim 1. The method as claimed in claim 3, wherein the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces that have to be kept free of these, are treat with from 0.01 to 1 kg / ha of at least one of compounds II to IV [sic] as set forth in claim 1.