MXPA00008479A - Fungicide mixtures based on triple oxime ether derivatives and other strobilurins - 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 (V) in a synergistically effective quantity.

Description

FUNGICIDE MIXTURES BASED ON TRIPELOXIMETER DERIVATIVES AND OTHER ESTROBILINS Description The present invention relates to mixtures for controlling harmful fungi, which contain a) phenylacetic acid derivatives of the formula I wherein the substituents and the Index have the following meanings: X NOCH3, CHOCH3, CHCH3; O, NR R1, R each independently of the other, hydrogen and C? -C-alkyl; R2 cyano, nitro, trifluoromethyl, halogen, C? -C -alkyl and C? -C-alkoxy; m O, 1 or 2, the radicals R2 being able to be different when m is 2; R3 hydrogen, cyano, C? -C4-alkyl, C? -C-haloalkyl, C3-C6-cycloalkyl; R, R6 each independently of the other, hydrogen, C? -C? -alkyl, C3-C6-cycloalkyl, C2-C? Or? Alkenyl, CC? O-alkynyl, C? -C? Or -alkylcarbonyl, CC? _-Alkenylcarbonyl, C3-C? or ~ alkynylcarbonyl or C? -C? or -alkylsulfonyl, which radicals may be partially or completely halogenated or carry from one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, to incarbonyl, aminothiocarbonyl, halogen , C? -C6-alkyl, C? -C6-haloalogyl, Ci-C? -alkylsulfonyl, Ci-Cd-alkylsulfoxyl, Ci-Cd-alkoxy, Ci-Cd-halo-alkoxy, Ci-Cd-alkoxycarbonyl, Ci-C? -alkylthio, C? -C6-alkylamino, di-Ci-Ce-alkylamino, C? -C6-alkylaminocarbonyl, di-C? -C6-alkylaminocarbonyl, Ci-Cd-alkylaminthiocarbonyl, di-Ci-Cg-al- quilaminothiocarbonyl, C2-C6-alkenyl, C-Cg-alkenyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkyloxy, heterocyclyl, heterocyclyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio, whose groups cyclical can be partly or completely halogenated or carry from one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C? -C6-alkyl, C? -C6-haloalkyl, Cx-Cd-alkyl-? sulfonyl, Ci-Cß-alkylsulfoxyl, C3-C6-cycloalkyl, Ci-Cd-alkoxy, Ci-Cβ-halogenoalkoxy, C? -C6-alkyloxycarbonyl, Ci-C-alkylthio, Ci-Cd-alkylamino , di-C? -C6-alkylamino, C? -C6-alkylaminocarbonyl, di-C? -C6-alkylaminocarbonyl, C? -C6-alkylamothiocarbonyl, di-C? -C6-alkylaminthiocarbonyl, c2-c6- alkenyl, C-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetthylthio or C (= NOR7) -An-R8; aryl, arylcarbonyl, arylsulfonyl, hetaryl, heteroarylcarbonyl or hetarylsulfonyl, the radicals of which may be partially or completely halogenated or carrying from one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C? -C6-alkyl, C? -C6-haloalkyl, C? -C6-alkyl- carbonyl, C6-alkylsulfonyl, C6-alkylsulfoxyl, C3-C6-cycloalkyl, C6-alkoxy, C6-d-haloalkoxy, C6-alkyloxycarbonyl, C6-C6 -alkylthio, C? -C6-alkylamino, di-C? -Cd-alkylamino, C? -C6-alkylaminocarbonyl, di- C? -C6-alkylaminocarbonyl, C-C-alkylaminthiocarbonyl, di-C? -Cg -alkylaminothiocarbonyl, C2-Cg-alkenyl, C2-C6-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy or C (= NOR7) -An-R8; R5 is hydrogen, C? -Cg-alkyl, C-Cg-alkenyl, C2-Cg-alkynyl, the hydrocarbon radicals of these groups may be partially or completely halogenated or carry from one to three of the following radicals: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C? -Cg-alkylaminocarbonyl, di-C? -C6-alkylaminocarbonyl, C? -C -alkylaminothiocarbonyl, di-C? -C6-alkylaminothiocarbonyl, C? -Cg-alkylsulfonyl, C? -Cg-alkyl-sulfoxyl, Ci-Cg-alkoxy, C-Cg-halogenoalkoxy, C? -Cg-alkoxycarbonyl, C? -C6-alkylthio, C? -Cg-alkylamino, di- C? -Cg-alkylamino, C2-Cg-alkenyloxy, C3-C6-cycloalkyl, C3-Cg-cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, Aryloxy, aryl-C? -C4-alkoxy, arylthio, aryl-C? -C4-al-quiltio, hetaryl, hetaryloxy, hetaryl-C? -C4-alkoxy, etarthylthio, hetaryl-C? -C -alkylthio, whose cyclic radicals may in turn be partially or completely halogenated and / or carry from one to three of The following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, C? -Cg-alkyl, C? -C6-haloalkyl, C? -C6-alkylsulfonyl, C? -Cg-alkylsulfoxyl, C3Cg -cycloalkyl, C? -Cg-alkoxy, C? -C6? haloalkyl, C? -C6-alkoxycarbonyl, C? -C6-alkylthio, C? -C6-alkyl-amino, di-C? -Cg- alkylamino, C? -Cg-alkylaminocarbonyl, di-C? -Cg-alkylaminocarbonyl, C? -Cg-alkylaminthiocarbonyl, di-C? -Cg-alkyl minotothiocarbonyl, C-Cg-alkenyl, C-Cg-alkenyloxy, Benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio and C (= NOR7) -An-R8; C3-C6-cycloalkyl, C3-Cg-cycloalkenyl, heterocyclyl, aryl, hetaryl, whose cyclic radicals may be partially or completely halogenated or carry from one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C? -C6-alkyl, C? -Cg-halogenoalkyl, C? -C6-alkylsulfonyl, C? -Cg-alkylsulfoxyl, C-Cg-cycloalkyl, C? -Cg-alkoxy , C? -Cg-halogenoalkoxy, C? -Cg-alkoxycarbonyl, C? -Cg-alkylthio, C? -Cg-alkylamino, di-C? -Cg-alkylamino, C? -C6-alkylaminocarbonyl, di-C? -Cg-alkylaminocarbonyl, C? -Cg-alkylaminthiocarbonyl, di-C? -Calkylaminothiocarbonyl, C-Cg-alkenyl, C-Cg-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl and hetaryloxy; meaning To oxygen, sulfur or nitrogen and carrying the nitrogen hydrogen or C? -Ce-alkyl; n 0 or 1; 25 R7 hydrogen or C? -Cg -alqui lo y R8 hydrogen or C? -Cg-alkyl, as well as its salts, 30 b) by at least one fungicide selected from the fungicides of formulas II to V fifteen The present invention has for its object to provide fungicidal mixtures, which have a good fungicidal action, which is superior to that of the mixture components alone, especially against fungal diseases in rice crops.

This object is achieved according to the invention by the mixtures according to 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 V are also known and described in the literature. In addition, they are obtained, if necessary, in the trade under the trade name indicated in brackets: II: common name: Azoxystrobin (trade name: Amistar®, Cia. Zeneca) III: EP- A 253,313, common name: Kresoxim-methyl (trade name Brio®, Cia. BASF) IV: EP 398,692, proposed common name: Methominostrobin (sign of development SSF-126, Cia. Shionogi); V: EP 398,692, CAS RN 162535-21-9, SSF 129, development product of the Shionogi Co., Ltd.) Compounds I can be obtained due to their C = C and C = N double bonds as isomeric mixtures E / Z, which can be separated, eg by crystallization or chromatography in a customary manner in the individual compounds.

Provided that isomeric mixtures are obtained in the synthesis, it is generally not absolutely necessary to separate them, since the individual isomers can be transformed into each other during the preparation and application (eg under the action of light, acid or bases). . Transformations of this type can also take place after the application, for example, in the treatment of the plants in the treated plant or in the fungus or noxious animal to be combated.

With respect to the C = X double bond, the E isomers of the compounds I (configuration with respect to the -OCH3 group or the -CH3 group in relation to the -CO2R1 group) are preferred in terms of their efficiency.

With respect to the double bond -C (R3) = NOCH2- the cis isomers of the compounds I (configuration with respect to the radical R3 in relation to the group -OCH2-) are preferred in terms of their efficiency.

In the above-mentioned definitions of compounds I, collective terms generally representative of the following groups were used: halogen: fluorine, chlorine, bromine and iodine; alkyl: linear or branched alkyl groups with 1 to 4, 6 or 10 carbon atoms, eg C? -Cg-alkyl wie methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl , 1-methylbutyl, 2-methyl-butyl, 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 -ethyl tert-butyl, 1,2-trimethylpropyl, 1,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; haloalkyl: linear or branched alkyl groups with 1 to 6 carbon atoms, in which groups the hydn atoms may be partially or completely substituted by halogen atoms, such as those mentioned above, eg C? -C-halogenoal < Guilo, eg chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2,2-tri-fluoroethyl, 2 chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl; cycloalkyl: monocyclic alkyl groups with 3 to 6 ring carbon members, eg cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; alkenyl: linear or branched alkenyl groups having 2 to 6 or 10 carbon atoms and a double bond at an arbitrary position, for example C2-Cg-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-bute-nilo, 1-methyl-l-propenyl, 2-methyl-l-propenyl, l-methyl-2-pro-penyl, 2-methyl-2-propenyl, 1- pentenyl, 2-pentenyl, 3-pen-tenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-l-butenyl, 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, l-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, 5-hexe-nyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-methyl pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-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, 1-dimethyl-2-bute-nile, 1,1-di-methyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-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-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-l-butenyl, l-ethyl-2-butenyl, l-ethyl-3-butenyl, 2-ethyl-l-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-methyl-2-propenyl; alkynyl: straight or branched having 2 to 10 carbon atoms and alkynyl groups a triple bond at an arbitrary position, for example C2-C6-alkynyl, 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-buty-nyl, 2-methyl-3-butynyl, 1, 1-dimethyl- 2-propynyl, l-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, l-methyl-3-pentynyl, 1-methyl til-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1, 1-dimethyl-2-buty-nyl, 1, l-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, l-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl- 3-butynyl and l-ethyl-1-methyl-2-propynyl; heterocyclyl or heterocyclyloxy, heterocyclylthio and hete-rociclilamino: heterocycles mono- or polycyclic, saturated or partially unsaturated, with three to six members, containing one to three heteroatoms selected from the group comprising oxygen, nitn and iufre, and which are linked? directly or (heterocyclyloxy) via an oxygen atom or (heterocyclylthio) via a sulfur atom or (heterocyclylamino) via a nitn atom to the skeleton, eg 2 - tetrahydrofuranyl, oxiranyl, 3-te-trahidrofuranilo, 2 - tetrahydrothienyl, 3 - tetrahydrothienyl, pyrrolidinyl, 3-pyrrolidinyl, 3 - isoxazoldinílo, 4-isoxazolidinyl, 5- isoxazolidinyl, 3 -isotiazolidinilo, 4 -isotiazoli -dinilo, 5-isothiazolidinyl, 3 -pyrazolidin4 -pirazolidi-nile, 5-pyrazolidinyl, 2 -oxazolidinilo, 4 -oxazolidinilo, 5-oxazolidinyl, 2 - thiazolidinyl, 4 - thiazolidinyl, 5-thiazolidinyl, 2 -imidazolidinilo, 4 -imidazolidinilo, 1, 2, 4 -oxadiazo-lidin-3-yl, 1, 2, 4-oxadiazolidin-5-yl, 1, 2, 4-thiadiazoli -din-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-dihydro-fur-3-yl, 2,3-dihydro-fur-4-yl, 2,3-dihydro-fur-5-yl, 2,5-dihydro-fur-2 -yl, 2, 5-dihydro-fur-3-yl, 2,3-dihydro-thien-2-yl, 2,3-dihydrothien-3-yl, 2,3-dihydrothien-4-yl, 2, 3 -dihydrothien-5-yl, 2, 5-dihydrothien-2-yl, 2,5-dihydro-thien-3-yl, 2,3-dihydropyrrol-2-yl, 2,3-dihydropyrrol-3-yl, 2 , 3-dihydropyrrol-4-yl, 2,3-dihydropyrrol-5-yl, 2,5-dihydro-pyrrol-2-yl, 2,5-dihydropyrrol -3-yl, 2,3-dihydroisoxa-zol-3 -yl, 2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxa- zol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxa-zol-4-yl, 4,5-dihydroisoxazol-5-yl, 2,5-dihydroisothia-zol-3-yl, 2, 5-dihydroisothiazol yl-5-yl -dihidroisopira-zol-4-5-dihydroisothiazol-4 -yl, 2, 2, 3 -dihidroisopirazol-3 -yl, 2, 3, 2, 3 -dihidroisopirazol- 5-yl, 4, 5 -dihidroisopira-zol-3-yl yl -dihidroisopira-zol-5-, 4, 5-dihidroisopirazol-4 -yl, 4, 5, 2, 5 -dihidroisopirazol-3 -yl, 2, 5-dihydroisopyral-zol-4-yl, 2,5-dihydroisopyrazol-5-yl, 2,3-dihydrooxa-zol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazole-5- ilo, 4, 5-dihydrooxazol-3-yl, 4,5-dihydrooxazol-4-yl, 4,5-dihi-drooxazol-5-yl, 2,5-dihydrooxazol-3-yl, 2,5-dihydrooxa- zol-4-yl, 2, 5-dihydrooxazol-5-yl, 2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl, 2,3-dihydrothiazol-5-yl, 4,5- dihydro-thiazol-2-yl, 4,5-dihydrothiazol-yl, 4,5-dihydrothia-zol-5-yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl, 2 , 5-dihydrothiazol-5-yl, 2,3-dihydroimidaz ol -2 -yl, 2,3-dihi-droimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4,5-dihydroxy-dazol-2-yl, 4,5-dihydroimidazol-4-yl, 4,5-dihydroimide-zol-5-yl, 2,5-dihydroimidazol-2-yl, 2,5-dihydroimide-zol-4-yl, 2,5-dihydroimidazol-5-yl, 2-morpholinyl, 3- morpho-linilo, 2 -piperidinyl, 3 -piperidinyl, 4 -piperidinyl, 3-tetrahidropiridacinilo, 4- tetrahidropiridacinilo, 2- etrahidro-pyrimidinyl, 4 - tetrahydropyrimidinyl, 5 - tetrahidropirimidi Nilo, tetrahidropiracinilo 2-, 1, 3, 5- tetrahydrotriazin-2-yl, 1,2,4-tetrahydrotriazin-3-yl, 1,3-dihydrooxacin-2-yl, 1,3-dithiane-2-yl, 2-tetrahydropyranyl, 1,3-dioxolan- 2-yl, 3,4,5,6-tetrahydropyridin-2-yl, 4H-1, 3-thiazin-2-yl, 4H-3, l-benzothiazin-2-yl, 1,1-dioxo-2, 3, 4, 5 -tetrahydro-thien-2-yl, 2H-1,4-benzothiazin-3-yl, 2H-1,4-benzoxacin-3-yl, 1,3-dihydrooxacin-2-yl, 1 3 -ditian-2-ilo, aryl or aryloxy, arylthio, arylcarbonyl and arylsulfonyl: mono or polycyclic aromatic hydrocarbon radicals, which are directly or (aryloxy) linked via an oxygen atom (-0-) or (arylthio) a sulfur atom (-S -), (aryl carbonyl) via a carbonyl group (-CO-) or (arylsulfo-nyl) via a sulfonyl group (-S02-) with the backbone, eg phenyl, naphthyl and phenanthrenyl or either phenyloxy, naphthyloxy and phenanthrenyloxy and the corresponding carbonyl and sulfonyl radicals; hetaryl or hetaryloxy, hetarylthio, hetarylcarbonyl and he-tarylsulfonyl: mono or aromatic polycyclic radicals, which contain together with carbon ring members additionally from one to four nitrogen atoms or from one to three nitrogen atoms and one oxygen atom, or a sulfur atom or an oxygen atom or a sulfur atom, and which are directly or (hetaryloxy) linked via an oxygen atom (-0-) or (hetarylthio) a sulfur atom (-S-) , (hetarylcarbonyl) via a carbonyl group (-CO-) or (hetaryl-sulfonyl) via a sulfonyl group (-S02-) with the backbone, e.g. ex. five-membered heteroaryl, containing one to three nitrogen atoms: pentacyclic heteroaryl groups, which may contain together with carbon atoms of one to three nitrogen atoms as ring members, eg 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 ?; five-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and a sulfur or oxygen atom, or an oxygen or sulfur atom: pentacyclic heteroaryl groups, which may contain together with atoms carbon of one to four nitrogen atoms or one to three nitrogen atoms and a sulfur or oxygen atom, or an oxygen or sulfur atom as ring members, eg 2-fu-ryl, 3- furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrazyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazyl-lyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazo-lyl, 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-oxadia-zol-2-yl, 1, 3, 4-thiadiazol-2-yl, 1, 3, 4-triazol-2-yl; heteroaryl benzofused five-membered, containing one to three nitrogen atoms or one nitrogen atom and / or an oxygen atom or sulfur: pentacyclic heteroaryl groups which may contain together with carbon atoms one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom, or one oxygen atom or one sulfur atom as ring members, and wherein two neighboring carbon ring members or an annular nitrogen member and a member carbon ring can be linked together by means of a buta-1,3-dien-1,4-diyl bridge; five-membered heteroaryl, linked via nitrogen, containing one to four nitrogen atoms, or benzo-condensed five-membered heteroaryl linked via nitrogen, containing one to three nitrogen atoms: pentacyclic heteroaryl groups, which may contain together with carbon atoms of one to four nitrogen atoms or one to three nitrogen atoms as ring members, and wherein two neighboring carbon ring members or an annular nitrogen ring and an annular carbon ring can be attached by means of a bridge of buta-1, 3-dien-l, 4-diyl, these rings being linked via one of the annular nitrogen members with the backbone; six-membered heteroaryl, containing one to three or one to four nitrogen atoms: heterocyclic hexacyclic groups, which may contain together with carbon atoms of one to three or one to four nitrogen atoms as ring members, eg 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1, 3, 5-triazinyl- 2-yl, 1, 2, 4-triazin-3-yl and 1,2,4,5-tetrazin-3-yl; benzo-condensed six-membered heteroaryl containing from one to four nitrogen atoms: benzocondensated hexacyclic heteroaryl groups in which two adjacent ring-like carbon members can be linked together by a buta-1,3-dien-1 bridge; 4 -diyl, eg quinoline, isoquinoline, quinazoline and quinoxaline, or the corresponding oxy, thiocarbonyl or sulfonyl groups.

Hetarylamino: mono or aromatic polycyclic radicals, which may contain, together with carbon ring members, additionally from one to four nitrogen atoms or from one to three nitrogen atoms and one oxygen or sulfur atom, and which are linked via a Nitrogen atom with the skeleton.

The indication "partially or completely halogenated" means that in the groups so characterized the hydrogen atoms may be partly or completely replaced by identical or different halogen atoms.

With respect to their biological action, the compounds of the formula I are preferred, wherein m is equal to 0.

Also preferred are compounds of the formula I, wherein R 1 signifies methyl.

In addition, compounds I are preferred, wherein R 3 is hydrogen, cyano, cyclopropyl, methyl, ethyl, 1-methylethyl or CF 3.

Additionally, compounds I, wherein R3 means methyl, are preferred.

Also preferred are compounds I, wherein R3 means cyano.

In addition, compounds I are preferred, wherein R3 means cyclopropyl.

Additionally, compounds I are preferred, wherein R3 means CF3.

Also preferred are compounds I, wherein R5 means hydrogen, cyclopropyl, methyl, ethyl, iso-propyl, aryl event. sust or hetarilo.

In addition, compounds I, in which R5 means methyl, are preferred.

Also preferred are compounds I, wherein R5 means ethyl.

In addition, compounds I are preferred, wherein R 5 means iso-propyl.

Additionally, compounds I, wherein R5 means cyclopropyl, are preferred.

In addition, compounds I are preferred, wherein R 5 means CF 3.

Also preferred are compounds I, where R 5 stands for aryl event. sust or hetarilo.

Also preferred are compounds I, wherein R 5 means pyridyl event. .sup.-pyrimidyl, pyrazinyl, pyridazinyl or triazinyl.

Also preferred are compounds I, wherein R5 means furyl event. subst., thienyl or pyrrolyl.

Also preferred are compounds I, wherein R 5 represents oxazolyl event. Substance, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl or imidazolyl.

Also preferred are compounds I, wherein R 5 represents oxdiazolyl event. subst., thiadiazolyl or triazolyl.

In addition, compounds I are preferred, wherein R5 means unsubstituted phenyl or one or two of the following groups: nitro, cyano, hydroxy, amino, aminocarbonyl, aminothiocarbonyl, halogen, C? -C4-alkyl, C? -C4-haloalkyl, C? -C4-alkoxy, C? -C4-halogenoalkoxy, C? -C4-alkylamino, di-C? -C4-alkylamino, C? -C4-alkylsulfonyl, C? -C4-alkoxycarbonyl , C? -C4-alkylaminocarbonyl or di-C? -C4-alkylaminocarbonyl.

In addition, compounds I are preferred, wherein R 4 is hydrogen, C? -Cg -alkyl, C 2 -C -alkenyl, C 2 -Cg-alkynyl, allyl, arylalkyl, hetarylalkyl, aryloxyalkyl, heteroaryloxyalkyl, aryl or hetarilo.

Also preferred are compounds I, wherein R 4 is C? -C6-alkyl.

Other preferred compounds I can be derived from WO 97 / 15,552.

The compounds I contained in the mixtures stand out for presenting an excellent effect against a broad spectrum of phytopathogenic fungi, especially of the class of Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes.

They are especially important for combating a myriad of fungi in different crop plants, such as cotton, legumes (eg cucumbers, beans, tomatoes, potatoes and cucurbits), barley, turf, oats, bananas, coffee, corn, fruits, rice, rye, soy, vine, barley, ornamental plants, sugar cane and countless seeds.

They are especially suitable for combating the following phytopathogenic fungi: Erysiphe graminis (oídio) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbitáces, Podosphaera leucotricha in apples, Uncinula necator in the vine, Puccinia species in cereals, species of Rhi -zoctonia in cotton , rice and grass, Ustilago species in cereals and sugarcane, Venturia inaequalis in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis ciñera (gray rot) in strawberries, legumes, ornamental plants and vine, Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticulture in the vine, Pseudope-ronospora species in cucurbits and hops, Alternate species in legumes and fruits, Mycosphaerella species in bananas, as well as Fusarium and Verticillium species.

Compounds II to V are obtained commercially as fungicides.

In the preparation of the mixtures, pure substances I and II to V are preferably used, to which other active substances can be added against harmful fungi or other parasites, such as insects, arachnoids or nematodes, or else herbicides or active substances regulating the growth, or fertilizers.

The mixtures from the compounds I and at least one compound II to V can be used simultaneously, in a joint or separate form, and are deadened by presenting an excellent effect against a phylopathogenic spectrum of fungi, especially of the ascomycetes class , basidiomycetes, phycomycetes and deuteromycetes. In part they are systemically active, so they can 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, tomatoes, potatoes and cucurbits), barley, turf, oats, bananas, coffee, corn, fruits, rice, rye, soy, 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 cucurbitas, Podosphaera leucotricha in apples, üncinula necator in the vine, Puccinia species in cereals, Rhi-zoctonia species in cotton , rice and grass, Ustilago species in cereals and sugarcane, Venturia inaequalis in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis ciñera (gray rot) in strawberries, legumes, ornamental plants and vine, Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticulture in the vine, Pseudope-ronospora species in cucurbits and hops, Alternate species in legumes and fruits, Mycosphaerella species in bananas, as well as Fusarium and Verticillium species.

The mixtures according to the invention are especially suitable for controlling Pyricularia oryuae.

The compounds I and at least one of the compounds II to V can be applied simultaneously, namely jointly or separately, the order of application in the separate application being generally unimportant for the success of the treatment.

The application rates of the mixtures according to the invention vary, above all, in agricultural crop areas, depending on the type of effect desired, from 0.01 to 8 kg / ha, preferably 0.1 to 5 kg / ha, especially 0, 5 to 3.0 kg / ha.

Application rates vary for compounds I from 0.01 to 2.5 kg / ha, preferably 0.05 to 2.5 kg / ha, especially 0.1 to 1.0 kg / ha.

Application rates vary for compounds II to V from 0.001 to 5 kg / ha, preferably 0.005 to 2 kg / ha, especially 0.01 to 1.0 kg / ha.

In the treatment of seeds, application rates of the mixture are generally used from 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 intended to combat phytopathogenic fungi, compounds I and at least one of compounds II to V, or mixtures of the compounds I and at least one of the compounds II, are applied together or separately. to V by spraying or spraying the seeds, plants or soil before or after planting the plants or before or after the emergence of the plants.

The mixtures according to the invention 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, pastes, spraying or spraying agents. , directly sprayable granules, by spraying, spraying, atomizing, spraying or spraying. 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 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 (eg 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 polyethylene glycol ether fatty alcohol, alkyl and aryl sulfonates) and dispersants, such as sulfuric waste liquors and methyl cellulose.

Suitable surface-active substances are the alkaline earth metal and ammonium salts of lignin sulphonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutyl naphthalene sulfonic acid, fatty acids, alkyl and alkylaryl sulfonates, alkyl sulfates, lau-rylether sulfates 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-octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tri-butylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol condensates, ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether ketole, sorbitol ester, lignin sulfite waste liquors s and methylcellulose.

The powders, spraying and spreading agents can be obtained by mixing or co-grinding the compounds I and at least one of the compounds II to IX or of the mixture from the compounds I and at least one of the compounds II up to IX 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 the compounds I and at least one of the compounds II to V or of the mixture from compounds I and at least one of compounds II to V. The active substances are used here in a purity of 90% to 100%, preferably 95% to 100% (according to HPLC spectrum).

The corresponding formulation is applied, treating the noxious fungi, their living space or the plants, seeds, soils, areas, materials or enclosures to be kept free thereof, with an active fungicidal amount of the compounds I and at least one of compounds II to V 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 cyclohexane, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 40 moles of ethylene oxide to 1 mole of Castor oil; 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 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 lignosulfonic acid from 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 spraying 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 oleic dispersion from 20 parts by weight of the active substances, 2 parts by weight of the cyclic salt of dodecylbenzenesulfonic acid, 8 parts by weight of the polyglycol ether fatty alcohol, 20 parts by weight of the sodium salt of a condensate of phenyl sulfonic acid 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..

The evaluation is done, determining the area of the leaves infested 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) -100 / ß a is equivalent to the fungal infection of the plants treated in 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 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 bx is the degree of action, translated in% of the untreated control, when using the active substance A in the concentration a and 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 Pyricularia oryzae (protective) The leaves of rice seedlings of the variety "Tai-Nong 67" are sprayed to run off with aqueous preparations of active substance prepared with a stock solution from 10% active substance, 63% cyclohexanone and 27% emulsifier. The next day the plants are inoculated with an aqueous spore suspension of Pyricularia oryzae. Next, the test plants are placed for 6 days in climatic chambers at 22 - 24 ° C and 95 - 99% relative humidity of the air. Next, the extent of the development of the infection on the leaves is visually evaluated.

The visually determined values for the percentage of the infected leaf surface are converted to degrees of action as% of the untreated control. A degree of action equal to 0 means the same infection as the untreated control, a degree of action equal to 100 means 0% infection. The expected action levels for the active substance combination are determined according to Colby's formula (Colby, SR (Calculating synergistic and antagonistic responses of herbi -cide Combinations ", Weeds, 15, S. 20-22, 1967) and compared with the observed degrees of action.

As component a) the following compound I 'is used: The results of the tests can be derived from the following tables 1 and 2: Table 1: Table 2: * calculated according to Colby's formula From the results of the tests it is clear that the degree of action is with all the mixing ratios higher than the degree of action precalculated according to the Colby formula.

Claims (1)

Claims

1. Mixtures for the protection of plants, which contain as active components a) phenylacetic acid derivatives of the formula I wherein the substituents and the index have the following meanings: X NOCH3, CHOCH3, CHCH3; O, NR R ^ R each independently of the other, hydrogen and C? -C4-alkyl; R2 cyano, nitro, trifluoromethyl, halogen, C? -C4-alkyl and C? -C4-alkoxy; m 0, 1 or 2, the radicals R2 being able to be different when m is 2; R3 hydrogen, cyano, C? -C4-alkyl, C? -C4? Halogen-alkyl, C3-Cg-cycloalkyl; R4, R6 each independently of the other, hydrogen, C? -C? Or? Alkyl, C3-C6-cycloalkyl, C? -alkenyl, C2-C? O-alkynyl, C? -C? -alkylcarbonyl, C2-C? or -alkenylcarbonyl, C3-C? or ~ alkynylcarbonyl or C? -C? or -alkylsulfonyl, whose radicals 10 can be partially or completely halogenated or carry from one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C? -Cg-alkyl, C? -Cg-halogen- Alkyl, C? -Cg-alkylsulfonyl, C? -Cg-alkylsulfoxyl, C? -Cg-alkoxy, C? -Cg-halogenoalkoxy, C? -Cg-alkoxycarbonyl, C? -C -alkylthio, C? Cg-alkylamino, di-C? -C6-alkylamino, C? -C -alkylaminocarbonyl, di-C? -Cg-alkylami¬ 20 -carbonyl, C? -Cg-alkylaminthiocarbonyl, di- C? -Cg-alkylaminthiocarbonyl, C-C-alkenyl, C-Cg-alkenyloxy, C3-Cg-cycloalkyl, C3-C6-cycloalkyloxy, heterocyclyl, heterocyclyloxy, benzyl , benzyloxy, aryl, aryloxy, arylthio, 25 hetaryl, hetaryloxy and hetarylthio, whose cyclic groups can themselves be partially or completely halogenated or carry from one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocar¬ 30 bonyl, aminothiocarbonyl, halogen, C? -Cg-alkyl, C? -C6-haloalkyl, C? -Cg-alkylsulphinyl, C? -C6-alkylsulfoxyl, C3-C5-cycloalkyl, 35 C? -Cg-alkoxy, C? -Cg-halogenoalkoxy, C? -C6-alkyloxycarbonyl, C-C6-alkylthio, C? -C6-alkylamino, di-C? -C6-alkylamino, C? -Cg-alkylaminocarbonyl, di-C? -Cg-alkylaminocarbonyl, C? -Cg-alkylaminthiocarbonyl, di-C? -Cg-alkylamothiocarbonyl, C2-Cg-alkenyl, C2-Cg-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio or C (= NOR7) -An-R8; 10 aryl, arylcarbonyl, arylsulfonyl, hetaryl, hetarylcarbonyl or hetarylsulfonyl, the radicals of which may be partially or completely halogenated or carry from one to three of the groups Next: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C? -Cg-alkyl, C? -C6-haloalkyl, C? -C-alkylcarbonyl, C? -Cg-alkylsulfonyl, C? -C -alkylsulfoxyl, C3-C6-cycloalkyl, C? -Cg-alkoxy, C? -Cg-halogenoalkoxy, C? -Cg-alkyloxycarbonyl, C? -Cg-alkylthio, C? -Cg-alkylamino, di-C? -Cg-alkylamino, C? -Cg-alkylaminocarbonyl, di- C? -Cg-alkylaminocarbonyl, C? -Cg-alkylamino-25 thiocarbonyl, di-C? -Cg-alkylaminthiocarbonyl, C-Cg-alkenyl, C -Cg- alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy OC (= NOR7) -An-R8; 30 R5 hydrogen, 35 C? -Cg-alkyl, C2-Cg-alkenyl, C-Cg-alkynyl, the hydrocarbon radicals of these groups being partially or completely halogenated or carrying from one to three of the following radicals: cyano, nitro, hydroxy, mercapto amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C? -Cg-alkylaminocarbonyl, di-C? -Cg-alkylaminocarbonyl, C? -Cg-alkylaminothiocarbonyl, di-C? -Cg-alkylaminothiocarbonyl, C? -C6-alkylsulfonyl, C? -C6-alkyl sulfoxyl, C? -Cg-alkoxy, C? -Cg-halogenoalkoxy, C? -Cg-alkoxycarbonyl, C? -Cg-alkylthio, C? -Cg -alkylamino, di-C? -Cg-alkylamino, C-Cg-alkenyloxy, C3-Cg-cycloalkyl, C3-C6-cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, aryl-C? -C4-alkoxy, arylthio, aryl-C? -C4-alkylthio, hetaryl, hetaryloxy, hetaryl-C? -C4-alkoxy, hetarylthio, Heteryl-C? -C4-alkylthio, whose cyclic radicals 20 may, for their part, be partially or completely halogenated and / or carry from one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, C? -Cg-alkyl, C? -Cg -halogen -alkyl, C? -Cg-alkylsulfonyl, C? -Cg-alkyl-sulfoxyl, C3Cg-cycloalkyl, C? -C6-alkoxy, C? -C6-halogenoalkoxy, C? -Cg-alkoxycarbonyl, C? Cg-alkylthio, C? -Cg-alkyl-amino, di- C? -Cg-alkylamino, C? -Cg-alkylaminocarbonyl, 30 di-C? -Cg-alkylaminocarbonyl, C? -C6-alkylammoniocarbonyl, di-C? -C-alkylaminothiocarbonyl, C2-C6-alkenyl, C2-Cg-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio and C (= NOR7) -An-R8; C3 -Cg-cycloalkyl, C3-Cg-cycloalkenyl, heterocyclyl, aryl, hetaryl, whose cyclic radicals may be partially or completely halogenated or carry from one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, amino¬ 10 thiocarbonyl, halogen, C? -Cg-alkyl, C? -C -haloalkyl, C? -C6-alkylsulfonyl, C? -Cg-alkylsulfoxyl, C3-Cg-cycloalkyl, C? -Cg-alkoxy, Cx-Cg- haloalkoxy, C? -Cg-alkoxycarbonyl, C? -Cg-alkylthio, C? -C6-15 alkylamino, di-C? -Cg-alkylamino, C? -C6 ~ alkylaminocarbonyl, di-C? -Cg -alkylaminocarbonyl, C? -Cg-alkylaminthiocarbonyl, di-C? -Cg-alkylaminothiocarbonyl, C-Cg-alkenyl, C2-Cg-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, he¬ 20 Taryl and hetaryloxy; meaning oxygen, sulfur or nitrogen and carrying the Hydrogen nitrogen or C? -Cg-alkyl; n 0 or 1; R7 hydrogen or C? -Cg-alkyl and R8 hydrogen or C? -C6-alkyl, 35 as well as its salts. and b) at least one compound of formulas II to V in an active synergetic quantity. The mixture according to claim 1, which is conditioned in two parts, the first part containing the compound I in a solid or liquid support and the other part containing at least one of the compounds II to V in a solid or liquid support. fifteen Procedure for combating harmful fungi, characterized because fungi, their living space or materials, plants, seeds, soils, surfaces or enclosures are treated to protect against fungal infection with fungi. A mixture according to one of claims 1 to 2, it being possible to apply the compound I and at least one of the compounds II to V simultaneously, namely jointly or separately, or in succession.- Method according to claim 3, characterized in that the fungi, their living space or the materials, plants, seeds, soils, surfaces or enclosures to be protected against fungal infection are treated with 0.005 to 1 kg / ha of a compound I according to the claim 30 tion 1. The method according to claim 3, characterized in that the fungi, their living space or the materials, plants, seeds, soils, surfaces or enclosures to be protected against fungal infection are treated with 0.01 to 1 kg / ha of minus one compound II to V according to claim 1. SUMMARY OF THE INVENTION. Fungicidal mixtures, which contain as active components a) phenylacetic acid derivatives of the formula I wherein the substituents and the index have the meanings indicated in the description, as well as their salts, Y b) at least one compound of formulas II to V fifteen in an active synergetic quantity. 25 30 35