WO1999048367A1

WO1999048367A1 - Fungicide mixtures based on triple oxime ether derivatives and other strobilurins

Info

Publication number: WO1999048367A1
Application number: PCT/EP1999/001909
Authority: WO
Inventors: Klaus Schelberger; Thomas Grote; Hubert Sauter; Eberhard Ammermann; Gisela Lorenz; Siegfried Strathmann
Original assignee: Basf Aktiengesellschaft
Priority date: 1998-03-24
Filing date: 1999-03-22
Publication date: 1999-09-30
Also published as: KR20010042148A; CN1149924C; ID26019A; CN1294487A; BR9909001A; CO5090844A1; TW548078B; CA2323598A1; KR100557363B1; EP1065930A1; IL138168A0; JP2002507552A; AU3416899A

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

Fungicidal mixtures based on triple oxime ether derivatives and other strobilurins

description

The present invention relates to fungicidal mixtures for combating harmful fungi which

a) Phenylacetic acid derivatives of the formula I.

CD

O

^• R o

in which the substituents and the index have the following meaning:

X STILL ₃ , CHOCH ₃ , CHCH ₃ ;

0, NO

R jR independently of one another hydrogen and -CC ₄ alkyl;

R ² cyano, nitro, trifluoromethyl, halogen, -CC alkyl and C] _- C alkoxy;

m is 0, 1 or 2, it being possible for the radicals R ^{2 to be} different if m is 2;

R ^{3 is} hydrogen, cyano, -CC alkyl, -C-haloalkyl, C ₃ -C ₅ cycloalkyl;

R ⁴ , R ^{6 are} independently hydrogen,

-C-Cιo-alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -Cκ) alkenyl, C -Cιo-alkynyl, Cι-Cιo-alkylcarbonyl, C ₂ -Cι ₀ -alkenylcarbonyl, C ₃ -Cιo-alkynylcarbonyl or -CC-alkyl sulfonyl, where these residues can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, 2

Mercapto, Ammo, Carboxyl, Ammocarbonyl, Ammothiocarbonyl, Halogen, Ci-Cg-Alkyl, Cχ-Cg-Halogenalkyl, Cι-C ₆ -Alkylsulfonyl, Ci-Cg-Alkylsulfoxyl, Cι-C ₆ -alkoxy, Cι-C ₆ -haloalkoxy , Ci-Cg-alkoxycarbonyl, Ci-Cg-alkyl-thio, Ci-Cg-alkylammo, Dι-Cι-Cg-alkylammo,

Ci-Cg-alkylammocarbonyl, di-Ci-Cg-alkylammocarbonyl, Ci-Cg-alkylammothiocarbonyl, Dι-Cι-Cg-alkylammothιo- carbonyl, C -C ₆ -alkenyl, C -C ₆ -alkenyloxy, C -Cg-cyclo- alkyl, C -Cs-cycloalkyloxy, heterocyclyl, heterocyclicoxy, benzyl, benzyloxy, aryl, aryloxy, arylthio,

Hetaryl, hetaryloxy and hetarylthio, where the cyclic groups can in turn be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, ammo, carboxyl, ammocarbonyl, ammothiocarbonyl, halogen, Ci-Cg -Alkyl, C] .- Cg-haloalkyl, -C-C ₆ alkylsulfonyl, Ci-Cg-alkylsulfoxyl, C -Cg-cycloalkyl, Cx-Cg-alkoxy, Cι-C ₆ -haloalkoxy, Ci-Cg-alkyl oxycarbonyl, C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -alkylammo, D 1 -C 8 -Cg-alkylammo, C ₁ -C ₆ -alkylammocarbonyl,

Dι-Cι-Cg-alkylammocarbonyl, Cι-Cg-alkylammothιo- carbonyl, di-Ci-Cg-alkylmothiocarbonyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio , Hetaryl, hetaryloxy, hetarylthio or C (= NOR ⁷ ) -A _n -R ⁸ ;

Aryl, arylcarbonyl, arylsulfonyl, hetaryl, hetarylcarbonyl or hetarylsulfonyl, where these residues can be partially or completely halogenated or can carry one to three of the following groups:

Cyano, Nitro, Hydroxy, Mercapto, Ammo, Carboxyl, Ammocarbonyl, Ammothiocarbonyl, Halogen, Ci-Cg-Alkyl, Cι-C ₆ -Halogenalkyl, Cι-C ₆ -Alkylcarbonyl, Ci-Cg-Alkyl- sulfonyl, Ci-Cg- Alkylsulfoxyl, C -C ₆ cycloalkyl, Ci-Cg-alkoxy, Ci-Cg-haloalkoxy, Ci-Cg-alkyloxy-carbonyl, Cι-Cg-alkylthio, Ci-Cg-alkylammo, Dι-Cι-Cg-alkylammo, Ci -Cg-alkylammocarbonyl, Dι-Cι-Cg-alkyl - ammocarbonyl, Ci-Cg-alkylammothiocarbonyl, Dι-Cι-Cg-alkylam othiocarbonyl, C ₂ -Cg-alkenyl, C ₂ -Cg-alkenyl - oxy, benzyl, benzyloxy, Aryl, aryloxy, hetaryl,

Hetaryloxy or C (= NOR ⁷ ) -A _n -R ⁸ ;

Hydrogen,

Ci-Cg-Alkyl, C ₂ -Cg-Alkenyl, C ₂ -Cg-Alkmyl, whereby the

Hydrocarbon radicals of these groups can be partially or completely halogenated or one to 3 can carry three of the following radicals: cyano, nitro, hydroxy, mercapto, amino, carboxyl, ammocarbonyl, ammothiocarbonyl, halogen, Ci-Cg-alkylaminocarbonyl, di-Ci-Cg-alkylaminocarbonyl, Ci-Cg-alkylaminothio-carbonyl, di- Ci-Cg-alkylaminothiocarbonyl, Ci-Cg-alkylsulfonyl, Ci-Cg-alkylsulfoxyl, Ci-Cg-alkoxy, Cχ-Cg-haloalkoxy, Ci-Cg-alkoxycarbonyl, Ci-Cg-alkylthio, Ci-Cg-alkylamino, Di-Ci-Cg-alkylamino, C ₂ -Cg-alkenyloxy, C -Cg-cycloalkyl, C ₃ -Cg-cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, aryl -CC -alkoxy,

Arylthio, aryl -CC -alkylthio, hetaryl, hetaryloxy, hetaryl -CC -alkoxy, hetarylthio, hetaryl -CC-C ₄ -alkyl - thio, where the cyclic radicals in turn can be partially or completely halogenated and / or one can carry up to three of the following groups:

Cyano, Nitro, Hydroxy, Mercapto, Amino, Carboxyl, Ammocarbonyl, Ammothiocarbonyl, Ci-Cg-Alkyl, Ci-Cg-Haloalkyl, Ci-Cg-Alkylsulfonyl, Ci-Cg-Alkylsulfoxyl, C ₃ Cg-Cycloalkyl, Ci-Cg- Alkoxy, Ci-Cg-haloalkoxy, Ci-Cg-alkoxycarbonyl, Ci-Cg-alkylthio, Ci-Cg-

Alkyla ino, di-Ci-Cg-alkylamino, Ci-Cg-alkylamino-carbonyl, di-Ci-Cg-alkylaminocarbonyl, Ci-Cg-alkylamino-thiocarbonyl, di-C-Cg-alkylaminothiocarbonyl, C ₂ -Cg-alkenyl, C ₂ -Cg alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio and C (= NOR ⁷ ) -A _n -R ⁸ ;

C ₃ -Cg cycloalkyl, C ₃ -Cg cycloalkenyl, heterocyclyl, aryl, hetaryl, where the cyclic radicals can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, Carboxyl, amino-carbonyl, aminothiocarbonyl, halogen, Ci-Cg-alkyl, Ci-Cg-haloalkyl, Ci-Cg-alkylsulfonyl, Ci-Cg-alkylsulfoxyl, C ₃ -Cg-cycloalkyl, Ci-Cg-alkoxy, Ci -Cg-haloalkoxy, Ci-Cg-alkoxycarbonyl, Ci-Cg-alkylthio, Cι ~ Cg- alkylamino, di-Ci-Cg-alkylamino, Ci-Cg-alkylamino-carbonyl, di-Ci-Cg-alkylaminocarbonyl, Ci -Cg-alkyl aminothiocarbonyl, di-Ci-Cg-alkylaminothiocarbonyl, C -Cg-alkenyl, C ₂ -Cg-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl and hetaryloxy;

in which represents oxygen, sulfur or nitrogen and the nitrogen carries hydrogen or Ci-Cg-alkyl;

n represents 0 or 1;

R ^{7 is} hydrogen or Ci-Cg-alkyl and

R ⁸ denotes hydrogen or Ci-Cg-alkyl,

and their salts,

and

b) at least one fungicide selected from fungicides of the formulas II to V

^^ N ^'' N

(II)

O ^' o ^'

CN, OMe

CH ₃ 0 ₂ C

; ιιi)

- ^ ^^

(IV)

O ^'

CH ₃ NH .OMe

N '

O (V)

.0.

^* CH,

The object of the present invention was to provide fungicidal mixtures which have a good fungicidal action which goes beyond the effectiveness of the mixture components, in particular against rice fungal diseases.

This object is achieved according to the invention by the mixtures according to claim 1.

The compounds of formula I are known per se and are described in the literature (WO 97/15552).

The fungicides of the formulas II to V are also known and described in the literature. In addition, they may be commercially available under the trade names given below in brackets:

II: Common name: Azoxystrobm (trade name: Amistar®, Zeneca)

III: EP-A 253,313, common name: Kresoxim-methyl (trade name Bπo®, from BASF)

IV: EP 398,692, proposed common name: Metommostrobm (development code SSF-126, Shionogi);

V: EP 398.692, CAS RN 162535-21-9, SSF 129, Entwicklungspro ^¬ domestic product of the company Shionogi & Co., Ltd.).

Due to their C = C and C = N double bonds, the compounds I can be produced as E / Z isomer mixtures which, for example, the individual compounds can be separated by crystallization or chromatography in the usual way.

If the synthesis of isomers occurs in the synthesis, a separation is generally not absolutely necessary, since the individual isomers are partially separated during processing 6 can convert the application into one another (e.g. under the influence of light, acid or base). Corresponding conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful fungus or animal pest to be controlled.

With regard to the C = X double bond, the E isomers of the compounds I are preferred in terms of their activity (configuration based on the -OCH ₃ or the -CH ₃ group in relation to the -CO ₂ R ¹ group).

With regard to the -C (R ³ ) = NOCH ₂ double bond, the cis isomers of the compounds I are preferred in terms of their activity (configuration based on the radical R ³ in relation to the -OCH ₂ group).

In the definitions of the compounds I given at the outset, collective terms were used which are generally representative of the following groups:

Halogen: fluorine, chlorine, bromine and iodine;

Alkyl: straight-chain or branched alkyl groups with 1 to 4, 6 or 10 carbon atoms, e.g. Ci-Cg-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 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, 1,2-trimethylpropyl, 1, 2, 2-trimethylpropyl, 1-ethyl-l-methylpropyl and 1-ethyl- 2-methylpropyl;

Haloalkyl: straight-chain or branched alkyl groups having 1 to 6 carbon atoms, wherein the hydrogen atoms constantly may be substituted as mentioned above by halogen atoms in these groups to be partially or fully ^¬ such as Cι-C ₂ -haloalkyl such as chloro ^¬ methyl, dichloromethyl, trichloromethyl, fluoromethyl, Difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoroethyl,

Chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2, 2-dichloro-2- fluoroethyl, 2, 2, 2-trichloroethyl and pentafluoroethyl; 7

Cycloalkyl: monocyclic alkyl groups with 3 to 6 carbon ring members, e.g. Cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;

Alkenyl: straight-chain or branched alkenyl groups with 2 to 6 or 10 carbon atoms and a double bond in any position, e.g. C -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, 1-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, l-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, l-dimethyl-2-propenyl, 1, 2-dimethyl-l-propenyl, 1, 2- Dimethyl-2-propenyl, 1-ethyl-l-propenyl, l-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-l-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, 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, l-dimethyl-2-butenyl, 1, l-dimethyl-3-butenyl, 1, 2-dimethyl-l- 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-1-butenyl, 1-ethyl-2-butenyl, 1-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-methyl-2-propenyl;

Alkynyl: straight-chain or branched alkynyl groups with 2 to 10 carbon atoms and a triple bond in any position, for example C ₂ -C 6 -alkynyl such as ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl , 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 1, l-dimethyl-2-propynyl, l-ethyl -2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, l-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3 pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1, l-dimethyl-2-butynyl, 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-l-methyl-2 -propinyl; 8th

Heterocyclyl or heterocyclyloxy, heterocyclylthio and heterocyclyllamino: three- to six-membered, saturated or partially unsaturated mono- or polycyclic heterocycles, which contain one to three herero atoms selected from a group consisting of oxygen, nitrogen and sulfur, and which directly or . (Heterocyclyloxy) via an oxygen atom or (Heterocyclylthio) via a sulfur atom or (Heterocyclyla ino) via a nitrogen atom are bound to the skeleton, such as 2-tetrahydrofuran, oxiranyl, 3-tetrahydrofranyl, 2-tetrahydrothienyl, _ 3 - Tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazoledinyl, 4 -isoxazolidinyl, 5-isoxazolidinyl, 3 -isothiazolidinyl, 4 -isothiazolidinyl, 5 -isothiazolidinyl, 3 -pyrazolidinyl, 4 -pyrazolidinyl, 5 - pyrazolidinyl Oxazolidinyl, 4 -oxazolidinyl, 5 -oxazolidinyl, 2 -thiazolidinyl, 4 -thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4 -I idazolidinyl, 1,2,4-oxadiazolidin-3 -yl, 1,2 , 4-oxadiazolidin-5 -yl, 1,2,4-thiadiazolidin-3-yl, l, 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-tri-azolidin-2 -yl, 2, 3 -dihydrofur-2 -yl, 2, 3 -dihydrofur- 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 -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-dihydropyrrole-2-yl, 2,3-dihydropyrrole -3-yl, 2,3-dihydropyrrole -4-yl, 2,3-dihydropyrrole- 5 -yl, 2, 5 -dihydropyrrole -2 -yl, 2,5-dihydropyrrole-3 -yl, 2,3 -dihydroisoxazole -3 -yl, 2, 3 -dihydroisoxazole -4 -yl, 2, 3 - Dihydroisoxazole -5 -yl, 4, 5 -Dihydroisoxazol - 3 -yl, 4, 5 -Dihydro ^¬ isoxazol -4 -yl, 4, 5 -Dihydroisoxazol -5 -yl, 2, 5 -Dihydroisothia- zol -3 -yl, 2,5-dihydroisothiazole -4 -yl, 2,5-dihydroisothiazole -5 -yl, 2,3-dihydroisopyrazole -3 -yl, 2, 3 -dihydroisopyrazole -4 -yl, 2,3-dihydroisopyrazole -5 -yl, 4, 5 -Dihydroisopyrazol - 3 -yl, 4, 5 -Dihydroisopyrazol -4 -yl, 4, 5 -Dihydroisopyrazole -5 -yl, 2, 5 -Dihydroisopyra ^¬ zol -3 -yl, 2, 5 -Dihydroisopyrazol -4 -yl, 2, 5 -Dihydroisopyrazol -5 -yl, 2, 3 -Dihydrooxazol-3 -yl, 2 , 3-dihydrooxazole -4 -yl, 2,3-dihydro-oxazol-5-yl, 4,5 -dihydrooxazole -3 -yl, 4,5 -dihydrooxazole -4 -yl, 4,5 -dihydrooxazole -5 -yl , 2, 5-dihydrooxazol - 3 -yl, 2,5-dihydro-oxazol-4-yl, 2, 5 -dihydrooxazol - 5 -yl, 2, 3 -dihydrothiazol-2 -yl, 2, 3 -dihydrothiazol-4 -yl, 2, 3 -dihydrothiazole - 5 -yl, 4,5-dihydro-thiazole -2 -yl, 4, 5 -dihydrothiazole -4 -yl, 4, 5 -dihydrothiazole -5 -yl, 2, 5 -dihydrothiazole -2 -yl, 2, 5 -dihydrothiazole -4 -yl, 2, 5 -dihydrothiazole -5 -yl, 2,3 -dihydroimidazol-2 -yl, 2, 3 -dihydroimidazole -4 -yl, 2, 3 -dihydroimidazole -5 -yl, 4, 5 -dihydroimidazole -2 -yl, 4, 5 -dihydroimidazole -4 -yl, 4, 5 -dihydroimidazole -5 -yl, 2, 5 -dihydroimidazol - 2-yl, 2, 5 -dihydroimidazole -4 -yl, 2, 5 -dihydroimidazole - 5 -yl, 2-morpholinyl, 3-morpholinyl, 2-piperidinyl, 3-piperidinyl,

4 - piperidinyl, 3-tetrahydropyridazinyl, 4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl, 5-tetrahydro- 9 pyrimidinyl, 2-tetrahydropyrazinyl, 1,3,5-tetrahydrotriazin-2 -yl, 1,2,4-tetrahydrotriazin-3 -yl, 1,3-dihydrooxazin-2 -yl, 1,3-dithian-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-benzothiazine-2 -yl, 1, l-dioxo-2, 3,4,5-tetrahydrothien-2 -yl, 2H-1, 4-benzothiazin-3 -yl, 2H-1, 4-benzoxazin-3 -yl, 1,3 Dihydro-oxazin-2-yl, 1,3-dithian-2-yl,

Aryl or aryloxy, arylthio, arylcarbonyl and arylsulfonyl: aromatic mono- or polycyclic hydrocarbon radicals which directly or (aryloxy) via an oxygen atom (-0-) or (arylthio) a sulfur atom (-S-), (arylcarbonyl) via a carbonyl group (-CO-) or (arylsulfonyl) are bonded to the skeleton via a sulfonyl group (-S0 -), for example Phenyl, naphthyl and phenanthrenyl or phenyloxy, naphthyloxy and phenanthrenyl - oxy and the corresponding carbonyl and sulfonyl radicals;

Hetaryl or hetaryloxy, hetarylthio, hetarylcarbonyl and hetarylsulfonyl: aromatic mono- or polycyclic radicals which in addition to carbon ring members additionally one to four

Nitrogen atoms or one to three nitrogen atoms and an oxygen or a sulfur atom or an oxygen or a sulfur atom and which directly or (hetaryloxy) via an oxygen atom (-0-) or (hetarylthio) a sulfur atom (-S-), (Hetarylcarbonyl) via a carbonyl group (-CO-) or

(Hetarylsulfonyl) are attached to the skeleton via a sulfonyl group (-S0 ₂ -), for example

5-membered heteroaryl containing one to three nitrogen atoms: 5-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three nitrogen atoms as ring members, e.g. 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, l, 2,4-triazol-3-yl and 1, 3, 4-triazol-2- yl;

5-membered heteroaryl, containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen or one sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms and may contain a sulfur 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-pyrazolyi, 4-pyrazolyl, 5-pyrazolyl, 2-0xazolyl, 4-0xazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 10

5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2, 4-oxadiazol-3-yl, 1,2, 4-oxadiazol-5-yl, 1, 2, 4-thiadiazol-3-yl, l, 2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3 4-triazol-2-yl;

Benzo-fused 5-membered heteroaryl, containing one to three nitrogen atoms or one nitrogen atom and / or one oxygen or sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom or one oxygen atom. or can contain a sulfur atom as ring members, and in which two adjacent carbon ring members or a nitrogen and an adjacent carbon ring member can be bridged by a buta-1, 3-diene-1, 4-diyl group;

5-membered heteroaryl bonded via nitrogen, containing one to four nitrogen atoms, or benzo-fused 5-membered heteroaryl bonded via nitrogen, containing one to three nitrogen atoms: 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms as ring members may contain, and in which two adjacent carbon ring members or a nitrogen and an adjacent

Carbon ring member can be bridged by a buta-1, 3-diene-1, 4-diyl group, these rings being bonded to the framework via one of the nitrogen ring members;

6-membered heteroaryl containing one to three or one to four nitrogen atoms: 6-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three or one to four nitrogen atoms as ring members, e.g. 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-triazin-3-yl and 1,2,4,5-etrazi-3 -yl;

benzo-fused 6-membered heteroaryl containing one to four nitrogen atoms: 6-ring heteroaryl groups in which two adjacent carbon ring members can be bridged by a buta- 1, 3 -diene-1, 4 -diyl group, e.g. Quinoline, isoquinoline, quinazoline and quinoxaline,

or the corresponding oxy, thio, carbonyl or sulfonyl groups. 11

Hetarylammo: aromatic mono- or polycyclic radicals which, in addition to carbon members, can additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom and which are bonded to the structure via a nitrogen atom.

The specification should be "partially or fully halogenated" to bring pressure from ^¬ that in groups characterized thus, the hydrogen atoms can be replaced entirely as mentioned above, by identical or different halogen atoms or in part.

With regard to their biological action, preference is given to compounds of the formula I in which m is 0.

Equally preferred are compounds of the formula I in which R ^{1 is} methyl.

In addition, compounds I are preferred in which R ^{3 represents} hydrogen, cyano, cyclopropyl, methyl, ethyl, 1-methylethyl or CF ₃ .

In addition, compounds I are preferred in which R ^{3 is} methyl.

In addition, compounds I are preferred in which R ^{3 is} cyano.

Compounds I are furthermore preferred, in which R ^{3 represents} cyclopropyl.

Furthermore, compounds I are preferred in which R ^{3 is} CF ₃ .

Furthermore, preference is given to compounds I in which R ^{5 is} hydrogen, cyclopropyl, methyl, ethyl, isopropyl, optionally subst. Aryl or hetaryl is.

In addition, compounds I are preferred in which R ^{5 is} methyl.

Furthermore, compounds I are preferred in which R ^{5 is} ethyl.

In addition, compounds I are preferred in which R ^{5 is} isopropyl. 12

In addition, compounds I are preferred in which R ^{5 is} cyclopropyl.

In addition, compounds I are preferred in which R ^{5 is} CF.

Furthermore, compounds I are preferred in which R ⁵ for optionally subst. Aryl or hetaryl is.

Furthermore, compounds I are preferred in which R ⁵ for optionally subst. Pyridyl, pyrimidyl, pyrazinyl, pyridazinyl or triazinyl.

Furthermore, compounds I are preferred in which R ⁵ for optionally subst. Furyl, thienyl or pyrrolyl.

Furthermore, compounds I are preferred in which R ⁵ for optionally subst. Oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl or imidazolyl.

Furthermore, compounds I are preferred in which R ⁵ for optionally subst. Oxdiazolyl, thiadiazolyl or triazolyl.

In addition, compounds I are preferred in which R ^{5 is} phenyl which is unsubstituted or carries one or two of the following groups: nitro, cyano, hydroxy, amino, ammocarbonyl, ammothiocarbonyl, halogen, C 1 -C 4 alkyl, C 1 -C 4 Haloalkyl, -C-C alkoxy, -C-C -halalkalkoxy, C -C -alkylamino, di-Cι-C - alkylamino, Cι-C -alkylsulfonyl, Cι-C -alkoxycarbonyl, Cι-C -alkyl- aminocarbonyl or di- -CC alkylaminocarbonyl.

In addition, compounds I are preferred in which R ^{4 represents} hydrogen, Ci-Cg-alkyl, C ₂ -Cg -alkenyl, C ₂ -C -alkynyl, allyl, arylalkyl, hetarylalkyl, aryloxyalkyl, hetaryloxyalkyl, aryl or hetaryl.

Furthermore, compounds I are preferred in which R ^{4 is} Ci-Cg-alkyl.

Further preferred compounds I can be found in WO 97 / 15,552.

The compounds I contained in the mixtures according to the invention are distinguished by an outstanding action against a broad spectrum of phytopathogenic fungi, in particular against 13

Mushrooms from the classes of Ascomycetes, Deuteromycetes, Phycomycetes and Basisiomycetes.

They are particularly important for combating a large number of fungi on various crops such as cotton, vegetables (e.g. cucumbers, beans, tomatoes, potatoes and squashes), barley, grass, oats, bananas, coffee, corn, fruit plants, rice, rye, soy , Wine, wheat, ornamental plants, sugar cane and a variety of seeds.

They are particularly suitable for combating the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on squash plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizo species Rice and lawn, Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthospori - um species on cereals, Septoria nodorum on wheat, Botrytis cinera (gray mold) on strawberries, vegetables, ornamental plants and vines, cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, Pseudoperonospora species in hops and cucumbers, Alternaria species on vegetables and fruit, Mycosphaerella species in Ba nanen and Fusarium and Verticillium species.

The compounds II to V are commercially available as fungicides.

Preferably employed in the preparation of the mixtures the pure active compounds I and II to V, where th further active ingredients against harmful fungi or against other pests, such as Insek ^¬, arachnids or nematodes, or else herbicidal or growth-regulating active compounds or fertilizers.

The mixtures of the compounds I and at least one compound II to V can be used simultaneously, together or separately and are distinguished by an excellent action against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes out. Some of them are systemically effective and can therefore also be used as leaf and soil fungicides. 14

They are particularly important for combating a large number of mushrooms on various crops such as cotton, vegetables (eg cucumber, beans, tomatoes, potatoes and squashes), barley, grass, oats, bananas, coffee, corn, fruit plants, rice, rye , Soy, who, wheat, ornamental plants, sugar cane and a variety of seeds.

They are particularly suitable for combating the following phytopathogenic fungi: Erysiphe grammis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuligmea on pumpkin plants, Podosphaera leucotricha on apples, Uncmula necator on vines, Puccmia cotton on cereals, Rhizo species Rice and lawn, üstilago species on cereals and sugar cane, Venturia maequalis (scab) on apples, Helm thosporium species on cereals and rice, Septoπa nodorum on wheat,

Botrytis cmera (gray mold) on strawberries, vegetables, ornamental plants and vines, Cercospora arachidicola on peanuts, Pseudo-cercosporella herpotπchoides on wheat and barley, Pyπcularia oryzae on rice and lawn, Phytophthora festans on potatoes and tomatoes, Plasmopara viticoperonosa on vines, Pseudo - in hops and cucumbers, Alternaria species in vegetables and fruits, Mycosp aerella species in bananas and Fusarium and Verticillium species.

The mixtures according to the invention can be used particularly preferably for controlling Pyπcularia oryzae.

The compounds I and at least one of the compounds II to V can be applied simultaneously, that is jointly or separately, or in succession, the sequence in the case of separate application generally not having any effect on the control success.

The application rates of the inventive mixtures are, in particular in agricultural crop surfaces, depending on the nature of the effect desired ge ^¬ from 0.01 to 8 kg / ha, preferably 0.1 to 5 kg / ha, in particular 0.5 to 3.0 kg /Ha.

The application rates for the compounds I are 0.01 to 2.5 kg / ha, preferably 0.05 to 2.5 kg / ha, in particular 0.1 to 1.0 kg / ha.

The application rates for the compounds II to V are accordingly 0.001 to 5 kg / ha, preferably 0.005 to 2 kg / ha, ms - particularly 0.01 to 1.0 kg / ha. 15

In the case of seed treatment, application rates of mixture of 0.001 to 250 g / kg of seed, preferably 0.01 to 100 g / kg, in particular 0.01 to 50 g / kg, are generally used.

If pathogenic harmful fungi are to be combated for plants, the separate or joint application of the compounds I and at least one of the compounds II to V is carried out by spraying or dusting the seeds, the plants or the soil before or after the plants have been sown or before or after the Emergence of plants.

The fungicidal synergistic mixtures according to the invention can be prepared, for example, in the form of directly sprayable solutions, powders and suspensions or in the form of high-strength aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules and by spraying, atomizing , Dusting, scattering or pouring. The form of application depends on the intended use; in any case, it should ensure that the mixture according to the invention is as fine and uniform as possible.

The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, where in the case of water as diluent other organic solvents can also be used as auxiliary solvents. The following are essentially considered as auxiliary substances: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine , Dimethylformamide) and water; Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.

The surface-active substances are the alkali, alkaline earth, and ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl and fatty alcohol sulfates, and salts of sulfated hexa -, hepta- and octadecanols or fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or,. the 16

Naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol or tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol - ethylene oxide condensates, ethoxylated alkoxylated alcohol, polyoxyethylene oxylacetyl ether, polyoxyethylene oxylacetyl ether, polyoxyethylene oxylacetyl ether, polyoxyethylene oxylacetyl ether, polyoxyethylene oxylacetyl ether, polyoxyethylene oxyethyl ether -Sulfite waste or methyl cellulose into consideration.

Powder sprinklers and dusts can be prepared by mixing or jointly grinding the compounds I and at least one of the compounds II to V or the mixture of the compounds I and at least one compound II to V with a solid carrier.

Granules (e.g. coating, impregnation or homogeneous granules) are usually produced by binding the active ingredient or ingredients to a solid carrier.

Mineral soils such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, boluses, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics and fertilizers are used as fillers or solid carriers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

The formulations generally contain from 0.1 to 95 wt .-%, preferably 0.5 to 90 wt .-% of one of the compounds I and min ^¬ least one of the compounds II to V or the mixture of the compounds I and at least one of the compounds II to V. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR or HPLC spectrum).

The corresponding formulations are used in such a way that the harmful fungi, their habitat or the plants, seeds, soils, surfaces, materials or spaces to be kept free of them are mixed with a fungicidally effective amount of the mixture or of the compounds I and at least one of the compounds II to IV for separate application.

The application can take place before or after infestation by the harmful fungi. 17

Examples of such preparations that contain the active ingredients are:

I. a solution of 90 parts by weight of the active ingredients and 10 parts by weight of N-methylpyrrolidone, which is suitable for use in the form of tiny drops;

II. A mixture of 20 parts by weight of the active ingredients, 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid , 5th

Parts by weight of the adduct 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 adduct 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 with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide 1 mole of castor oil;

V. a mixture, ground in a hammer mill, of 80 parts by weight of the active ingredients, 3 parts by weight of the sodium salt of diisobutylnaphthalene-1-sulfonic acid, 10 parts by weight of the sodium salt of lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of powder Silica gel; by fei ^¬ nes distributing the mixture in water gives a spray mixture; VI. an intimate mixture of 3 parts by weight of the active ingredients and 97 parts by weight of finely divided kaolin; this dust contains 3% by weight of 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 preparation gives the active ingredient good adhesion;

VIII. A stable aqueous dispersion of 40 parts by weight of the active ingredients, 10 parts by weight of the sodium salt of a phenol-sulfonic acid-urea-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water, which is further diluted can be;

IX. a stable oily dispersion of 20 parts by weight of the active ingredients, 2 parts by weight of the calcium salt of dodecylbenzene sulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid urine 18 substance-formaldehyde condensates and 88 parts by weight of a paraffinic mineral oil.

The synergistic effect of the mixtures according to the invention can be demonstrated by the following experiments:

The active ingredients are prepared separately or together as a 10% emulsion in a mixture of 63% by weight cyclohexanone and 27% by weight emulsifier and diluted with water in accordance with the desired concentration.

The evaluation is carried out by determining the affected leaf areas in percent. These percentages are converted into efficiencies. Efficiency (W) is determined using Abbot's formula as follows:

W = (1 - α) -100 / ß

α corresponds to the fungal attack of the treated plants in% and ß corresponds to the fungal attack of the untreated (control) plants in%

With an efficiency of 0, the infection of the treated plants corresponds to that of the untreated control plants; at an efficiency of 100, the treated plants showed no infection.

The expected efficacies of active compound mixtures were [15 RS Colby, Weeds, 20-22 (1967)] according to the Colby formula ermit ^¬ telt and compared with the observed efficacies.

Colby formula: E = x + y - x-y / 100

E expected efficiency, expressed in% of the untreated control, when using the mixture of active ingredients A and B in concentrations a and bx the efficiency, expressed in% of the untreated control, when using active ingredient A in concentration ay, the efficiency, expressed in% of the untreated control when using the active ingredient B in the concentration b

Example of use 1 - Activity against Pyricularia oryzae (protective) 19

Leaves of "Tai-Nong 67" rice seedlings grown in pots were sprayed to runoff point with aqueous active compound preparation which was prepared with a stock solution of 10% active compound, 63% cyclohexanone and 27% emulsifier. The following day, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The test plants were then placed in climatic chambers at 22-24 ° C and 95-99% relative humidity for 6 days. The extent of the development of the infestation on the leaves was then determined visually

The visually determined values for the percentage of leaf areas affected were converted into efficiencies as% of the untreated control. Efficiency 0 is the same as in the untreated control, efficiency 100 is 0%. The expected efficacies for combinations of active substances were determined using the Colby formula (Colby, S.R. (Calculating synergistic and antagonistic responses of herbicide combinations ", Weeds, 15, pp. 20-22, 1967) and compared with the observed efficacies.

The following compound I 'was used as component a):

H ₃ C-

_/ O-CH,

The results of the tests are shown in Tables 1 and 2 below:

Table 1:

For example, active ingredient conc in ppm efficiency in% of unhindered control

IV without (100% infestation) 0

2V connection I '2.0 20 0.5 0

3V connection II 0.5 20 (common name: Azoxystrobin)

4V connection III 2.0 0

(common name: Kre- 0.5 0 soxim-methyl)

20th

Table 2

For example, the mixture of calculated calculated (conc. In ppm) efficiency according to the invention efficiency *

5 0.5 ppm 1 + 0.5 ppm II 40 20

6 2 ppm 1 + 2 ppm III 80 20

7 0.5 ppm 1 + 0.5 ppm III 20 0

calculated according to the Colby formula

The results of the tests show that the observed efficiency in all mixing ratios is higher than the efficiency calculated according to the Colby formula.

Claims

21 patent claims

1 . Mixtures for plant protection, containing as active components

a) Phenylacetic acid derivatives of the formula I.

(I)

m where the substituents and the index have the following meaning:

X STILL ₃ , CHOCH ₃ , CHCH ₃ ;

Y 0, NO

R ^ R independently of one another hydrogen and Cι ~ C alkyl;

R ² cyano, nitro, trifluoromethyl, halogen, -C ~ alkyl and -C -C alkoxy;

R ^{3 is} hydrogen, cyano, -CC alkyl, -C -C halogen alkyl, C ₃ -C ₆ cycloalkyl;

R ⁴ , R ^{6 are} independently hydrogen,

-C-Cιo-alkyl, C -C ₆ -cycloalkyl, C ₂ -Cιo-alkenyl, C -Cιo-alkmyl, Cι-Cιo-alkylcarbonyl,

C ₂ -Co-alkenylcarbonyl, C ₃ -C o-alkmylcarbonyl or Cι-Cιo-alkylsulfonyl, where these residues can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, Ammo,

Carboxyl, ammocarbonyl, ammothiocarbonyl, halogen, Ci-Cg-alkyl, Ci-Cg-haloalkyl, 22

Ci-Cg-alkylsulfonyl, Ci-Cg-alkylsulfoxyl, Ci-Cg-alkoxy, Ci-Cg-haloalkoxy, Cι ~ Cg-alkoxy-carbonyl, Ci-Cg-alkylthio, Ci-Cg-alkylamino, di-Ci-Cg- alkylamino,

Ci-Cg-alkylaminocarbonyl, di-Ci-Cg-alkylamino-carbonyl, Ci-Cg-alkylaminothiocarbonyl, di-Ci-Cg-alkylaminothiocarbonyl, C -Cg-alkenyl, C ₂ -Cg-alkenyloxy, C ₃ -Cg-cycloalkyl, C ₃ -Cg-Cycloalky- _ loxy, heterocyclyl, heterocyclyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio, where the cyclic groups can in turn be partially or completely halogenated or can carry one to three of the following groups : Cyano, Nitro,

Hydroxy, mercapto, amino, carboxyl, ammocarbonyl, aminothiocarbonyl, halogen, Ci-Cg-alkyl, Ci-Cg-haloalkyl, Ci-Cg-alkylsulfonyl, Ci-Cg-alkylsulfoxyl, C ₃ -Cg-cycloalkyl, Ci-Cg-alkoxy , Ci-Cg-haloalkoxy, Ci-Cg-alkyloxycarbonyl, Ci-Cg-alkylthio, Ci-Cg-alkylamino, di-Ci-Cg-alkylamino, Ci-Cg-alkylaminocarbonyl, di-Ci-Cg-alkylaminocarbonyl , Ci-Cg-alkylaminothiocarbonyl, di-Ci-Cg-alkylaminothiocarbonyl, C -Cg alkenyl, C ₂ -Cg alkenyloxy, benzyl, benzyloxy, aryl, aryloxy,

Arylthio, hetaryl, hetaryloxy, hetarylthio or C (= NOR ⁷ ) -A _n -R ⁸ ;

Aryl, arylcarbonyl, arylsulfonyl, hetaryl, hetarylcarbonyl or hetarylsulfonyl, these being

Radicals can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, ammocarbonyl, aminothiocarbonyl, halogen, Ci-Cg-alkyl, Ci-Cg-haloalkyl,

Ci-Cg-alkylcarbonyl, Ci-Cg-alkylsulfonyl, Ci-Cg-alkylsulfoxyl, C-Cg-cycloalkyl, Ci-Cg-alkoxy, Ci-Cg-haloalkoxy, Ci-Cg-alkyloxycarbonyl, Ci-Cg-alkylthio, Ci Cg-alkylamino, di-Ci-Cg-alkylamino, Ci-Cg-alkylaminocarbonyl, di-Ci-Cg-alkylaminocarbonyl, Ci-Cg-alkylaminothiocarbonyl, di-Ci-Cg-alkylaminothiocarbonyl, C -Cg-alkenyl, C ₂ -Cg alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy or C (= NOR ⁷ ) -A _n -R ⁸ ;

Hydrogen, 23

Ci-Cg-alkyl, C ₂ -Cg-alkenyl, C -Cg-alkmyl, where the hydrocarbon radicals of these groups can be partially or completely halogenated or can carry one to three of the following radicals: cyano, nitro, hydroxy, mercapto, Am o Carboxyl

Ammocarbonyl, ammothiocarbonyl, halogen, Ci-Cg-alkylammocarbonyl, Dι-Cι-Cg-alkylammocarbonyl, Ci-Cg-alkylammothiocarbonyl, Dι-Cι-Cg-alkylammothiocarbonyl, Ci-Cg-alkylsulfonyl, Ci-Cg-alkylsulfoxyl, Ci-Cg-alkoxy, Cι ~ Cg-

Haloalkoxy, Ci-Cg-alkoxycarbonyl, Cι ~ Cg-alkyl-thio, Cι ~ C -alkylammo, Dι-Cι-Cg-alkylammo, C ₂ -Cg-alkenyloxy, C ₃ -Cg-cycloalkyl, C ₃ -Cg-cycloalky - loxy, heterocyclyl, heterocyclyloxy, aryl, aryl - oxy, aryl-Cι ~ C ₄ -alkoxy, arylthio, aryl-Cι ~ C -alkyl - thio, hetaryl, hetaryloxy, hetaryl-Cι-C -alkoxy, hetarylthio, hetaryl- -CC alkylthio, where the cyclic radicals can in turn be partially or completely halogenated and / or can carry up to three of the following groups: cyano, nitro,

Hydroxy, Mercapto, Ammo, Carboxyl, Ammocarbonyl, Ammothiocarbonyl, Ci-Cg-Alkyl, Ci-Cg-Haloalkyl, Ci-Cg-Alkylsulfonyl, Ci-Cg-Alkylsulfoxyl, C ₃ Cg-Cycloalkyl, Ci-Cg-Alkoxy, Ci Cg-haloalkoxy, Ci-Cg-alkoxycarbonyl, Ci-Cg-alkylthio, Ci-Cg-

Alkylammo, Dι-Cι-Cg-alkylammo, Ci-Cg-alkylammocarbonyl, Dι-Cι-Cg-alkylammocarbonyl, Ci-Cg-alkyl ammothiocarbonyl, Dι-Cι-Cg-alkylammothιocarbonyl, C ₂ -Cg-alkenyl, C -Cg-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy,

Hetarylthio and C (= N0R ⁷ ) -A _n -R ⁸ ;

_C3 -CG-cycloalkyl, C ₃ -C cycloalkenyl, heterocyclyl, aryl, hetaryl, where the cyclic radicals may be partially or fully halogenated or NEN carry one to three of the following groups Kgs ^¬: cyano, nitro, hydroxy, mercapto, Ammo, carboxyl, ammocarbonyl, ammothiocarbonyl, halogen, Ci-Cg-alkyl, Ci-Cg-haloalkyl, Ci-Cg-alkyl-sulfonyl, Ci-Cg-alkylsulfoxyl, C ₃ -Cg-cycloalkyl,

Ci-Cg-alkoxy, Ci-Cg-haloalkoxy, Ci-Cg-alkoxy-carbonyl, Ci-Cg-alkylthio, Ci-Cg-alkylammo, Dι-Cι-Cg-alkylammo, Ci-Cg-alkylammocarbonyl, Dι-Cι- Cg-alkylammocarbonyl, Cι-Cg-alkylammothιocarbonyl, Dι-Cι-Cg-alkylammothιocarbonyl, 24

C -Cg alkenyl, C ₂ -Cg alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl and hetaryloxy;

in which

represents oxygen, sulfur or nitrogen and the nitrogen carries hydrogen or Ci-Cg-alkyl;

n represents 0 or 1;

R ^{7 is} hydrogen or Ci-Cg-alkyl and

R ⁸ denotes hydrogen or Ci-Cg-alkyl,

and their salts,

and

at least one compound of the formulas II to V

I II)

OMe

: ιιi)

! iv)

OMe

(V)

in a synergistically effective amount.

A fungicidal mixture as claimed in claim 1, which is conditioned in two parts, one part containing the compound I in a solid or liquid carrier and the other part at least one of the compounds II to V containing a solid or liquid carrier.

Process for combating harmful fungi, characterized in that the fungi, their habitat or the materials, plants, seeds, soil, areas or spaces to be protected against fungal attack are treated with a fungicidal mixture according to one of Claims 1 to 2, the application of the Compound I and at least one of the compounds II to V can be carried out simultaneously, that is together or separately, or in succession.

Process according to Claim 3, characterized in that the harmful fungi, their habitat or the plants, seeds, soil, areas, materials or spaces to be kept free by them are treated with 0.005 to 1 kg / ha of a compound I according to Claim 1.

A method according to claim 3, characterized in that the harmful fungi, their habitat or the plants, seeds, soil, surfaces, materials or 26

Spaces treated with 0.01 to 1 kg / ha of at least one of the compounds II to V according to claim 1.