EP1082009A1 - Fungicide mixtures based on triple oxime ether derivatives and insecticides - Google Patents

Abstract

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

Description

Fungicidal mixtures based on triple oxime ether derivatives and insecticides

description

The present invention relates to mixtures for controlling harmful fungi and insects which

a) Phenylacetic acid derivatives of the formula I.

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

X STILL ₃ , CHOCH ₃ or CHCH ₃ ;

Oxygen or NR;

R ^ R independently of one another hydrogen or C] _. -C alkyl;

R ² cyano, nitro, trifluoromethyl, halogen, -CC alkyl or -CC alkoxy;

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

R ³ hydrogen f, cyano, -CC alkyl, -C-C haloalkyl or C ₃ -C ₆ cycloalkyl;

R ⁴ , R ⁶ independently of one another hydrogen,

Cι-Cιo-alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₁₀ alkenyl, C -Cιo alkynyl, Cι-Cι ₀ -alkylcarbonyl, C ₂ -Cι ₀ -alkenyl - carbonyl, C3-Cχo-alkynylcarbonyl or -CC-alkyl sulfonyl, where these residues can be partially or completely halogenated or one to three of the following can carry the groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, Aminothio- carbonyl, halo, Cι-C ₆ -alkyl, C ₆ haloalkyl, Cι-C ₆ alkylsulfonyl, Cι-C ₆ alkylsulfoxyl, Cι-C ₆ -alkoxy, C ₆ haloalkoxy, _Cι-C6 alkoxycarbonyl, Cι-C ₆ -alkylthio, Cι-C ₆ alkylamino, di-Ci-COE-alkylamino, Ci- Cö-alkylaminocarbonyl, di-Cι-C ₆ -alkylaminocarbonyl, Ci-Cδ-alkylaminothiocarbonyl, di-Ci-Cö-alkylaminothio-carbonyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, C ₃ -C ₆ -Cycloalkyl, C ₃ -C ₆ -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 one can carry up to three of the following groups: cyano, nitro, hydroxy,

Mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci-Cö-alkyl, Cx-Cg-haloalkyl, Ci-Cθ-alkylsulfonyl, Ci-Cβ-alkylsulfoxyl, C ₃ -C ₆ cycloalkyl, Cι- C ₆ -alkoxy, -C-C ₆ -haloalkoxy, -C-C ₆ -alkyl-oxycarbonyl, Ci-C _δ -alkylthio, Ci-Cg-alkylamino,

Di-Ci-C _ß alkylamino, Ci-C _ö alkylaminocarbonyl, Di-Ci-Cg-alkylaminocarbonyl, Ci-Cg-alkylaminothiocarbonyl, di-Ci-Cg-alkylaminothiocarbonyl, C ₂ ~ C ₆ - alkenyl, C ₂ -C6-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, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen , C _ß -alkyl, C ₆ haloalkyl, Ci-Cβ alkyl-carbonyl, _Cι-C6 alkyl sulfonyl, Cι-C ₆ alkylsulfoxyl, C ₃ -C ₆ cycloalkyl,

Cι-C ~ ₆ alkoxy, Cι-C ₆ haloalkoxy, Ci-C _ö alkyloxy- carbonyl, Ci-CSS-alkylthio, Ci-Cβ alkylamino, di-Ci-Cδ- alkylamino, Ci-Cg-alkylaminocarbonyl, di -Ci-Cg-alkyl aminocarbonyl, Ci-Cg-alkylaminothiocarbonyl, di-Ci-C _δ - alkylaminothiocarbonyl, C ₂ -C ₆ alkenyl, C ₂ -C6 alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl , Hetaryloxy or C (= NOR ⁷ ) -A _n -R ⁸ ;

Hydrogen, C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, 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, amino, carboxyl, aminocarbonyl,

Aminothiocarbonyl, halogen, _Cι-C6 alkylaminocarbonyl, di-Cι-C ₆ alkylaminocarbonyl, Cι-C ₆ -Alkylaminothio- carbonyl, di-Ci-Cβ-alkylaminothiocarbonyl, C _ö alkyl sulfonyl, Cι-C ₆ -Alkylsulfoxyl, -CC ₆ alkoxy, -C- ₆ - haloalkoxy, -C- ₆ alkoxycarbonyl, -C- ₆ alkylthio,

C ₁ -C ₆ alkylamino, di-C ₁ -C ₆ alkylamino, C ₂ -C ₆ alkenyloxy, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, aryl Cx -alkoxy, arylthio, aryl-Cι-C -alkylthio, hetaryl, hetaryloxy, _{hetaryl-Cι-C4-alkoxy,} hetarylthio, hetaryl-Cι-C ₄ -alkylthio, where the cyclic radicals in turn may be partially or fully halogenated can be and / or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, Ci-Cβ-alkyl,

Cι-C ₆ haloalkyl, Cι-C ₆ alkylsulfonyl, Ci-C _δ alkyl- sulfoxyl, C ₃ C ₆ cycloalkyl, Cι-C ₆ -alkoxy, halo-C ₆ alkoxy, Ci-Cδ- Alkoxycarbonyl, Ci-Cβ-alkylthio, Cι-C ₆ - alkylamino, di-Ci-Cβ-alkylamino, Ci-Cβ-alkylamino-carbonyl, di-Ci-Cg-alkylaminocarbonyl, Ci-C _δ -alkyl- aminothiocarbonyl, di- Cι-C ₆ -alkylaminothiocarbonyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, hetarylthio and C (= NOR ⁷ ) -A _n -R ⁸ ;

C ₃ - C_ -Cycioalkyl, C ₃ -C ₆ -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, aminocarbonyl, aminothiocarbonyl, halogen, Ci-Cβ-alkyl, Ci-C _ö -haloalkyl, Ci-Ce-alkylsulfonyl, Cι-C ₆ alkyl sulfoxyl, C -C ₆ cycloalkyl, Cι-C ₆ alkoxy , -CC ₆ -haloalkoxy, -C-C ₆ -alkoxycarbonyl, -C-C ₆ -alkylthio, -C-C ₆ - alkylamino, di-Cι-C ₆ -alkylamino, Cι-C ₆ -alkylamino-carbonyl, Di -Ci-Cg-alkylaminocarbonyl, -C-C ₆ alkyl aminothiocarbonyl, di-Ci-Cg-alkylaminothiocarbonyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl and Hetaryloxy;

in which A stands for oxygen, sulfur or nitrogen and wherein the nitrogen carries hydrogen or -CC ₆ alkyl;

n represents 0 or 1;

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

R ^{8 is} hydrogen or -CC ₆ alkyl,

and their salts,

and

b) at least one insecticide selected from insecticides of the formulas II to XI

.N

0 ι ι ₊

The object of the present invention was to provide mixtures which, on the one hand, have a good fungicidal action, in particular against fungal diseases in rice, and at the same time have a good insecticidal action. Since pests are usually found in large numbers in the climatic regions in which rice is grown, a combination of fungicidal and insecticidal activity is desirable.

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

The compounds of formula I and their preparation are known per se and are described in the literature (WO 97/15,552).

The insecticides of formulas II to IX are also known and are described in the literature. They are also commercially available under the trade names below in brackets:

II: EP-A 192.060, common name: Imidacloprid (trade name: Ad ire ^®, Gaucho ^®, Bayer.);

III: Common name: Acetamiprid (trade name: Mospilan, Nipon Soda)

IV: CAS RN 120738-89-8, common name: nitenpyram (trade name: Bestgard ^®, from Takeda Chemicals.); V: Colliot et al., Proc. Br. Conf. Dis. 1992, 1, 29, common name: Fipronil (trade name: Regent, Rhone-Poulenc);

VI: US 3,474,170; US 3,474,171 and DE-C 1,493,646; Common name: C Caarrbboofuran (trade name Curaterr ^®, Bayer; Furadan ^®, from FMC.);

VII: Proc. .... Br Crop Prot Conf, 1979, Vol 2, 557, common name: carbosulfan (trade name: Marshall ^®, from FMC.);

VIII: FR-A 2,489,329; Proc. Int. Congr. . Plant Prot Loth, 1983, 2, 360, common name: benfuracarb (trade name:; Furacon ^®, Fa Siapa Chem Oncol ^®, from Otsuka...);

IX: CAS RN 111 988-49-9, common name: thiacloprid (development product from Bayer);

X: Proc. of the 1998 Brighton Conference "Pests and Diseases",

Vol. 1, pp. 21-26 (MTI 446, Mitsui);

XI: Proc. of the Brighton Conference on Pests and Diseases,

Vol. 1, pp. 27-36 (CGA 293 343, Novartis).

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

If isomer mixtures are obtained during the synthesis, however, a separation is generally not absolutely necessary, since the individual isomers can partially convert into one another during preparation for use or during use (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-Cβ-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-dimethylbucyl, 2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2, 2- Trimethylpropyl, i-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;

Haloalkyl: straight-chain or branched alkyl groups with 1 to 6 carbon atoms, in which groups the hydrogen atoms can be partially or completely replaced by halogen atoms as mentioned above, for example C ₁ -C ₂ -haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl , Trif luormethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodif luormethyl, 1-fluoroethyl, 2-fluoroethyl, 2, 2-difluoroethyl, 2, 2, 2-trif luorethyl, 2-chloro-2-f luorethyl, 2-chloro-2, 2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;

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

Alkenyl: straight-chain or branched alkenyl groups with 2 to 6 or 10 carbon atoms and a double bond in any position, for example C ₂ -C ₆ 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-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, 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- pentinyl, 2-methyl-4-pentinyl, 3-methyl-4-pentinyl, 4-methyl-2-pentinyl, 1, l-dimethyl-2-butinyl, 1, l-dimethyl-3-butinyl, 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, -

Heterocyclyl or heterocyclyloxy, heterocyclyl thio and heterocycliclamino: 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 (Heterocyclylamino) via a nitrogen atom are bound to the structure, such as, for example, 2-tecrahydrofuranyl, oxiranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydr 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4 -isoxazolidinyl, 5 -isoxazolidinyl, 3 -isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3 -pyrazolidinyl, 4 -pyrazolidinyl, 5 -pyrazolidinyl, 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 -yl, 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, -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-dihydro-thien-3-yl, 2,3-dihydrothien-4-yl, 2,3-dihydrothiene 5 -yl, 2, 5-dihydrothien-2-yl, 2, 5 -dihydrothien-3 -yl, 2,3-dihydropyrrol-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 -dihydroisoxazole-3 -yl, 4, 5 -dihydroisoxazole -4 -yl, 4, 5 -dihydroisoxazole -5 -yl, 2, 5-dihydroisothiazol-3-yl, 2,5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol -5-yl, 2,3-dihydroisopyrazol-3-yl, 2,3-dihydroisopyrazole-yl, 2 , 3-Dihydroisopyrazol-5-yl, 4, 5 -dihydroisopyrazol - 3 -yl, 4, 5 -dihydroiso - pyrazol-4-yl, 4, 5 -dihydroisopyrazol- 5-yl, 2, 5 -dihydroisopyrazole -3 -yl, 2, 5 -dihydroisopyrazole -4 -yl, 2, 5 -dihydroisopyrazole -5 -yi, 2, 3 -dihydrooxazol-3 -yl, 2, 3 -dihydrooxazole -4 -yl, 2,3-dihydrooxazole -5-y 1,5-dihydrooxazole -3 -yl, 4,5-dihydrooxazole -4 -yl, 4,5-dihydrooxazole -5-yl, 2,5-dihydrooxazole - 3 -yl, 2,5-dihydro-oxazole- 4-yl, 2,5-dihydrooxazole -5 -yl, 2,3-dihydrothiazole -2-yl, 2,3-dihydrothiazole -4-yl, 2,3-dihydrothiazole - 5-yl, 4,5-dihydro thiazol-2-yl, 4,5-dihydrothiazole -4 -yl, 4,5-dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazole - 4 -yl, 2,5- Dihydro-thiazol-5-yl, 2,3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4,5-dihydroimidazol-2-yl, 4, 5-dihydroimidazole - -yl,, 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-tetrahydropyrimidinyl, 2-tetrahydropyrazinyl, 1,3,5-tetrahydrotriazin-2 -yl, 1,2,4-tetrahydrotriazine 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-benzothiazin-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-dithiane-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 (-SO ₂ -), 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: 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) via a sulfonyl group (-S0 ₂ -) are bound to the skeleton, 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, 1, 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- Pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2, 4-oxadiazo I- 3-yl, 1,2, 4-oxadiazol-5-yl, 1, 2, 4-thiadiazol-3-yl, 1, 2, 4-thiadiazol-5-yl, 1, 2, 4-triazol-3- yl,

1,3,4-oxadiazol-2-yl, 1,3,4-thiddiazoi-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 may contain a sulfur atom as ring members, and in which two adjacent carbon ring members or a nitrogen and an adjacent carbon ring member may be bridged by a buta-1, 3-diene-1, 4-diyl group;

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

Carbon ring member can be bridged by a buta-1, 3-diene-1, 4-diyl group, these rings being bonded to the device 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-tetrazin-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.

Hetarylamino: aromatic mono- or polycyclic radicals which, in addition to carbon ring 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 expression “partially or fully halogenated” is intended to express that the hydrogen atoms in the groups characterized in this way can be replaced in part or in full by the same or different halogen atoms as mentioned above.

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

Likewise preferred are compounds of 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.

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

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

Furthermore, compounds I are preferred 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.

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

In addition, compounds I are preferred in which R ^{5 is} CF ₃ .

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, aminocarbonyl, aminothiocarbonyl, halogen, Cχ-C -alkyl, Cι- C -haloalkyl, -C-C alkoxy, Cχ-C-haloalkoxy, C ₁ -C -alkylamino, di-Cι-C - alkylamino, C ₁ -C -alkylsulfonyl, Cι-C -alkoxycarbonyl, Cχ-C -alkyl- aminocarbonyl or Di-Cι-C-alkylaminocarbonyl.

In addition, compounds I are preferred in which R ^{4 represents} hydrogen, -CC ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, allyl, arylalkyl, hetarylalkyl, aryloxyalkyl, hetaryloxyalkyl, aryl or hetaryl .

Furthermore, compounds I are preferred in which R ^{4 is} C ₁ -C ₆ -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 fungi from the classes of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes.

They are of particular importance for combating a large number of fungi on various crops such as cotton, vegetable plants (eg cucumber, 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 pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia cotton species on cereal species, Rhiz , Rice and lawn, Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals and rice, Septoria nodorum on wheat, Botrytis cinera (gray mold) on strawberries, vegetables, ornamental plants and vines, Cercospora arachidicola on peanuts, Pseudo-cercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice and lawn, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, pseudoperon - ten in hops and cucumbers, Alternaria species in vegetables and fruits, Mycosphaerella species in bananas and Fusarium and Verticillium species.

The compounds of the formulas II to IX are used to control animal pests from the class of the insects, arachnids and nematodes. They can be used in crop protection as well as in the hygiene, storage protection and veterinary sectors to control animal pests. They are particularly suitable for controlling the following animal pests:

• Insects from the order of the butterflies (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argilla- cea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobone brumoneurumuraisumuraisumuraisumanaurumura, chorus unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Helithiothiothiothiella, Helithiothiothiothi, Helithium, Helithiothiothiothiothi, Helithiothiothiothi, Helithiothiothiothi, Helithiothiothiothiothi, Helithiothiothiothi, Helithiothiothi, Helithiothiothiothi, Helithiothiothiothi, Helithiothiothi undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersi- cella, Lambdina fiscellaria, Laphygma exigua, Leucoptera cof - feella, Leucoptera sciteila, Lithocolletis blancardella, Lobe- sia botrana, Licalidia triaxia triaxia triaxia, loxidia paria, Loxidia paria, Loxidia moniaxia triaxia, loxidia paria, Loxidia moniaxia triaxia Malacosoma neustria, Mamest ra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella,

Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula abso- luta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Trumocampidia nia, Thaumocampia- nia, Thaumocampia- poira phera canadensis,

• Beetles (Coleoptera), e.g. Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bru, Bruchus pis Byctiscus betulae, Cassida nebu- losa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-punc- tata, Diabrotica virgifera, Epilachna varivestis, Epitrix hir- tipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus commander, Meligethes aeneus, Melolonhynus, Melolontha melolonus chrysocephala, Phyllophaga sp., Phyl - lopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria,

• Two-winged (Diptera), e.g. Aedes aegypti, Aedes vexans, Anas- trepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macella- ria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pi piens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, fan- nia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata pectoral, Lyco- rica pomica, lyco- rica, lorica- rica, lalica- rorica p , Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami,

Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula ole-racea and Tipula paludosa,

Thrips (Thysanoptera), e.g. Frankliniella fusca, Frankiiniella occidentalis, Franklinielia tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,

Dermatoptera (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta,

Bugs (Heteroptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara quadrantulais, Pyanma viridula, Pies

Plant suckers (Homoptera), e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Ce-rosipha gossypii, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Empoasca fabae, Macrosiphum avenae, Macrosiaodumeodona Maconia phiumisodumophone, Macrosia diaumodis, Macrosia diumusumica, Macrosia diodiahumacophus, Macrosia diumusi Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sappaphis mala, Sap- paphis mali, Schizaphis graminum, Viz.

Termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus and Termes natalensis,

Straight wing aircraft (Orthoptera), e.g. Acheta domestica, Blatta orien- talis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melano- plus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguini-pes, Melanoplus spretus, Schomannacana america, Nomadascocata americana Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus,

Arachnoid such as arachnids (Acarina), e.g. Amblyomma america- num, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoeni-eis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyalundxnobinium, Hyalommxxusodusunc me- gnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllo- coptruta oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabieus, Tetranychus Tinnabarinus tawchychanyus, Tetranychany Tawchanyus, Tetranych

• Nematodes such as root-bile nematodes, eg Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, eg Globodera rostochiensis, Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolius, longica- lodum, undelongeluityu, stock- and leafelenchia dipsaci, Heliocotylenchus mul- ticinetus, Longidorus elongatus, Radopholus similis, Rotylen- chus robustus, Trichodorus primitivus, Tylenchorhynchus clay- toni, Tylenchorhynchus dubius, Pratylenchus neglectus, Praty- lenchusususatati curatusi, Praty- lenchususususatatiatusi, Praty- lusus penetraty curatus, Praty- lenchusususususatati curatusi, Praty- lenchusususususatati curatusi, Praty- lenchusususususatati curatus, Praty- undususususatansi. The amount of active ingredient used to control animal pests is generally from 0.01 to 2.0, preferably from 0.02 to 1.0, kg / ha under field conditions.

The mixtures according to the invention can particularly preferably be used to control plant diseases and insect pests in rice.

The compounds I and at least one of the compounds II to XI 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 mixtures according to the invention, especially for agricultural crop areas, are from 0.01 to 8 kg / ha, preferably 0.1 to 5 kg / ha, in particular 0.5 to 3.0 kg / ha, depending on the type of effect desired.

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.

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 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 XI or

Mixtures of the compounds I and at least one of the compounds II to IX by spraying or dusting the seeds, the plants or the soil before or after sowing the plants or before or after emergence of the plants.

The 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 can be applied. 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, for example by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, and in the case of water as diluent, other organic solvents can also be used as auxiliary solvents. The following are essentially considered as auxiliaries: 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 (eg kaolins, clays, talc, chalk) and synthetic stone powder (eg highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.

The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as from

Fatty acids, alkyl and alkyl aryl sulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as 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 naphthalene and phenol and sulfonic acids with phenol formaldehyde, Polyoxyethylenoctyl - Phenol, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenol or Tributylphenylpolyglycolether, alkylaryl polyglycol ether-isotridecylalcohol, Fettalkoholethylenoxid- con- condensates, ethoxylated castor oil, polyoxyethylene or Poiyoxypropylen, Laurylalkoholpolyglycoletheracetat, sorbitol esters, lignin-sulfite waste liquors or methylcellulose .

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

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

Mineral earths 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, serve, for example, as fillers or solid carriers. ground plastics, as well as fertilizers 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 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 XI or the mixture of the compounds I and at least one of the compounds II to XI. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR or HPLC spectrum).

The use of the compounds I and at least one of the compounds II to XI, the mixtures or the corresponding formulations takes place 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 with a fungicidally effective amount of the mixture, or of the compounds I and at least one of the compounds II to XI treated separately.

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

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, 5 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 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 a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of powder Silica gel; a spray mixture is obtained by finely distributing the mixture in water;

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 phenolsulfonic acid-urea-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water, which further dilutes 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-urea-formaldehyde condensate 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:

= (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 the active ingredient mixtures were calculated using the Colby formula [R.S. Colby, Weeds 15_, 20-22 (1967)] and compared with the observed efficiencies.

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)

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 combinations expected efficacies for Wirkstoffko were determined using Colby's formula (Colby, SR "Calculating synergistic and Toggle tagonistic 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):

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

Table 1

Table 2:

*> calculated according to the Colby formula

The results of the experiments show that the observed efficiency in all mixing ratios is higher than the efficiency calculated in advance using the Colby formula.

Claims

claims

1. Mixtures for crop protection, containing as active components

a) P enylacetic acid derivatives of the formula I.

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

X STILL ₃ , CHOCH ₃ or CHCH ₃ ;

Y is oxygen or NR;

R!, R independently of one another are hydrogen or C] _- C -alkyl;

R ² cyano, nitro, trifluoromethyl, halogen, -C ~ alkyl or -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, C] _- C alkyl, -C -C haloalkyl or C ₃ -C ₆ cycloalkyl;

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

Cι-Cιo-alkyl, C ₃ -C ₆ cycloalkyl, C -Cιo-alkenyl, C ₂ -Cιo-alkynyl, Cι-Cιo-alkylcarbonyl, C ₂ -Cιo-alkenylcarbonyl, C ₃ -Cιo-alkynylcarbonyl or Cι -Cχo-alkyl-sulfonyl, where these radicals can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci-Cβ-alkyl, Ci-C _ß -haloalkyl, Ci-C _ß -alkylsulfonyl, Cι-C ₆ -alkylsulfoxyl, Ci-Cg-alkoxy,

Cι-C ₆ haloalkoxy, Cι-C ₅ alkoxycarbonyl, Cι-C ₆ -alkylthio, Cι-C6-alkylamino, di-Ci-Cg-alkylamino, Ci-Cg-alkylaminocarbonyl, di-Ci-Cg-alkylaminocarbonyl, Ci-Cg-alkylaminothiocarbonyl, di-Ci-Cg-alkylaminothio-carbonyl, C ₂ -Cg-alkenyl, C -Cg-alkenyloxy, C ₃ -Cg-cyclo- alkyl, C ₃ -C ₆ 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, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci-Cg-alkyl , Ci-Cg-haloalkyl, Ci-C _ß- alkylsulfonyl, Cχ-Cg-alkylsulfoxyl, C ₃ -Cg-cycloalkyl, Ci-Cg-alkoxy, Cι-C ₆ -haloalkoxy, Ci-Cg-alkyloxycarbonyl, Ci-Cg-alkylthio, Ci-Cg-alkylamino, di-Ci-Cg-alkylamino, Cχ-Cg-alkylaminocarbonyl,

Di-Ci-Cg-alkylaminocarbonyl, Ci-Cg-alkylaminothiocarbonyl, di-Ci-Cg-alkylaminothiocarbonyl, C ₂ -Cg-alkenyl, C ₂ -Cg-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, Hetaryloxy, hetarylthio or C (= NO R 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, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci-C _ß- alkyl, Ci-Cg-haloalkyl, Ci-Cg-alkylcarbonyl, Ci-Cg-alkylsulfonyl, Ci-Cg-alkylsulfoxyl , C3-Cg-cycloalkyl, Ci-Cg-alkoxy, Ci-Cg-haloalkoxy, Ci-Cg-alkyloxycarbonyl, Ci-Cg-alkylthio, Ci-Cg-alkylamino, di-Cχ-Cg-alkylamino, Ci-Cg -Alkylaminocarbonyl, Di-Ci-Cg-Alkyl- aminocarbonyl, Ci-Cg-Alkylaminothiocarbonyl, Di-Ci-Cg-Alkylaminothiocarbonyl, C ₂ -Cg-Alkenyl, C ₂ -Cg-Alkenyloxy, 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-alkynyl, 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, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci-Cg-alkylaminocarbonyl,

Di-Ci-Cg-alkylaminocarbonyl, Ci-Cg-alkylaminothiocarbonyl, di-Ci-Cg-alkylaminothiocarbonyl, Cχ-Cg-alkyl- sulfonyl, Ci-Cg-alkylsulfoxyl, Ci-Cg-alkoxy, Ci-Cg-haloalkoxy, Ci-Cg-alkoxycarbonyl, Ci-Cg-alkylthio, Ci-Cg-alkylamino, di-Cχ-Cg-alkylamino, C ₂ -Cg Alkenyloxy, C ₃ -C _e -cycloalkyl, C ₃ -Cg-cycloalkyloxy, heterocyclyl, heterocyclyloxy, aryl, aryloxy, aryl -CC -alkoxy,

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

Cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, Ci-Cg-alkyl, Ci-Cg-haloalkyl, Ci-Cg-alkylsulfonyl, Ci-Cg-alkylsulfoxyl, C ₃ C ₅ -cycloalkyl, Ci -Cg-alkoxy, Cχ-Cg-haloalkoxy, Ci-Cg-alkoxycarbonyl, Ci-Cg-alkylthio, Ci-Cg-

Alkylamino, di-Ci-Cg-alkylamino, Cχ-Cg-alkylaminocarbonyl, di-Ci-Cg-alkylaminocarbonyl, Ci-Cg-alkylaminothiocarbonyl, di-Ci-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 ;

_C3 -CG-cycloalkyl, _C3 -CG-cycloalkenyl, heterocyclyl, aryl, hetaryl, where the cyclic radicals may be partially or fully halogenated or may carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, Carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, Ci-Cg-alkyl, Ci-Cg-haloalkyl, Ci-Cg-alkylsulfonyl, Ci-Cg-alkylsulfoxyl, C ₃ -Cg-cycloalkyl, Ci-Cg-alkoxy, Ci-Cg -Halogen- alkoxy, Ci-Cg-alkoxycarbonyl, Ci-Cg-alkylthio, Cι ~ Cg- alkylamino, di-Ci-Cg-alkylamino, Ci-Cg-alkylamino-carbonyl, di-Ci-Cg-alkylaminocarbonyl, Cι ~ Cg Alkyl aminothiocarbonyl, di-Ci-Cg-alkylaminothiocarbonyl, C -Cg-alkenyl, C ₂ -Cg-alkenyloxy, benzyl, benzyloxy,

Aryl, aryloxy, hetaryl and hetaryloxy;

in which

A 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 is} hydrogen or -C ~ C ₆ alkyl,

and their salts,

and

b) at least one compound of the formulas II to XI

NO.

CH.

CH ₃ CH (CH ₃ ) ₂

.N

0 11 +

in a synergistically effective amount.

2. Mixture according to claim 1, which is conditioned in two parts, one part containing the compound I in a solid or liquid carrier and the other part containing at least one of the compounds II to XI in a solid or liquid carrier.

3. A method of combating harmful fungi, characterized in that the fungi, their habitat or the materials, plants, seeds, soils, areas or spaces to be protected from fungal attack are treated with a mixture according to one of claims 1 or 2, the application the compound I and at least one of the compounds II to XI can be carried out simultaneously, namely together or separately, or in succession.

4. The method according to claim 3, characterized in that treating the harmful fungi, their habitat or the plants, seeds, soils, surfaces, materials or spaces to be kept free by them with 0.005 to 1 kg / ha of a compound I according to claim 1.