WO2007003643A1 - Fungicidal mixtures based on 3,4-disubstituted pyrazolecarboxylic acid biphenylamides - Google Patents

Abstract

The invention relates to fungicidal mixtures containing the following as active components 1) at least one 3,4-disubstituted pyrazole carboxylic acid biphenylamide of formula (I), where X = O or S, R1 and R2 independently = fluorine, chlorine, methyl, cyano, nitro, methoxy or trifluoromethyl and R3 = difluoromethyl or trifluoromethyl and 2) at least one agent (II) selected from the following groups A) to F): A) azoles, B) strobilurines, C) carboxamides, D) heterocyclic compounds, E) carbamates, F) other fungicides in synergistically effective amounts, method for prevention of fungal pests with mixtures of at least one compound (I) and at least one compound (II), the use of compound(s) (I) with agents (II) for the production of said mixtures and agents and seed containing said mixtures.

Description

Fungicidal mixtures based on 3,4-disubstituted pyrazolecarboxylic acid biphenylamides

description

The present invention relates to fungicidal mixtures containing as active components

1) at least one 3,4-disubstituted pyrazolecarboxylic acid biphenylamide of the formula I

in the X for oxygen or sulfur, R ¹ and R ² independently of

Fluorine, chlorine, methyl, cyano, nitro, methoxy or trifluoromethyl and R ³ are difluoromethyl or trifluoromethyl, and 2) at least one active compound II selected from the following groups A) to F):

A) Azoles selected from bitertanol, bromuconazole, cyproconazole, difenocynazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, Simecanolazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamide, benomyl, carbenzimine, thiabendazole, fuberidazole, ethaboxam, etridiazole, hymexazole;

B) strobilurins selected from azoxystrobin, dimoxystrobin, enestroburin,

Fluoxastrobin, kresoxime-methyl, methominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, enestroburine, (2-chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl) -carbamic acid methyl ester, (2-chloro Methyl 5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) carbamate and 2-ortho - [(2,5-dimethylphenyl-oxymethylene) phenyl] -3-methoxy-acrylic acid methyl ester ;

C) Carboxylic acid amides selected from carboxin, benalaxyl, boscalid, fenhumamide, flutolanil, furametpyr, mepronil, metalaxyl, mefenoxam, ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, 3,4-dichloro-N- (2 cyanophenyl) -isothiazole-5-carboxamide, dimethomorph, flumorph, fl uidover, fluopicolide (picobenzamide), zoxamide, carpropamide, diclocymet, Mandipropamide, N- (2- (4- [3- (4-Chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methanesulfonylamino-3-methyl-butyrannide, N- (2- (4- [3- (4-Chloro-phenyl) -prop-2-ynyloxy] -3-methoxy-phenyl) -ethyl) -2-ethanesulfonyl-amino-3-methylbutyramide, 3- (4-chloro -phenyl) -3- (2-isopropoxycarbonylamino-3-methyl-butyrylannino) -propionic acid-n-methyl ester, compounds of the formula III

in which R ^{4 is} methyl or ethyl,

4-Difluoromethyl-2-methyl-thiazole-5-carboxylic acid N- (4'-bromo-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid N- (4 ' -trifluoromethyl-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid N- (4'-chloro-3'-fluorobiphenyl-2-yl) -amide, 3 Difluoromethyl-1-methyl-pyrazole-4-carboxylic acid (3 ', 4'-dichloro-4-fluoro-biphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-pyrazole-4-carboxylic acid N- (3 ', 4'-dichloro-5-fluoro-biphenyl-2-yl) -amide and 3,4-dichloro-isothiazole-5-carboxylic acid N- (2-cyano-phenyl) -amide;

D) Heterocyclic compounds selected from fluazinam, pyrifenox, bu- pirimat, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil, triforin, fenpiclonil, fludioxonil, aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, procymidone , Vinclozolin, fenoxadone, fenamidone, octhilinone, probenazole, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1, 2, 4] triazolo [1,5-a] pyrimidine, anilazine, diclomethine, pyroquilone, proquinazide, tricyclazole, the compound of formula IV (2-Bu

Acibenzolar-S-methyl, captafol, captan, dazomet, folpet, fenoxanil, quinoxyfen and 3- (3-bromo-6-fluoro-2-methyl-indole-1-sulfonyl) - [1, 2,4] triazole -1- sulfonic acid di

E) Carbamates selected from Mancozeb, Maneb, Metam, Metiram, Ferbam, Propineb, Thiram, Zineb, Ziram, Diethofencarb, Iprovalicarb, Flubenthiava- licarb, propamocarb, N- (1- (1 - (4-cyanophenyl) ethanesulfonyl) -but-2-yl) -carbamic acid (4-fluorophenyl) ester, 3- (4-chloro-phenyl) -3- (2 -isopropoxy-carbonylamino-3-methyl-butyrylannino) -propanoic acid-n-ethyl ester of the formula VI

and carbamato oxime ethers of formula VII

Z is N or CH;

F) Other fungicides selected from

Guanidines: dodin, iminoctadine, guazatine,

Antibiotics: kasugamycin, streptomycin, polyoxin, validamycin A, nitrophenyl derivatives: binapacryl, dinocap, dinobutone, sulfur-containing heterocyclyl compounds: dithianone, isoprothiolane, organometallic compounds: fentin salts such as fentin acetate,

Organophosphorus Compounds: Edifenphos, Iprobenfos, Fosetyl,

Fosetyl-aluminum, Phosphorous acid and its salts, pyrazophos,

Tolclofos-methyl,

Organochlorine compounds: chlorothalonil, dichlofluanid, flusulfamide, hexachlorobenzene, phthalide, pencycuron, quintozene, thiophanate-methyl, toluylfluanid,

Inorganic active ingredients: Bordeaux broth, copper acetate, copper hydroxide, copper oxychloride, basic copper sulphate, sulfur, others: cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone and spiroxamine;

in a synergistically effective amount.

In addition, the invention relates to a method for controlling harmful fungi with mixtures of at least one compound I and at least one of the active compounds II, the use of the compounds I and II for the preparation of such mixtures and agents and seeds containing these mixtures.

Substituted biphenylanilides of the formula I are known from EP-A 589301, in which a process for their preparation and a list of possible mixing partners from the series of fungicides, bactericides, acaricides, nematicides or insecticides.

From WO 01/42223 also substituted biphenylanilides are known, which are monosubstituted on the phenyl ring.

From JP 09/132567 disubstituted biphenylanilides are known which are substituted on the phenyl ring by trifluoromethyl.

2,4-disubstituted biphenylanilides are known from WO 2005/123689 and WO 2005/123690, and 3,4-disubstituted biphenylanilanes are known from the earlier German Application No. 102005007160.0.

WO 2005/034628 discloses mixtures of 3,4-disubstituted biphenylanilides with other fungicides.

However, the 3,4-disubstituted biphenylanilides described can not be fully satisfied, especially at low application rates.

The active compounds II mentioned above as component 2, their preparation and their action against harmful fungi are generally known (cf.: http://www.hclrss.demon.co.uk/index.htrnl); they are commercially available.

Benalaxyl, methyl N- (phenylacetyl) -N- (2,6-xylyl) -DL-alaninate (DE 29 03 612); Metalaxyl, methyl N- (methoxyacetyl) -N- (2,6-xylyl) -DL-alaninate (GB 15 00 581);

Ofurace, (RS) -α- (2-chloro-N-2,6-xylylacetamido) -γ-butyrolactone [CAS RN 58810-48-3];

Oxadixyl, N- (2,6-dimethylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) acetamide (GB

20 58 059);

Aldimorph, "4-alkyl-2,5 (or 2,6) -dimethylmorpholine" containing 65-75% 2,6-dimethylmorpholine and 25-35% 2,5-dimethylmorpholine containing more than 85% 4- dodecyl

2,5 (or 2,6) -dimethylmorpholine, wherein "alkyl" also includes octyl, decyl, tetradecyl and

Hexadecyl having a cis / trans ratio of 1: 1 [CAS RN 91315-15-0];

Dodin, 1-dodecylguanidinium acetate (Plant Dis. Rep. 41, p.1029 (1957));

Dodemorph, 4-cyclododecyl-2,6-dimethylmorpholine (DE-A 1198125); Fenpropimorph, (RS) -cis-4- [3- (4-tert-butylphenyl) -2-methylpropyl] -2,6-dimethylmorpholine (DE-A 27 52 096);

Fenpropidin, (RS) -I - [3- (4-tert-butylphenyl) -2-methylpropyl] piperidine (DE-A 27 52 096);

Guazatine, mixture of the reaction products obtained from the amidation of technical lminodi (octamethylene) diamine containing various guanidines and polyamines [CAS RN 108173-90-6];

Iminoctadin, 1, 1'-lminodi (octamethylene) diguanidine (Congr. Plant Pathol., 1, p

(1968); Spiroxamine, (8-tert-butyl-1,4-dioxaspiro [4.5] dec-2-yl) diethylannin (EP-A 281 842);

Tridemorph, 2,6-dimethyl-4-tridecylmorpholine (DE-A 11 64 152);

Pyrimethanil, 4,6-dimethylpyrimidin-2-yl-phenyl-amine (DD-A 151 404);

Mepanipyrim, (4-methyl-6-prop-1-ynyl-pyrimidin-2-yl) -phenylamine (EP-A 224 339); Cyprodinil, (4-cyclopropyl-6-methylpyrimidin-2-yl) -phenylamine (EP-A 310550);

Cycloheximide, 4 - {(2R) -2 - [(1S, 3S, 5S) -3,5-dimethyl-2-oxocyclohexyl] -2-hydroxyethyl} piperidine-2,6-dione [CAS RN 66-81 -9];

Griseofulvin, 7-chloro-2 ', 4,6-triethoxy-6'-methylpiro [benzofuran-2 (3H), 1'-cyclohex-2'-ene] -3,4'-dione [CAS RN 126-07 -8th]; Kasugamycin, 3-O- [2-Amino-4 - [(carboxymiminomethyl) amino] -2,3,4,6-tetradeoxy-α-D-arabino-hexopyranosyl] -D-chiro-inositol [CAS RN 6980-18 -3];

Natamycin, (8E, 14E, 16E, 18E, 20E) - (1R, 3S, 5R, 7R, 12R, 22R, 24S, 25R, 26S) -22- (3-amino-3,6-dideoxy- β-D-mannopyranosyloxy) -1,3,26-trihydroxy-12-methyl-10-oxo-6,11,28-trioxatricyclo [22.3.1.0 ⁵ φctacosa-8,14,16,18,20-pentaene-25 carboxylic acid [CAS RN 7681-93-8];

Polyoxine, 5- (2-Amino-5-O-carbamoyl-2-deoxy-L-xylonamido) -1- (5-carboxy-1,2,3,4-tetrahydro-2,4-dioxopyrimidin-1-yl ) -1, 5-dideoxy-.beta.-D-allofuranuronic acid [CAS RN

22976-86-9];

Streptomycin, 1, 1 '- {1-L- (1,3,5 / 2,4,6) -4- [5-deoxy-2-O- (2-deoxy-2-n-ethylannino-α-L) glucopyranosyl) -3-C-formyl-α-L-xyxofuranosyloxy] -2,5,6-trihydroxycyclohex-1, 3-ylene} diguanidine (J. Am. Chem. Soc. 69, p.1234 (1947));

Bitertanol, β - ([1,1'-biphenyl] -4-yloxy) -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol

(DE-A 23 24 020);

Bromuconazole, 1 - [[4-bromo-2- (2,4-dichlorophenyl) tetrahydro-2-furanyl] methyl] -1H-1, 2,4-triazole (Proc. 1990 Br. Crop. Prot. Conf. - Pests Dis., Vol. 1, p. 459);

Cyproconazole, 2- (4-chlorophenyl) -3-cyclopropyl-1 - [1, 2,4] triazole-1-yl-butan-2-ol

(US 4,664,696);

Difenoconazole, 1 - {2- [2-chloro-4- (4-chlorophenoxy) phenyl] -4-methyl- [1,3-dioxolan-2-ylmethyl} -1 H- [1,2,4] triazole ( GB-A 2 098 607); Diniconazole, (βE) -β - [(2,4-dichlorophenyl) methylene] -α- (1, 1-dimethylethyl) -1H-1, 2,4-triazole-1-ethanol (Noyaku Kagaku, 1983, Vol 8, p. 575);

Enilconazole (imazalil), 1- [2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl] -1H-imidazole

(Fruits 28, p. 545, 1973);

Epoxiconazole, (2RS, 3SR) -1 - [3- (2-chlorophenyl) -2,3-epoxy-2- (4-fluorophenyl) propyl] -1H-1,2,4-triazole (EP-A 196 038);

Fenbuconazole, α- [2- (4-chlorophenyl) ethyl] -α-phenyl-1H-1, 2,4-triazole-1-propanenitrile

(Proc., 1988 Br. Crop Prot. Conf. - Pests Dis., Vol. 1, p. 33);

Fluquinconazole, 3- (2,4-dichlorophenyl) -6-fluoro-2- [1,2,4] triazole-1-yl-3H-quinazolin-4-one

(Proc. Br. Crop Prot. Conf.-Pests Dis., 5-3, 411 (1992)); Flusilazole, 1 - {[bis (4-fluorophenyl) methylsilanyl] methyl} -1 H- [1,2,4] triazole (Proc. Br. Crop

Prot. Conf.-Pests Dis., Vol. 1, p. 413 (1984));

Flutriafol, α- (2-fluorophenyl) -α- (4-fluorophenyl) -1H-1, 2,4-triazole-1-ethanol (EP-A 15,756); Hexaconazole, 2- (2,4-dichlorophenyl) -1- [1,2,4] triazol-1-yl-hexan-2-ol (CAS RN

79983-71-4);

Ipconazole, 2 - [(4-chlorophenyl) methyl] -5- (1-methylethyl) -1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol (EP-A 267,778); Metconazole, 5- (4-chlorobenzyl) -2,2-dimethyl-1 - [1, 2,4] triazole-1-ylmethylcyclopentanol

(GB 857,383);

Myclobutanil, 2- (4-chlorophenyl) -2- [1,2,4] triazol-1-ylmethylpentanenitrile (CAS RN 88671-

89-0);

Penconazole, 1- [2- (2,4-dichlorophenyl) pentyl] -1 H- [1,2,4] triazole (Pesticide Manual, 12th Edition 2000, p. 712);

Propiconazole, 1 - [[2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl] methyl] -1H-1, 2,4-triazole (BE 835,579);

Prochlorazole, imidazole-1-carboxylic acid-propyl- [2- (2,4,6-trichlorophenoxy) -ethyl] -annide

(US 3,991,071); Prothioconazole, 2- [2- (1-Chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2,4-dihydro- [1,2,4] triazole-3-thione (WO 96/16048) ;

Simeconazole, α- (4-fluorophenyl) -α - [(trimethylsilyl) methyl] -1H-1, 2,4-triazole-1-ethanol

[CAS RN 149508-90-7],

Tebuconazole, 1- (4-chlorophenyl) -4,4-dimethyl-3- [1,2,4] triazole-1-ylmethylpentan-3-ol (EP-A 40 345);

Tetraconazole, 1 - [2- (2,4-dichlorophenyl) -3- (1,1,2,2-tetrafluoroethoxy) propyl] -1H-1, 2,4-triazole (EP-A 234 242);

Triadimefon, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1, 2,4-triazol-1-yl) -2-butanone (BE

793 867); Triadimenol, β- (4-chlorophenoxy) -α- (1, 1-dimethylethyl) -1H-1, 2,4-triazole-1-ethanol (DE-A

23 24 010);

Triflumizole, (4-chloro-2-trifluoromethylphenyl) - (2-propoxy-1 - [1, 2,4] triazole-1-yl-ethylidene) -amine (JP-A 79/119 462);

Triticonazole, (5E) -5 - [(4-chlorophenyl) methylene] -2,2-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol (FR 26 41 277);

Iprodione, 3- (3,5-dichlorophenyl) -2,4-dioxo-imidazolidine-1-carboxylic acid isopropylannide (GB

13 12 536);

Myclozoline, (RS) -3- (3,5-dichlorophenyl) -5-methoxymethyl-5-methyl-1,3-oxazolidine-2,4-dione [CAS RN 54864-61-8]; Procymidone, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboxinnide (US Pat

3,903,090);

Vinclozoline, 3- (3,5-dichlorophenyl) -5-methyl-5-vinyl-oxazolidine-2,4-dione (DE-A

22 07 576);

Ferbam, iron (3+) dimethyldithiocarbamate (US 1,972,961); Nabam, disodium ethylenebis (dithiocarbamate) (U.S. 2,317,765);

Maneb, manganese ethylene bis (dithiocarbamate) (US 2 504 404); Mancozeb, manganese ethylene bis (dithiocarbamate) polymer conjugate zinc salt (GB

996 264);

Metam, methyldithiocarbamic acid (US 2,791,605);

Metiram, zinc ammonium ethylenebis (dithiocarbamate) (U.S. 3,248,400); Propineb, zinc propylene bis (dithiocarbamate) polymer (BE 611 960);

Polycarbamate, bis (dimethylcarbamodithioato-κS, κS ') [μ - [[1,2-ethanediylbis [carbamoedithioato-κS, κS']] (2 -)]] di [zinc] [CAS RN 64440-88-6 ];

Thiram, bis (dimethylthiocarbamoyl) disulfide (DE-A 642 532);

Ziram, dimethyldithiocarbamate [CAS RN 137-30-4]; Zineb, zinc ethylene bis (dithiocarbamate) (US 2 457 674);

Anilazine, 4,6-dichloro-N- (2-chlorophenyl) -1, 3,5-triazin-2-amine (US 2,720,480);

Benomyl, 2-acetylaminobenzimidazole-1-carboxylic acid butylamide (US 3,631,176);

Boscalid, 2-chloro-N- (4'-chlorobiphenyl-2-yl) nicotinamide (EP-A 545 099);

Carbendazim, (1 H-benzimidazol-2-yl) -carbamic acid methyl ester (US 3,657,443); Carboxin, 5,6-dihydro-2-methyl-N-phenyl-1,4-oxathiin-3-carboxamide (US 3,249,499);

Oxycarboxine, 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide 4,4-dioxide (US

3 399 214);

Cyazofamide, 4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -1H-imidazole-1-sulfonamide (CAS RN 120116-88-3]; dazomet, 3,5-dimethyl- 1, 3,5-thiadiazinan-2-thione (Bull. Soc. Chim. Fr. Vol. 15, p. 891

(1897));

Diflufenzopyr, 2- {1- [4- (3,5-difluorophenyl) semicarbazono] ethyl} nicotinic acid [CAS RN

109293-97-2];

Dithianone, 5,10-dioxo-5,10-dihydronaphtho [2,3-b] [1,4] dithiine-2,3-dicarbonitrile (GB 857,383);

Famoxadone, (RS) -3-anilino-5-methyl-5- (4-phenoxyphenyl) -1,3-oxazolidine-2,4-dione

[CAS RN 131807-57-3];

Fenamidone, (S) -1-anilino-4-methyl-2-methylthio-4-phenylimidazolin-5-one [CAS RN

161326-34-7]; Fenarimol, α- (2-chlorophenyl) -α- (4-chlorophenyl) -5-pyrimidinemethanol (GB 12 18 623);

Fuberidazole, 2- (2-furanyl) -1H-benzimidazole (DE-A 12 09 799);

Flutolanil, α, α, α-trifluoro-3'-isopropoxy-o-toluanilide (JP 1104514);

Furametpyr, 5-chloro-N- (1,3-dihydro-1,1,3-trimethyl-4-isobenzofuranyl) -1,3-dimethyl-1H-pyrazole-4-carboxamide [CAS RN 123572-88-3 ]; Isoprothiolane, diisopropyl 1, 3-dithiolan-2-ylidenmalonate (Proc. Insectic. Fungic. Conf.

Vol. 2, p. 715 (1975));

Mepronil, 3'-isopropoxy-o-toluanilide (U.S. 3,937,840);

Nuarimol, α- (2-chlorophenyl) -α- (4-fluorophenyl) -5-pyrimidinemethanol (GB 12 18 623);

Fluopicolide (picobenzamide), 2,6-dichloro-N- (3-chloro-5-trifluoromethylpyridin-2-ylmethyl) benzamide (WO 99/42447);

Probenazole, 3-Allyloxy-1,2-benzothiazole 1,1-dioxide (Agric., Biol. Chem. 37, p

(1973); Proquinazide, 6-iodo-2-propoxy-3-propylquinazolin-4 (3H) -one (WO 97/48684);

Pyrifenox, 2 ', 4'-dichloro-2- (3-pyridyl) acetophenone (EZ) -O-methyloxime (EP 49 854);

Pyroquilone, 1,2,5,6-tetrahydropyrrolo [3,2,1-ij] quinolin-4-one (GB 139 43 373);

Quinoxyfen, 5,7-dichloro-4- (4-fluorophenoxy) quinoline (U.S. 5,240,940); Silthiofam, N-allyl-4,5-dimethyl-2- (triethylsilyl) thiophene-3-carboxannide [CAS RN

175217-20-6];

Thiabendazole, 2- (1, 3-thiazol-4-yl) benzimidazole (U.S. 3,017,415);

Thifluzamide, 2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4-trifluoromethyl-1, 3-thiazole-5-carboxanilide [CAS RN 130000-40-7]; Thiophanate-methyl, 1, 2-phenylenebis (iminocarbonothioyl) bis (dimethylcarbannate) (DE-A

19 30 540);

Tiadinil, S'-chloro '' - dimethyl-1S-thiadiazole-6-carboxanilide [CAS RN 223580-51-6];

Tricyclazole, S -methyl-i ^^ triazolose ^ -bHi ^ benzothiazole [CAS RN 41814-78-2];

Triforin, N, N '- {piperazine-1, 4-diyl-bis [(trichloromethyl) nethylenes]} diformannanide (DE-A 19 01 421);

5-Chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine (WO 98/46607);

Bordeaux broth, mixture of CuSO ₄ .3Cu (OH) ₂ .3CaSO ₄ [CAS RN 8011-63-0];

Copper acetate, Cu (OCOCH ₃ ) ₂ [CAS RN 8011-63-0]; Copper oxychloride, Cu ₂ Cl (OH) ₃ [CAS RN 1332-40-7];

Basic copper sulfate, CuSO ₄ [CAS RN 1344-73-6];

Binapacryl, (RS) -2-sec-butyl-4,6-dinitrophenyl 3-methylcrotonate [CAS RN 485-31-4];

Dinocap, a mixture of 2,6-dinitro-4-octylphenylcrotonate and 2,4-dinitro-6-octyl-phenylcrotonate, where "octyl" is a mixture of 1-methylheptyl, 1-ethylhexyl and 1-propylpentyl (US Pat. No. 2,526,660 );

Dinobutone, (RS) -2-sec-butyl-4,6-dinitrophenyl isopropyl carbonate [CAS RN 973-21-7];

Nitrothal isopropyl, diisopropyl 5-nitroisophthalate (Proc. Br. Insectic. Fungic. Conf.

Vol. 2, p. 673 (1973));

Fenpiclonil, 4- (2,3-dichlorophenyl) -1H-pyrrole-3-carbonitrile (Proc. 1988 Br. Crop Prot. Conf. - Pests Dis., Vol. 1, p.

Fludioxonil, 4- (2,2-difluorobenzo [1,3] dioxol-4-yl) -1H-pyrrole-3-carbonitrile (The Pesticide

Manual, Ed .: The British Crop Protection Council, 10th Edition 1995, p. 482);

Acibenzolar-S-methyl, methyl 1,2,3-benzothiadiazole-7-carbothioate [CAS RN 135158-

54-2]; Flubenthiavalicarb (benthiavalicarb), {(S) -1 - [(1 R) -1 - (6-fluorobenzothiazol-2-yl) ethylcarbamoyl] -2-methylpropyl} -carbamic acid isopropyl ester (JP-A 09/323 984);

Carpropamide, 2,2-dichloro-N- [1- (4-chlorophenyl) ethyl] -1-ethyl-3-methylcyclopropane carboxamide [CAS RN 104030-54-8];

Chlorothalonil, 2,4,5,6-tetrachloroisophthalonitrile (US 3,290,353); Cyflufenamide, (Z) -N- [α- (Cyclopropylmethoxyimino) -2,3-difluoro-6- (trifluoromethyl) benzyl] -

2-phenylacetamide (WO 96/19442);

Cymoxanil, 1- (2-cyano-2-methoxyiminoacetyl) -3-ethylurea (U.S. 3,957,847); Diclomethine, 6- (3,5-dichlorophenyl-p-tolyl) -pyridazine-3 (2H) -one (U.S. 4 052 395);

Diclocymet, (RS) -2-cyano-N - [(R) -1- (2,4-dichlorophenyl) ethyl] -3,3-dinethyl butyrannide

[CAS RN 139920-32-4];

Diethofencarb, isopropyl 3,4-diethoxycarbanilate (EP-A 78 663); Edifenphos, O-ethyl S, S-diphenyl phosphorodithioate (DE-A 14 93 736);

Ethaboxam, N- (cyano-2-thienylmethyl) -4-ethyl-2- (ethylamino) -5-thiazolecarboxannide

(EP-A 639 574);

Fenhexamide, N- (2,3-dichloro-4-hydroxyphenyl) -1-methylcyclohexanecarboxamide (Proc.

Br. Crop Prot. Conf. - Pests Dis., 1998, vol. 2, p. 327); Fentin acetate, triphenyltin (US 3 499 086);

Fenoxanil, N- (1-cyano-1,2-dimethylpropyl) -2- (2,4-dichlorophenoxy) propanamide (EP-A

262 393);

Ferimzone, (Z) -2'-methylacetophenone-4,6-dimethylpyrimidin-2-ylhydrazone [CAS RN

89269-64-7]; Fluazinam, S-chloro-N-IS-chloro-1-dinitro (3-fluoro-fluoro-phenyl-S-rifluoromethyl) -pyridinamine (The Pesticide Manual, ed. The British Crop Protection Council, 10.

Edition 1995, p. 474);

Fosetyl, Fosetyl Aluminum, Ethyl Phosphonate (FR 22 54 276);

Iprovalicarb, [(1S) -2-methyl-1- (1-p-tolyl-ethylcarbamoyl) -propyl] -carbamic acid isopropyl ester (EP-A 472 996);

Hexachlorobenzene (C.R. Seances Acad. Agric. Fr., Vol. 31, p. 24 (1945);

Mandipropamide, (RS) -2- (4-chlorophenyl) -N- [3-methoxy-4- (prop-2-ynyloxy) phenethyl] -2-

(prop-2-ynyloxy) acetamide (WO 03/042166);

Metrafenone, 3'-bromo-2,3,4,6'-tetramethoxy-2 ', 6-dinethylbenzophenone (U.S. 5,945,567);

Pencycuron, i - ^ - chlorobenzy ^ -i-cyclopentyl-S-phenylurea (DE-A 27 32 257);

Penthiopyrad, (RS) -N- [2- (1, 3-dimethylbutyl) -3-thienyl] -1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carboxamide (JP 10/130268);

Propamocarb, 3- (dimethylamino) propylcarbamic acid isopropyl ester (DE-A 1567 169); Phthalide (DE-A 16 43 347);

Toloclofos-methyl, O-2,6-dichloro-p-tolyl O, O-dimethyl phosphorothioate (GB 14 67 561);

Quintoene, pentachloronitrobenzene (DE-A 682 048);

Zoxamide, (RS) -3,5-dichloro-N- (3-chloro-1-ethyl-1-methyl-2-oxopropyl) -p-toluamide [CAS

RN 156052-68-5]; Captafol, N- (1,1,2,2-tetrachloroethylthio) cyclohex-4-ene-1,2-dicarboximide

(Phytopathology 52, p. 754 (1962));

Captan, N- (trichloromethylthio) cyclohex-4-ene-1,2-dicarboximide (US 2,553,770);

Dichlofluanid, N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfannide (DE-A

11 93 498); Folpet, N- (trichloromethylthio) phthalimide (US 2 553 770);

Tolylfluanid, N-dichlorofluoromethylthio-N ', N'-dimethyl-N-p-tolylsulfannide (DE-A

11 93 498); Dimethomorph, 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) -1-morpholin-4-yl-propenone

(EP-A 120 321);

Flumetover, 2- (3,4-Dinethoxyphenyl) -N-ethyl-α, α, α-trifluoro-N-methyl-p-toluanide

[AGROW No. 243, 22 (1995)]; Flumorph, 3- (4-fluorophenyl) -3- (3,4-dimethoxyphenyl) -1-morpholin-4-yl-propenone (EP-A

860 438);

4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-bromo-biphenyl-2-yl) -amide,

4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-trifluoromethyl-biphenyl-2-yl) -amide,

4-Difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-chloro-3'-fluorobiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-pyrazole-4-carboxylic acid (3 ', 4'-dichloro-4-fluoro-biphenyl-2-yl) -amide

(WO 03/66610);

3,4-Dichloro-isothiazole-5-carboxylic acid (2-cyano-phenyl) -amide (WO 99/24413);

N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methanesulfonylamino-3-methylbutyramide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-ethanesulfonylamino-3-methylbutyramide (WO 04/49804);

3- [5- (4-Chloro-phenyl) -2,3-dimethyl-isoxazolidin-3-yl] -pyridine (EP-A 10 35 122);

2-butoxy-6-iodo-3-propyl-chromen-4-one (WO 03/14103);

3- (3-Bromo-6-fluoro-2-methylindol-1-sulfonyl) - [1, 2,4] triazole-1-sulfonic acid dimethylamide

(EP-A 10 31 571); (2-chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl) -carbamic acid methyl ester,

(2-Chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) -carbamic acid methyl ester (EP-A 12 01 648);

Methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propionate (EP-A 10 28 125); Azoxystrobin, 2- {2- [6- (2-cyano-1-vinyl-penta-1,3-dienyloxy) -pyrimidin-4-yloxy] -phenyl} -

3-methoxy-acrylic acid methyl ester (EP-A 382 375);

Dimoxystrobin, (E) -2- (methoxyimino) -N-methyl-2- [α- (2,5-xylyloxy) -o-tolyl] -acetamide (EP-

A 477 631);

Fluoxastrobin, (E) - {2- [6- (2-chlorophenoxy) -5-fluoropyrimidin-4-yloxy] phenyl} (5,6-dihydro-1,2,2-dioxazin-3-yl) methanone-O methyloxime (WO 97/27189);

Kresoxim-methyl, (E) -methoxyimino [α- (o-tolyloxy) -o-tolyl] acetic acid methyl ester (EP-A

253 213);

Metominostrobin, (E) -2- (methoxyimino) -N-methyl-2- (2-phenoxyphenyl) acetamide (EP-A

398 692); Orysastrobin, (2E) -2- (methoxyimino) -2- {2 - [(3E, 5E, 6E) -5- (methoxyimino) -4,6-dinethyl-

2,8-dioxa-3,7-diazanon-3,6-dien-1-yl] phenyl} -N-methylacetamide (WO 97/15552);

Picoxystrobin, 3-methoxy-2- [2- (6-trifluoromethyl-pyridin-2-yloxymethyl) -phenyl] -acrylic acid methyl ester (EP-A 278 595);

Pyraclostrobin, N- {2- [1- (4-chlorophenyl) -1H-pyrazol-3-yloxymethyl] phenyl} (N-methoxy) carbamic acid methyl ester (WO 96/01256);

Trifloxystrobin, (E) -methoxyimino-{(E) -α- [1- (α, α, α-trifluoro-m-tolyl) ethylideneaminooxy] -o-tolyl} -acetic acid methyl ester (EP-A 460 575); 2- [ortho- (2,5-dimethylphenyl-oxynnethylen) phenyl] -3-nnethoxy-acrylsäurennethylester

(EP-A 226 917);

5-Chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine (WO 98/46608); 3,4-dichloro-N- (2-cyanophenyl) -isothiazole-5-carboxylic acid amide (WO 99/24413);

Compounds of formula IM (WO 04/049804);

N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methanesulfonylamino-3-methylbutyramide and N- (2 - (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-ethanesulfonylamino-3-methyl-butyrannide (WO 03/66609);

2-butoxy-6-iodo-3-propyl-chromen-4-one of the formula IV (WO 03/14103);

3- (3-bromo-6-fluoro-2-methylindol-1-sulfonyl) - [1, 2,4] triazole-1-sulfonic acid dimethylamide of the formula V (WO 03/053145);

Methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propanoate of the formula VI (EP-A 1028125).

In view of a reduction in the application rates and broadening of the spectrum of action of the compounds I and II, the present invention mixtures were the object of having an improved action against harmful fungi, especially for certain indications with reduced total amount of applied active substances.

Accordingly, the mixtures of active ingredients I and II defined above were found. It has also been found that it is possible to combat harmful fungi more effectively than by using at least one compound I and at least one of the active compounds II, or at least one compound I and at least one of the active compounds II in succession, both together and separately Single compounds alone (synergistic mixtures).

The compounds I can be used as synergists for a variety of different fungicidal agents. By simultaneous joint or separate application of at least one compound I with at least one active compound II, the fungicidal efficacy is increased to a superadditive extent.

The compounds I can be present in various crystal modifications, which may differ in their biological activity.

The 3,4-disubstituted biphenylanilides of the formula I are known from the earlier German Application No. 102005007160.0 and WO 2005/034628 or can be prepared in the manner described there. The compounds I in which X is sulfur can be prepared, for example, by sulfurization of the corresponding compounds I in which X is oxygen (cf., for example, D. Petrova & K. Jakobcic, Croat. Chem. Acta 48, 49 (1976 ) and WO 2001/42223).

On the one hand, among the 3,4-disubstituted biphenylanilides I, those in which X is oxygen are preferred.

On the other hand, those compounds I are preferred in which X is sulfur.

For the mixtures according to the invention compounds of the formula I are preferred in which R ¹ and R ^{2 are} independently fluorine, chlorine, methyl, methoxy or trifluoromethyl.

Particular preference is given to compounds of the formula I in which R ¹ and R ² independently of one another are fluorine, chlorine, cyano or methoxy. Very particular preference is given to compounds of the formula I in which R ¹ and R ² independently of one another are fluorine or chlorine.

Particular preference is given to the compounds I listed in the following Table 1, in which X is oxygen.

Table 1

Very particularly preferred compounds of formula I are 1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxylic acid-N- (3 ^1, 4'-dichlorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl 1-H-pyrazole-4-carboxylic acid N- (3'-chloro-4 ¹ -fluorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoro-methyl-1H-pyrazole-4-carboxylic acid N - (3 ^l , 4 ^l -difluorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ^l -fluoro-4 ^l -chlorobiphenyl-2-yl ) - amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-chloro-4 ¹ -fluorobiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1 H-pyrazole-4-carboxylic acid N- (3 ', 4 ¹ -difluorobiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3', 4 ^1- Dichlorobiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-fluoro-4'-chlorobiphenyl-2-yl) -amide, 1 - Methyl 3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-methyl-4'-chlorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4 carboxylic acid N- (3'-methyl-4 ¹ -fluorobiph enyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-methyl-4 ¹ -fluorobiphenyl-2-yl) -amide, 1-methyl- 3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-methyl-4 ¹ -chlorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- ^(3-nitro-l 4 ^l -chlorbiphenyl-2-yl) - amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid-N- (3 ', 4 ¹ -dimethylbiphenyl-2- yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ¹ -trifluoromethyl-4 ¹ -chlorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl- 1 H-pyrazole-4-carboxylic acid N- (3'-trifluoromethyl) - nitrobiphenyl-1-yl-amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-methyl -4 ¹ -methoxybiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ¹ , 4 ¹ -dimethoxybiphenyl-2-yl) -amide, 1- Methyl 3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-fluoro-4 ¹ -methoxybiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4 carboxylic acid N- (3 ^L -methoxy-4 ^L -chlorobiph enyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-chloro-4 ¹ -methylbiphenyl-2-yl) -amide, 1-methyl- 3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-trifluoromethyl-4 ¹ -fluorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-cyano-4'-methoxybiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-cyano-4 ¹ -methoxybiphenyl- 2-yl) amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-methoxy-4 ¹ -cyanobiphenyl-2-yl) -amide, 1-methyl-3- Difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ¹ -methoxy-4 ¹ -cyanobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ¹ -fluoro-4 ¹ -methylbiphenyl-2-yl) amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-nitro-4 ¹ -methoxybiphenyl-2-yl) yl) amide and 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (S'-chloro-methoxybiphenyl) -yl-J-amide.

Preference is given to mixtures of a compound of the formula I with at least one active compound selected from the group of A) azoles. Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of B) strobilurins.

Preference is given to mixtures of a compound of the formula I with at least one active substance selected from the group of C) carboxylic acid amides.

Also preferred are mixtures of a compound of the formula I with at least one active compound selected from the group of the D) heterocyclic compounds.

Also preferred are mixtures of a compound of formula I with at least one active ingredient selected from the group of E) carbamates.

Also preferred are mixtures of a compound of formula I with at least one active ingredient selected from the group of F) other fungicides.

Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of A) azoles selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole , Triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamide, benomyl, carbenzimid, ethaboxam.

Particular preference is also given to mixtures of a compound of the formula I with at least one active ingredient selected from the group of A) azoles selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, propiconazole, prothioconazole, triadimefon , Triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamide, benomyl and carbendazim.

Very particular preference is also given to mixtures of a compound of the formula I with at least one active substance selected from the group of A) azoles selected from epoxiconazole, fluquinconazole, flutriafol, metconazole, tebuconazole, triticonazole, prochloraz and carbendazim.

Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group consisting of b) strobilurins selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyracoltrobin and trifloxystrobin. Particular preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group consisting of B) strobilurins selected from kresoxim-methyl, orysastrobin and pyraclostrobin.

Very particular preference is also given to mixtures of a compound of the formula I with pyraclostrobin.

Preference is also given to mixtures of a compound of the formula I with at least one active substance selected from the group of C) carboxylic acid amides selected from hexadexamide, metalaxyl, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolide (picobenzamide), zoxamide, carpropamide and mandipropamide ,

Particular preference is also given to mixtures of a compound of the formula I with at least one active substance selected from the group consisting of C) carboxylic acid amides selected from fenhexamide, metalaxyl, mefenoxam, ofurace, dimethomorph, zoxamide and carpropamide.

Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group consisting of d) heterocyclic compounds selected from fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforin, fludiooxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin , Iprodione, vinclozolin, famoxadone, fenamidone, probenazole, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1,5-a] pyrimidine, proquinazide, acibenzolar-S-methyl, capotafol, folpet, fenoxanil and quinoxyfen, especially fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforin, fludioxonil, dodemorph, fenpropimorph, tridemorph , Fenpropidin, iprodione, vinclozolin, famoxadone, fenamidone, probenazole, proquinazide, acibenzolar-S-methyl, captafol, folpet, fenoxanil and quinoxyfen.

Particular preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group consisting of d) heterocyclic compounds selected from pyrimethanil, dodemorph, fenpropimorph, tridemorph, iprodione, vinclozoline, 5-chloro-7- (4-methyl -piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1,5-a] pyrimidine and quinoxyfen, in particular pyrimethanil, dodemorph, fenpropimorph, Tridemorph, iprodione, vinclozolin and quinoxyfen.

Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group consisting of E) carbamates selected from mancozeb, metiram, propineb, thiram, iprovalicarb, flubenthiavalicarb and propamocarb.

Particular preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of E) carbamates selected from mancozeb and metiram. Preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of F) other fungicides selected from dithianone, fentin salts such as fentin acetate, fosetyl, fosetyl aluminum, phosphorous acid and salts thereof, chlorothalonil, dichlofluanide , Thiophanate-methyl, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur, cymoxanil, metrafenone and spiroxamine.

Particular preference is also given to mixtures of a compound of the formula I with at least one active compound selected from the group of F) Other fungicides selected from phosphorous acid and its salts, chlorothalonil and metrafenone.

Also preferred are tri-mixtures of a compound of the formula I with two of the abovementioned active compounds II.

Preferred active substance combinations are listed in the following Tables 2 to 8:

Table 2

Active substance combinations of compounds of the formula I with active compounds II of the group A):

Table 3

Active substance combinations of compounds of the formula I with active ingredients II of group B):

Table 4

Active substance combinations of compounds of the formula I with active ingredients II of group C):

Table 5 Active substance combinations of compounds of the formula I with active ingredients II of group D):

Table 6

Active substance combinations of compounds of the formula I with active ingredients II of group E):

Table 7

Active substance combinations of compounds of the formula I with active ingredients II of the group F):

Table 8

Active substance combinations of compounds I with two active substances II:

The mixtures of compound (s) I and at least one of the active compounds II, or the simultaneous joint or separate use of at least one compound I with at least one of the active compounds II, are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn. Oomycetes). They are partially systemically effective and can be used in crop protection as foliar, pickling and soil fungicides. They can also be used for seed treatment.

They are of particular importance for the control of a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, turf, bananas, cotton, soy, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as cucumbers. Beans, tomatoes, potatoes and pumpkins, as well as the seeds of these plants.

In particular, they are suitable for controlling the following plant diseases:

Alternaria species on vegetables, rapeseed, sugar beets and fruits and rice, e.g. A. solani or A. alternata on potatoes and tomatoes,

Aphanomyces species of sugar beets and vegetables, Ascochyta species of cereals and vegetables, Bipolaris and Drechslera species on corn, cereals, rice and turf, eg D. maydis on corn,

Blumeria graminis (powdery mildew) on cereals,

Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and vines, - Bremia lactucae on salad,

Cercospora species on maize, soybeans, rice and sugar beet,

Cochliobolus species on maize, cereals, rice, e.g. Cochliobolus sativus on cereals,

Cochliobolus miyabeanus on rice,

Colletotricum species on soybeans and cotton, - Drechslera species, Pyrenophora species on corn, cereals, rice and turf, e.g. D. teres to barley or D. tritici-repentis to wheat,

Esca at grapevine, caused by Phaeoacremonium chlamydosporium, Ph.

Aleophilum and Formitipora punctata (syn. Phellinus punctatus),

Exserohilum species on maize, - Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,

Fusarium and Verticillium species on various plants, e.g. F. graminearum or F. culmorum on cereal or F. oxysporum on a variety of plants, e.g. Tomatoes,

Gaeumanomyces graminis on cereals, - Gibberella species on cereals and rice (e.g., Gibberella fujikuroi on rice),

Grainstaining complex on rice,

Helminthosporium species on corn and rice,

Michrodochium nivale on cereals,

Mycosphaerella species on cereals, bananas and peanuts, e.g. M. graminicola on wheat or M. fijiesis on bananas,

Peronospora species on cabbage and bulbous plants, e.g. P. brassicae on cabbage or P. destructor on onion,

Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans,

Phomopsis species on soybeans and sunflowers, - Phytophthora infestans on potatoes and tomatoes,

Phytophthora species on various plants, e.g. P. capsici on paprika,

Plasmopara viticola on vines,

Podosphaera leucotricha on apple,

Pseudocercosporella herpotrichoides on cereals, Pseudoperonospora on various plants, e.g. P. cubensis on cucumber or

P. humili on hops,

Puccinia species on various plants, e.g. P. triticina, P. striformins, P. hordei or P. graminis on cereals or P. asparagi on asparagus,

Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum, Entlyoma oryzae on rice,

Pyricularia grisea on lawn and cereals, Pythium spp. on grass, rice, maize, cotton, rapeseed, sunflower, sugar beets, vegetables and other plants, eg P. ultiumum on various plants, P. aphanidermatum on lawn,

Rhizoctonia species on cotton, rice, potatoes, turf, corn, oilseed rape, sugar beets, vegetables and on various plants, e.g. R. solani on turnips and various plants,

Rhynchosporium secalis on barley, rye and triticale, Sclerotinia species on rape and sunflower, Septoria tritici and Stagonospora nodorum on wheat, - Erysiphe (syn. Uncinula) necator on grapevine, Setospaeria species on maize and turf, Sphacelotheca reilinia on maize, Thievaliopsis species Soybeans and cotton, Tilletia species on cereals, - Ustilago species on cereals, corn and sugar cane, eg U. maydis on corn, Venturia species (scab) on apples and pears, e.g. V. inaequalis to apple.

The mixtures according to the invention are also suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. In wood preservation, particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyomyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover, in the protection of the following yeasts: Candida spp. and Saccharomyces cerevisae.

The compound (s) I with at least one of the active ingredients II can be applied simultaneously, namely jointly or separately, or in succession, the sequence in the case of separate application generally having no effect on the control result.

The pure active substances I to II are preferably used in the preparation of the mixtures, to which other active substances can be added against harmful fungi or against other pests such as insects, spider animals or nematodes or else herbicidal or growth-regulating active substances or fertilizers.

Such mixtures of three active substances consist of a mixture of a compound of formula I, particularly 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid-N- (3 ', 4 ¹ - difluorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ', 4 ¹ - dichlorobiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1 H-pyrazole-4-carboxylic acid-N- (3 ', 4 ¹ - difluorobiphenyl-2-yl) amide or 1-methyl-3- difluoromethyl-1H-pyrazole-4-carboxylic acid N- (S ')' - dichlorobiphenyl-1-yl-amide, an azole from group A), in particular epoxiconazole, metconazole, triticonazole or fluquinconazole, and an insecticide, wherein especially fipronil and neonicotinoids such as acetamipride, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam.

Usually, mixtures of at least one compound I and at least one active ingredient II are used. In this case, mixtures of at least one compound I with two or optionally several active components can offer particular advantages.

As further active components in the above sense, especially the above-mentioned active compounds II and in particular the above-mentioned preferred active compounds II come into question.

Compound (s) I and active compound (II) II are usually used in a weight ratio of 100: 1 to 1: 100, preferably 20: 1 to 1:20, in particular 10: 1 to 1:10.

If desired, the further active components are mixed in a ratio of from 20: 1 to 1:20 to give compound I.

The application rates of the mixtures according to the invention, especially in agricultural crops, depending on the nature of the compounds I and II and the desired effect, at 5 g / ha to 2000 g / ha, preferably 20 g / ha to 1500 g / ha, in particular 50 g / ha to 1000 g / ha.

The application rates for the compound (s) I are accordingly generally 1 to 1000 g / ha, preferably 10 to 900 g / ha, in particular 20 to 750 g / ha.

The application rates for the active compounds II are correspondingly generally 1 to 2000 g / ha, preferably 10 to 1500 g / ha, in particular 40 to 1000 g / ha.

In the seed treatment, application rates of mixture of 1 to 1000 g per 100 kg of seed, preferably 1 to 750 g per 100 kg, in particular 5 to 500 g per 100 kg of seed are generally used.

The method for controlling harmful fungi is carried out by the separate or combined application of compound (s) I and at least one of the active compounds II, or a mixture of compound (s) I with at least one of the active compounds II, 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, or the compound (s) I and at least one of the active compounds II, can be converted into the customary formulations, for example Solutions, emulsions, suspensions, dusts, powders, pastes or granules. The application form depends on the respective purpose; It should in any case ensure the finest possible and uniform distribution of the mixture according to the invention.

The formulations are prepared in a manner known per se, e.g. by stretching the active compounds with solvents and / or carriers, if desired using emulsifiers and dispersants. Suitable solvents / auxiliaries are essentially:

Water, aromatic solvents (for example Solvesso ^® products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol),

Ketones (e.g., cyclohexanone, gamma-butyrolactone), pyrrolidones (N-methylpyrrolidone, N-octylpyrrolidone), acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids, and fatty acid esters. In principle, solvent mixtures can also be used. Excipients such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkyl sulfonates and arylsulfonates) and dispersants such as lignin-sulphite liquors and methylcellulose.

The surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristerylphenyl polyglycol ethers, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene , Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration. For the production of directly sprayable solutions, emulsions, pastes or oil dispersions, mineral oil fractions of medium to high boiling point, such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg toluene, Xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, metha- nol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules (e.g., coated, impregnated or homogeneous granules) can be prepared by binding the active ingredients to at least one solid carrier. Solid carriers are e.g. Mineral earths such as silica gels, silicates, talc, kaolin, ataclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, 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 from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the compound (s) I and at least one of the active compounds II or of the mixture of compound (I) I with at least one of the active ingredients II. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR or HPLC spectrum).

Examples of formulations are: 1. Products for dilution in water

A) Water-soluble concentrates (SL) 10 parts by weight of a mixture according to the invention are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with an active substance content of 10% by weight.

B) Dispersible Concentrates (DC)

20 parts by weight of a mixture according to the invention are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersing agent, e.g. Polyvinylpyrrolidone, dissolved. Dilution in water gives a dispersion. The active ingredient content is 20% by weight

C) Emulsifiable Concentrates (EC)

15 parts by weight of a mixture according to the invention are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate in each case 5 parts by weight). Dilution in water results in an emulsion. The formulation has an active substance content of 15% by weight. D) Emulsions (EW, EO)

25 parts by weight of a mixture according to the invention are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is added by means of an emulsifying machine (for example Ultraturrax) in 30 parts by weight of water and brought to a homogeneous emulsion. Dilution in water results in an emulsion. The formulation has an active ingredient content of 25% by weight.

E) Suspensions (SC, OD) 20 parts by weight of a mixture according to the invention are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to give a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient. The active ingredient content in the formulation is 20% by weight.

F) Water-dispersible and water-soluble granules (WG, SG)

50 parts by weight of a mixture according to the invention are finely ground with the addition of 50 parts by weight of dispersing and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient. The formulation has an active ingredient content of 50% by weight.

G) Water-Dispersible and Water-Soluble Powders (WP, SP) 75 parts by weight of a mixture according to the invention are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight.

2. Products for direct application

H) dusts (DP)

5 parts by weight of a mixture according to the invention are finely ground and intimately mixed with 95 parts by weight of finely divided kaolin. This gives a dust with an active ingredient content of 5 wt .-%.

J) Granules (GR, FG, GG, MG)

0.5 parts by weight of a mixture according to the invention are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with an active ingredient content of 0.5 wt .-%. K) ULV solutions (UL)

10 parts by weight of a mixture according to the invention are dissolved in 90 parts by weight of an organic solvent, e.g. XyIoI, solved. This gives a product for direct application with an active ingredient content of 10 wt .-%.

The active compounds may be used as such, in the form of their formulations or the forms of use prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, misting, dusting, scattering or pouring. The forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of active ingredients.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders, oil dispersions) by adding water. For the preparation of emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetter, tackifier, dispersant or emulsifier. However, it is also possible to prepare from active substance wetting, adhesion, dispersing or emulsifying agents and any solvents or oil concentrates which are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.

To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, other pesticides, bactericides, if desired, also just immediately before use (tank mix), can be added. These agents are usually mixed to give the mixtures according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.

As adjuvants in this sense are in particular: organically modified polysiloxanes, eg Break Thru S 240 ^® ; Alcohol alkoxylates, eg. As Atplus 245 ^®, Atplus MBA 1303 ^®, Plurafac LF 300 ^® and Lutensol ON 30 ^®; EO-PO block polymers, eg. B. Pluro- never RPE 2035 and Genapol ^® B ^®; Alcohol ethoxylates, eg. As Lutensol XP 80 ^®; and sodium dioctylsulfosuccinate, e. B. Leophen RA ^®. The compounds I and II, or the mixtures or the corresponding formulations are applied by the harmful fungi, their habitat or the plants, seeds, soils, areas, materials or spaces to be kept free of them with a fungicidally effective amount of the mixture, or the compound (s) I and at least one of the active ingredients II when applied separately. The application can be made before or after the attack by the harmful fungi.

Preparation Examples

1.) Synthesis of ortho- (3,4-dichlorophenyl) -aniline

To a solution of 20.47 g of 2-bromoaniline, 24.98 g of 2,4-dichlorophenylboronic acid and 25.23 g of sodium carbonate in a mixture of 150 ml of water and 450 ml of ethylene glycol dimethyl ether were added 0.14 g of tetrakistriphenylphosphine palladium (O) given. The mixture was stirred for 48 hours under reflux. The batch was concentrated under reduced pressure. The residue was taken up in methyl tert-butyl ether, washed once with aqueous sodium bicarbonate solution and four times with water, dried over sodium sulfate and concentrated under reduced pressure. Chromatographic purification with a mixture of toluene and cyclohexane (1: 2) gave 15.5 g of the product as a pale yellow powder.

2.) Synthesis of 1-methyl-3-trifluoromethyl-N- (ortho- (3,4-dichlorophenyl) phenyl) -pyrazole-4-carboxylic acid amide.

In 10 ml of toluene were dissolved 0.32 g of 1-methyl-3-trifluoromethyl-pyrazole-4-carboxylic acid chloride, 0.36 g of ortho- (3,4-dichlorophenyl) aniline and 0.23 g of triethylamine. After 4 hrs. Was stirred at room temperature, 20 ml of methyl tert-butyl ether were added, washed twice with 5% hydrochloric acid, twice with 5% sodium hydroxide solution and once with aqueous sodium chloride solution. The organic phase was dried over sodium sulfate and concentrated under reduced pressure. After chromatographic purification with a mixture of toluene and methyl tert-butyl ether, 0.32 g of the product was obtained as a colorless powder; Mp: 131-133 ° C.

In addition to the compound I described above, the following Table 9 lists, by way of example, further 3,5-disubstituted pyrazolecarboxylic acid biphenylamides of the formula I which were prepared or can be prepared in the same way. Table 9

example

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

The active compounds were prepared separately or together as a stock solution with 25 mg of active ingredient, which with a mixture of acetone and / or dimethyl sulfoxide and the emulsifier Uniperol ^® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) in the volume ratio solvent- Emulsifier from 99 to 1 ad 10 ml was filled. It was then made up to 100 ml with water. This stock solution was diluted with the described solvent-emulsifier-water mixture to the drug concentration given below.

Alternatively, the active ingredients epoxiconazole, triticonazole and pyraclostrobin were used as a commercially available ready-made formulation and diluted with water to the stated active substance concentrations.

The visually determined values for the percentage of affected leaf areas were converted into efficiencies as% of the untreated control.

The efficiency (W) was calculated according to the formula of Abbot as follows:

W = (1-α / β) 100

α corresponds to the fungal infestation of the treated plants in% and β corresponds to the fungal infestation of the untreated (control) plants in%

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

The expected efficiencies of the drug mixtures were determined according to the Colby formula [RS Colby, Calculating synergistic and antagonistic responses of herbicide combinations, Weeds ^ 5, 20-22 (1967)] and compared with the observed efficiencies. Colby formula: E = x + y - xy / 100

E expected efficiency, expressed as% of untreated control, when using the mixture of Active Agents A and B at concentrations a and b; x the efficiency, expressed in% of the untreated control, when using active substance A at concentration a; y the efficiency, expressed in% of the untreated control, when using active substance B in concentration b.

Use Example 1 - Efficacy against tomato blight caused by Alternaria solani

Leaves of potted tomato plants were sprayed to drip point with an aqueous suspension in the drug concentration below. The following day, the leaves were infected with an aqueous spore suspension of Alternaria solani in 2% biomalt solution with a density of 0.17 × 10 ⁶ spores / ml. The plants were then placed in a water vapor-saturated chamber at temperatures between 20 and 22 ⁰ C. After 5 days, the disease on the untreated, but infected control plants had developed so strongly that the infestation could be determined visually in%.

Application Example 2 - Activity against gray mold on pepper leaves caused by Botrytis cinerea at 1 day of protective application

Paprika seedlings of the cultivar "Neusiedler Ideal Elite" were sprayed to drip point with an aqueous suspension in the concentration of active compound stated below, after 2-3 leaves had developed well. The next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 x 10 ⁶ spores / ml in a 2% aqueous biomalt solution. Subsequently, the test plants were placed in a climatic chamber with 22 to 24 ⁰ C, darkness and high humidity. After 5 days, the extent of fungal attack on the leaves could be determined visually in%.

Use Example 3 Activity against tomato late blight on tomatoes caused by Phytophthora infestans in protective treatment

Leaves of potted tomato plants were sprayed to drip point with an aqueous suspension in the concentration of active compound specified below. The following day, the leaves were infected with an aqueous sporangium suspension of Phytophthora infestans. Subsequently, the plants were placed in a water vapor-saturated chamber at temperatures between 18 and 20 ⁰ C. After 6 days, the late blight on the untreated but infected control plants had developed so strongly that the infestation could be determined visually in%.

Use Example 4 - Activity against wheat powdery mildew caused by Erysiphe [syn. Blumeria] graminis fomna specialis. tritici

Leaves of potted wheat seedlings were sprayed to drip point with aqueous suspension in the concentration of active compound given below. The suspension or emulsion was prepared as described above. 24 hours after the spray coating began to dry, the plants were dusted with spores of the wheat powdery mildew (E- rysiphe [syn.blumeria] graminis fomna specialis.tritici). The test plants were then placed in a greenhouse at temperatures between 20 and 24 ° C and 60 to 90% relative humidity. After 7 days, the extent of mildew development was determined visually in% infestation of the entire leaf area.

Use Example 5 - Curative activity against wheat brown rust caused by Puccinia recondita

Leaves of potted wheat seedlings of the variety "Chancellor" were inoculated with a spore suspension of the brown rust (Puccinia recondita). Thereafter, the pots were placed for 24 hours in a high humidity chamber (90 to 95%) and 20 to 22 ⁰ C. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. The infected plants were sprayed the next day with the above-described active ingredient solution in the drug concentration indicated below to drip point. After the spray coating had dried on, the test plants were cultivated in the greenhouse at temperatures between 20 and 22 ^° C. and 65 to 70% relative atmospheric humidity for 7 days. Then the extent of rust fungus development on the leaves was determined.

Use Example 6 Protective Efficacy Against Puccinia recondita on Wheat (Wheat Brown Rust)

Leaves of potted wheat seedlings of the variety "Chancellor" were sprayed to drip point with an aqueous suspension in the active ingredient concentration given below. The next day, the treated plants were inoculated with a spore suspension of the wheat brown rust (Puccinia recondita). Subsequently, the plants were placed in a high humidity chamber (90-95 %) at 20 to 22 ⁰ C. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. The following day, the test plants were returned to the greenhouse and cultured at temperatures between 20 and 22 ⁰ C and 65 to 70% relative humidity for a further 7 days. Then the extent of rust fungus development on the leaves was visually determined.

Application Example 7 - Efficacy against barley spot disease caused by Pyrenophora teres at 1 day of protective application

Leaves of potted barley seedlings were sprayed to drip point with aqueous suspension in the concentration of active compound given below. 24 hours after the spray coating had dried on, the test plants were incubated with an aqueous spore suspension of Pyrenophora [syn. Drechslera] teres, the causative agent of net blotch inoculation. Subsequently, the test plants were placed in the greenhouse at temperatures between 20 and 24 ⁰ C and 95 to 100% relative humidity. After 6 days, the extent of disease development was determined visually as% of total leaf area.

Claims

claims

1. Fungicidal mixtures for controlling phytopathogenic harmful fungi, containing as active components

1) at least one 3,4-disubstituted pyrazolecarboxylic acid biphenylamide of the formula I

in which X is oxygen or sulfur, R ¹ and R ² independently of one another are fluorine, chlorine, methyl, cyano, nitro, methoxy or trifluoromethyl and R ^{3 is} difluoromethyl or trifluoromethyl, and

2) at least one active ingredient II selected from groups A) to F):

A) Azoles selected from bitertanol, bromuconazole, cyproconazole, difonoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, triadimefon , Triadimol, tebuconazole, tetraconazole, triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamide, benomyl, carbendazim, thiabendazole, fuberidazole, ethaboxam, etridiazole, hymexazole;

B) strobilurins selected from azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, methominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, enestroburine, (2-chloro-5- [1- (3-methylbenzyloxyimino) -ethyl ] benzyl) -carbamic acid methyl ester, (2-chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) -carbamic acid methyl ester and 2-ortho - [(2,5-dimethylphenyl - oxymethylene) phenyl] -3-methoxy-acrylic acid methyl ester;

C) Carboxylic Acid Amides Selected from Carboxine, Benalaxyl, Boscalid, Fenhexamide, Flutolanil, Furametpyr, Mepronil, Metalaxyl, Mefenoxam, Ofurace, Oxadixyl, Oxycarboxine, Penthiopyrad, Thifluzamide, Tiadinil, 3,4-Dichloro-N- (2) cyanophenyl) isothiazole-5-carboxamide, Dimethomorph, flumorph, flumetover, fluopicolide (picobenzamide), zoxamide, carpropamide, diclocymet, mandipropamide, N- (2- [4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxy-phenyl ) -ethyl) -2-methanesulfonylamino-3-methylbutyramide, N- (2- [4- [3- (4-chlorophenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) 2-ethanesulfonylamino-3-methyl-butyranedione, 3- (4-chloro-phenyl) -3- (2-isopropoxy-carbonylamino-3-methyl-butyrylamino) -propionic acid methyl ester, compounds of the formula III

in which R ^{4 is} methyl or ethyl,

4-Difluoromethyl-2-methyl-thiazole-5-carboxylic acid N- (4'-bromo-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid N- (4 ' - trifluoromethyl-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid N- (4'-chloro-3'-fluorobiphenyl-2-yl) -amide, 3 Difluoromethyl-1-methyl-pyrazole-4-carboxylic acid N- (3 ', 4'-dichloro-4-fluoro-biphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-pyrazole-4-carboxylic acid N- (3 ', 4'-dichloro-5-fluoro-biphenyl-2-yl) -amide and 3,4-dichloro-isothiazole-5-carboxylic acid N- (2-cyano-phenyl) -amide;

Heterocyclic compounds selected from fluazinam, pyrifenox,

Bupirimate, cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil, triforin, fenpiclonil, fludioxonil, aldimorph, dodermorph, fenpropimorph, tridemorph, fenpropidin, iprodione, procymidon, vinclozolin, famoxadone, fenamidone, octhilinone, probenazole, 5 Chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, anilazine , Diclomezine, pyroquilone, proquinazide, tricyclazole, the compound of formula IV (2-butoxy-6-iodo-3-propylchromen

Acibenzolar-S-methyl, Captafol, Captan, Dazomet, Folpet, Fenoxanil,

Quinoxyfen, 3- (3-bromo-6-fluoro-2-methyl-indol-1-sulfonyl) - [1, 2,4] triazole-1-sulfonic acid dimethylamide of the formula V

E) carbamates selected from Mancozeb, Maneb, Metam, Metiram,

Ferbam, Propineb, Thiram, Zineb, Ziram, Diethofencarb, Iprovalicarb, Flubenthiavalicarb, Propamocarb, N- (1- (1- (4-cyanophenyl) ethanesulfonyl) -but-2-yl) carbamic acid (4-fluorophenyl) ester, 3 - (4-chloro-phenyl) -3- (2-isopropoxycarbonylamino) -3-met el VI

and carbamato oxime ethers of formula VII

Z is N or CH;

F) Other fungicides selected from guanidines: dodin, iminoctadine, guazatine,

Antibiotics: Kasugamycin, Streptomycin, Polyoxin, Validamycin A, Nitrophenyl derivatives: Binapacryl, Dinocap, Dinobuton, Sulfur-containing heterocyclyl compounds: Dithianone, Isoprothiolane, Organometallic compounds: Fentin salts such as Fentin acetate, Organophosphorus compounds: Edifenphos, Iprobenfos, Fosetyl,

Fosetyl-aluminum, phosphorous acid and its salts, pyrazophos, tolclofos-methyl,

Organochlorine compounds: chlorothalonil, dichlofluanid, flusulfamide, hexachlorobenzene, phthalide, pencycuron, quintozene, thiophanate-methyl, tolylfluanid,

Inorganic active ingredients: Bordeaux broth, copper acetate, copper hydroxide, copper oxychloride, basic copper sulphate, sulfur, others: cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone and spiroxamine;

r synergistically effective amount.

2. Fungicidal mixtures according to claim 1, comprising as component 1) a 3,4-disubstituted Pyrazolcarbonsäurebiphenylamid of formula I, wherein R ¹ and R ^{2 are} independently fluorine, chlorine, methyl, cyano, methoxy or trifluoromethyl.

3. Fungicidal mixtures according to claim 1, comprising as component 1) a 3,4-disubstituted Pyrazolcarbonsäurebiphenylamid of formula I, wherein R ¹ and R ^{2 are} independently fluorine, chlorine, cyano or methoxy.

4. Fungicidal mixtures according to claim 1, comprising as component 1) a 3,4-disubstituted Pyrazolcarbonsäurebiphenylamid of formula I, wherein R ¹ and R ^{2 are} independently fluorine or chlorine.

5. Fungicidal mixtures according to claim 1, containing as component 1) 1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxylic acid N- (3 ', 4 ¹ -dichlorbiphenyl-2-yl) - amide, 1 - Methyl 3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-chloro-4 ¹ -fluorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4 carboxylic acid N- (S ')' - difluorobiphenyl-1-yl-amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-fluoro-4 ¹ -chlorobiphenyl-2-yl ) -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-chloro-4 ¹ -fluorobiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1 H-pyrazole-4-carboxylic acid N- (3 ¹ , 4 ¹ -difluorobiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ^l , 4 ¹ -dichlorobiphenyl-2-yl) amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-fluoro-4'-chlorobiphenyl-2-yl) -amide, 1 - Methyl 3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (S'-methyl-1-chlorobiphenyl) -YO-amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- ( 3'-methyl-4 ¹ -flu orbiphenyl-2-yl) -amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ¹ -methyl-4 ¹ -fluorobiphenyl-2-yl) -amide, 1-methyl- 3- difluoromethyl-1 H-pyrazole-4-carboxylic acid-N- ^(3-methyl-l 4 ^l -chlorbiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ^L -nitro-4 ^L -chlorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxylic acid N- (3 ', 4 ¹ -dimethylbiphenyl-2- yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ¹ -trifluoromethyl-4 ¹ -chlorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl- 1 H-pyrazole-4-carboxylic acid N- (3 ¹ -trifluoromethyl-4 ¹ -nitrobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1 H-pyrazole-4-carboxylic acid N- (3 ^{l-methyl-4'-methoxy-biphenyl-2-yl)} - amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid-N- (3 ', 4 ¹ - dimethoxybiphenyl-2-yl) -amide , 1-Methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-fluoro-4 ¹ -methoxybiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole -4-carboxylic acid N- (3'-methoxy-4 ¹ -chlorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ^l -chloro-4 ^l -methylbiphenyl-2-yl) -amide, 1-methyl 3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3'-trifluoromethyl-4 ¹ -fluorobiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid -N- (S'-cyano) -1-methoxybiphenyl-1-yl-amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4 carboxylic acid N- (3 ¹ -cyano-4 ¹ -methoxybiphenyl-2-yl) -amide, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ^l -nethoxy-4 ^l - cyanobiphenyl-2-yl) amide, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ¹ -methoxy-4 ¹ -cyanobiphenyl-2-yl) -amide, 1-methyl- 3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (S'-fluoM'-methylbiphenyl) -yO-1-ol, 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ^1- nitro-4 ¹ -methoxybiphenyl-2-yl) -amide or 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid N- (3 ^l -chloro-4 ^l -nethoxybiphenyl-2-yl) - amid.

6. Fungicidal mixtures according to one of claims 1 to 5, comprising at least one compound of formula I and at least one active compound of formula II in a weight ratio of 100: 1 to 1: 100.

7. A composition containing a fungicidal mixture according to claims 1 to 5 and at least one liquid or solid carrier.

8. A method for controlling phytopathogenic harmful fungi, characterized in that the harmful fungi, their habitat or the plants to be protected against fungal attack, the soil, seeds, areas, materials or spaces with an effective amount of at least one compound I and at least one active ingredient Il treated according to claims 1 to 5.

9. The method according to claim 8, characterized in that the components 1) and 2) according to claims 1 to 5 at the same time, and jointly or separately, or successively auszustingt.

10. The method according to claim 8 or 9, characterized in that the components 1) and 2) according to claims 1 to 5 in an amount of 5 g / ha to 2000 g / ha expends.

11. The method according to claim 8 or 9, characterized in that applying the components 1) and 2) according to claims 1 to 5 in an amount of 1 g to 1000 g per 100 kg of seed.

12. Seed containing the mixture according to claims 1 to 5 in an amount of 1 g to 1000 g per 100 kg of seed.

13. Use of the compounds I and II according to claims 1 to 5 for the preparation of a suitable for controlling phytopathogenic harmful fungi agent.