JP2009500311A - Disinfectant mixture based on 3,5-disubstituted N-biphenylpyrazole carboxamide - Google Patents

Abstract

The present invention relates to 1): Formula (I) wherein X represents oxygen or sulfur; R ¹ and R ² are cyano, nitro, halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -halogen Alkyl, methoxy, difluoromethoxy or trifluoromethoxy; R ³ represents halogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkyl halide; R ⁴ represents hydrogen or halogen) At least one 3,5-disubstituted pyrazolecarboxylic acid biphenylamide, and 2) the following groups A) to F): group A) containing azoles, group B) containing strobilurins, carboxylic acid amides Group C), heterocyclic group D), carbamates group E), and other fungicides group F) synergistically effective with at least one active substance II It is related with the disinfectant mixture contained in a proper amount. Furthermore, a method for controlling harmful fungi with a mixture of at least one compound I and at least one active substance II, the use of said compound I and active substance II to produce such a mixture, and a medicament containing said mixture and Seeds are also listed.

Description

As an active ingredient, the present invention
1) At least one formula I:

(Wherein the substituents are as defined below:
X is oxygen or sulfur;
R ¹ and R ² are independently of one another cyano, nitro, halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, methoxy, difluoromethoxy or trifluoromethoxy;
R ³ is halogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -haloalkyl;
R ⁴ is hydrogen or halogen)
3,5-disubstituted N-biphenylpyrazole carboxamide represented by:
2) The following groups A) to F):
A) Viteltanol, bromconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriahol, hexaconazole, imibenconazole, ipconazole, metconazole, Microbutanyl, penconazole, propiconazole, prothioconazole, cimeconazole, triadimethone, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, pefrazoate, imazalyl, triflumizole, cyazofamide, benomyl, carbendazim, thiabendazole Azoles selected from the group consisting of ethaboxam, etridiazole, and himexazole;
B) Azoxystrobin, Dimoxystrobin, Enestrobrin, Fluoxastrobin, Cresoxime-methyl, Metominostrobin, Orisatrobin, Picoxystrobin, Pyraclostrobin, Trifloxystrobin, Enestrobrin, Methyl (2-Chloro-5- [1- (3-methylbenzyloxyimino) ethyl] benzyl) carbamate, methyl (2-chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl ) Strobilurins selected from the group consisting of carbamate and methyl 2- (ortho- (2,5-dimethylphenyloxymethylene) phenyl) -3-methoxyacrylate;
C) Carboxin, Benalaxyl, Boscalid, Fenhexamide, Flutolanil, Frametopyr, Mepronil, Metalaxyl, Mefenoxam, Offras, Oxadixyl, Oxycarboxyl, Penthiopyrad, Thifluzamide, Thiazinyl, 3,4-Dichloro-N- (2-cyanophenyl) ) Isothiazole-5-carboxamide, dimethomorph, flumorph, flumetvar, fluopicolide (picobenzamide), zoxamide, carpropamide, diclosimet, mandipropamide, N- (2- (4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl) ethyl) -2-methanesulfonylamino-3-methylbutyramide, N- (2- (4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl) ethyl ) -2-ethanesulfonylamino-3-methylbutyramide, methyl 3- (4-chloro) Eniru) -3- (2-isopropoxycarbonyl-3-methyl-butyryl-amino) - propionate, formula III:

(Wherein R ⁵ is methyl or ethyl)
N- (4′-bromobiphenyl-2-yl) -4-difluoromethyl-2-methylthiazole-5-carboxamide, N- (4′-trifluoromethylbiphenyl-2-yl)- 4-difluoromethyl-2-methylthiazole-5-carboxamide, N- (4′-chloro-3′-fluorobiphenyl-2-yl) -4-difluoromethyl-2-methylthiazole-5-carboxamide, N- ( 3 ', 4'-dichloro-4-fluorobiphenyl-2-yl) -3-difluoromethyl-1-methylpyrazole-4-carboxamide and N- (2-cyanophenyl) -3,4-dichloroisothiazole-5 -Carboxamides selected from the group consisting of carboxamides;
D) Fluazinam, pyriphenox, bupirimate, cyprodinil, phenalimol, ferrimzone, mepanipyrim, nuarimol, pyrimethanyl, trifoline, fenpicuronyl, fludioxonil, aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, procymidone, vinclozoline, , Phenamidon, octyrinone, probenazole, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl)-[1,2,4] triazolo [1, 5-a] pyrimidine, anilazine, dichromedin, pyroxylone, proquinazide, tricyclazole, Formula IV:

Embedded image (2-butoxy-6-iodo-3-propylchromen-4-one), acibenzoral-S-methyl, captahol, captan, dazomet, holpet, phenoxanyl, quinoxyphene, and formula V:

N, N-dimethyl-3- (3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1,2,4] triazole-1-sulfonamide represented by A heterocyclic compound;
E) Mancozeb, Maneb, Metam, Methylam, Farbum, Propineb, Tiram, Zineb, Zillam, Dietofencarb, Iprovaricarb, Fullbenchalicarb, Propamocarb, 4-Fluorophenyl N- (1- (1- (4-Cyanophenyl) -Ethanesulfonyl) but-2-yl) carbamate, formula VI:

Methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propionate represented by the formula:

(Wherein Z is N or CH) carbamates selected from the group consisting of carbamate oxime ethers;
F) Guanidines: dodin, iminotadine, guazatine,
Antibiotics: kasugamycin, streptomycin, polyoxin, validamycin A,
Nitrophenyl derivatives: Binapacryl, Zinocup, Dinobutone,
Sulfur-containing heterocyclyl compounds: dithianone, isoprothiolane,
Organometallic compounds: fentin salts, such as fentin acetate,
Organophosphorus compounds: edifenphos, iprobenphos, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, pyrazophos, tolcrophos-methyl,
Organochlorine compounds: chlorothalonil, diclofuranide, fursulfamide, hexachlorobenzene, phthalide, pencyclone, quintozene, thiophanate-methyl, tolylfuranide,
Inorganic active compounds: Bordeaux solution, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur,
Other: relates to a fungicide mixture comprising a synergistically effective amount of another fungicide selected from the group consisting of cyflufenamide, simoxanyl, dimethymol, ethylimol, flaxyl, metolaphenone and spiroxamine.

  Furthermore, the present invention provides a method for controlling harmful fungi using a mixture of at least one compound I and at least one active compound II, the use of compounds I and II for preparing such mixtures, and further a mixture thereof. Containing compositions and seeds.

  Substituted biphenylamides of the formula I are known from EP-A 589 301. This EP-A 589 301 also discloses its method of preparation and a list of possible mixed partners selected from the group consisting of fungicides, bactericides, acaricides, nematicides or insecticides.

  Substituted biphenylamides are also known from WO 01/42223. However, these compounds are only monosubstituted in the biphenyl group.

  JP-A 09-132567 (JP-A 09/132567) describes disubstituted biphenylanilides in which the phenyl ring is substituted with trifluoromethyl.

  WO 2005/34628 describes in particular mixtures of pyrazole carboxamides with various other fungicidal active compounds. The pyrazole carboxamides described in this publication differ from the present compound I particularly in terms of the substitution pattern of the biphenyl group.

  2,4-disubstituted N-biphenylamides are known from WO 2005/123689 and WO 2005/123690, and 3,5-disubstituted biphenylamides are known from the prior German application 102005007160.0.

  However, the biphenylamides described and their known mixtures are not fully satisfactory, especially with low application rates.

The active compounds II mentioned above as component 2), their preparation and their action against harmful fungi are generally known (see eg http://www.hclrss.demon.co.uk/index.html ) These 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);
Oflas, (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, 85% The above is 4-dodecyl-2,5 (or 2,6) -dimethylmorpholine, where “alkyl” may be octyl, decyl, tetradecyl and hexadecyl with a 1: 1 cis / trans ratio. [CAS RN 91315-15-0];
Dodin, 1-dodecylguanidinium acetate (Plant Dis. Rep., Vol. 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) -1- [3- (4-tert-butylphenyl) -2-methylpropyl] piperidine (DE-A 27 52 096);
Guazatine, a mixture of reaction products obtained by amidation of industrial great iminodi (octamethylene) diamine, containing various guanidines and polyamines [CAS RN 108173-90-6];
Iminotadine, 1,1'-iminodi (octamethylene) diguanidine (Congr. Plant Pathol., 1., p.27 (1968));
Spiroxamine, (8-tert-butyl-1,4-dioxaspiro [4.5] dec-2-yl) diethylamine (EP-A 281 842);
Tridemorph, 2,6-dimethyl-4-tridecylmorpholine (DE-A 11 64 152);
Pyrimethanil, 4,6-dimethylpyrimidin-2-ylphenylamine (DD-A 151 404);
Mepanipyrim, (4-methyl-6-prop-1-ynylpyrimidin-2-yl) phenylamine (EP-A 224 339);
Cyprodinil, (4-cyclopropyl-6-methylpyrimidin-2-yl) phenylamine (EP-A 310 550);
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-trimethoxy-6'-methylspiro [benzofuran-2 (3H), 1'-cyclohexa-2'-ene] -3,4'-dione [CAS RN 126-07 -8];
Kasugamycin, 3-O- [2-amino-4-[(carboxyiminomethyl) amino] -2,3,4,6-tetradeoxy-α-D-arabino-hexopyranosyl] -D-kilo-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 ^5,7 ] octacosa-8,14, 16,18,20-pentaene-25-carboxylic acid [CAS RN 7681-93-8];
Polyoxin, 5- (2-amino-5-O-carbamoyl-2-deoxy-L-xylonamide) -1- (5-carboxy-1,2,3,4-tetrahydro-2,4-dioxopyrimidine-1 -Yl) -1,5-dideoxy-β-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-methylamino-α-L -Glucopyranosyl) -3-C-formyl-α-L-lyxofuranosyloxy] -2,5,6-trihydroxycyclohexa-1,3-ylene} diguanidine (J. Am. Chem. Soc. Vol. 69, p.1234 (1947));
Vitertanol, β-([1,1′-biphenyl] -4-yloxy) -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol (DE 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] triazol-1-ylbutan-2-ol (US 4 664 696);
Diphenoconazole, 1- {2- [2-chloro-4- (4-chlorophenoxy) phenyl] -4-methyl- [1,3] dioxolan-2-ylmethyl} -1H- [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 (imazalyl), 1- [2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl] -1H-imidazole (Fruits, 1973, Vol. 28, p. 545);
Epoxyconazole, (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] -triazol-1-yl-3H-quinazolin-4-one (Proc. Br. Crop Prot. Conf .-Pests Dis., 5-3, 411 (1992));
Flusilazole, 1-{[bis- (4-fluorophenyl) methylsilanyl] methyl} -1H- [1,2,4] triazole (Proc. Br. Crop Prot. Conf.-Pests Dis., Vol. 1, p. 413 (1984));
Flutriahole, 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-ylhexan-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] triazol-1-ylmethylcyclopentanol (GB 857 383);
Microbutanyl, 2- (4-chlorophenyl) -2- [1,2,4] triazol-1-ylmethylpentanenitrile (CAS RN 88671-89-0);
Penconazole, 1- [2- (2,4-dichlorophenyl) pentyl] -1H- [1,2,4] triazole (Pesticide Manual, 12th Ed. 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);
Prochloraz, N- (propyl- [2- (2,4,6-trichlorophenoxy) ethyl]) imidazole-1-carboxamide (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);
Cimeconazole, 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] triazol-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 );
Triazimephone, 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] triazol-1-ylethylidene) -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, N-isopropyl-3- (3,5-dichlorophenyl) -2,4-dioxoimidazolidine-1-carboxamide (GB 13 12 536);
Microzoline, (RS) -3- (3,5-dichlorophenyl) -5-methoxymethyl-5-methyl-1,3-oxazolidine-2,4-dione [CAS RN 54864-61-8];
Procimidone, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide (US 3 903 090);
Vinclozoline, 3- (3,5-dichlorophenyl) -5-methyl-5-vinyloxazolidine-2,4-dione (DE-A 22 07 576);
Farbum, iron dimethyldithiocarbamate (3+) (US 1 972 961);
Narbum, disodium ethylenebis (dithiocarbamate) (US 2 317 765);
Maneb, ethylenebis (dithiocarbamate) manganese (US 2 504 404);
Mancozeb, ethylenebis (dithiocarbamic acid) manganese polymer complex zinc salt (GB 996 264);
Metam, methyldithiocarbamic acid (US 2 791 605);
Methylam, ethylenebis (dithiocarbamate) zinc ammonialate (US 3 248 400);
Propinebu, propylene bis (dithiocarbamate) zinc polymer (BE 611 960);
Polycarbamate, bis (dimethylcarbamodithioato-κS, κS ') [μ-[[1,2-ethanediylbis [carbamo-dithioato-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];
Dinebu, ethylenebis (dithiocarbamate) zinc (US 2 457 674);
Anilazine, 4,6-dichloro-N- (2-chlorophenyl) -1,3,5-triazine-2-amine (US 2 720 480);
Benomyl, N-butyl-2-acetylaminobenzimidazole-1-carboxamide (US 3 631 176);
Boscalid, 2-chloro-N- (4′-chlorobiphenyl-2-yl) nicotinamide (EP-A 545 099);
Carbendazim, methyl (1H-benzimidazol-2-yl) carbamate (US 3 657 443);
Carboxin, 5,6-dihydro-2-methyl-N-phenyl-1,4-oxathiin-3-carboxamide (US 3 249 499);
Oxycarboxin, 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide 4,4-dioxide (US 3 399 214);
Cyazofamid, 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-thiadiazin-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] dithiin-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];
Fenamidon, (S) -1-anilino-4-methyl-2-methylthio-4-phenylimidazolin-5-one [CAS RN 161326-34-7];
Phenalimol, 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);
Furametopyr, 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-dithiolane-2-ylidene malonate (Proc. Insectic. Fungic. Conf. 8. Vol. 2, p. 715 (1975));
Mepronil, 3'-isopropoxy-o-toluanilide (US 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. Vol. 37, p. 737 (1973));
Proquinazide, 6-iodo-2-propoxy-3-propylquinazolin-4 (3H) -one (WO 97/48684);
Pyriphenox, 2 ', 4'-dichloro-2- (3-pyridyl) acetophenone (EZ) -O-methyloxime (EP 49 854);
Pyrrolochilone, 1,2,5,6-tetrahydropyrrolo [3,2,1-ij] quinolin-4-one (GB 139 43 373);
Quinoxyphene, 5,7-dichloro-4- (4-fluorophenoxy) quinoline (US 5 240 940);
Silthiofam, N-allyl-4,5-dimethyl-2- (trimethylsilyl) thiophene-3-carboxamide [CAS RN 175217-20-6];
Thiabendazole, 2- (1,3-thiazol-4-yl) benzimidazole (US 3 017 415);
Tifluzamide, 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 (dimethylcarbamate) (DE A 19 30 540);
Thiazinyl, 3'-chloro-4,4'-dimethyl-1,2,3-thiadiazole-5-carboxanilide [CAS RN 223580-51-6];
Tricyclazole, 5-methyl-1,2,4-triazolo [3,4-b] [1,3] benzothiazole [CAS RN 41814-78-2];
Trifolin, N, N ′-{piperazine-1,4-diylbis [(trichloromethyl) methylene]} diformamide (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 solution, CuSO ₄ × 3Cu (OH) ₂ × 3CaSO ₄ mixture [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];
A mixture of dinocup, 2,6-dinitro-4-octylphenyl crotonate and 2,4-dinitro-6-octylphenyl crotonate, where “octyl” refers to 1-methylheptyl, 1-ethylhexyl and 1 A mixture of -propylpentyl (US 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. 7., Vol. 2, p. 673 (1973));
Fenpiclonyl, 4- (2,3-dichlorophenyl) -1H-pyrrole-3-carbonitrile (Proc. 1988 Br. Crop Prot. Conf.-Pests Dis., Vol. 1, p. 65);
Fludioxonil, 4- (2,2-difluorobenzo [1,3] dioxol-4-yl) -1H-pyrrole-3-carbonitrile (The Pesticide Manual, publ. The British Crop Protection Council, 10th edition 1995, p. 482);
Acibenzoral-S-methyl, methyl 1,2,3-benzothiadiazole-7-carbothioate [CAS RN 135158-54-2];
Full bench avaricarb (bench avaricarb), isopropyl {(S) -1-[(1R) -1- (6-fluorobenzothiazol-2-yl) -ethylcarbamoyl] -2-methylpropyl} carbamate ( 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);
Siflufenamide, (Z) -N- [α- (cyclopropylmethoxyimino) -2,3-difluoro-6- (trifluoromethyl) -benzyl] -2-phenylacetamide (WO 96/19442);
Simoxanyl, 1- (2-cyano-2-methoxyiminoacetyl) -3-ethylurea (US 3 957 847);
Dichromedin, 6- (3,5-dichlorophenyl-p-tolyl) pyridazin-3 (2H) -one (US 4 052 395);
Diclocimet, (RS) -2-cyano-N-[(R) -1- (2,4-dichlorophenyl) ethyl] -3,3-dimethylbutyramide [CAS RN 139920-32-4];
Dietophenecarb, 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-thiazolecarboxamide (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);
Phenoxanyl, N- (1-cyano-1,2-dimethylpropyl) -2- (2,4-dichlorophenoxy) propanamide (EP-A 262 393);
Ferrimzone, (Z) -2′-methylacetophenone-4,6-dimethylpyrimidin-2-ylhydrazone [CAS RN 89269-64-7];
Fluazinam, 3-chloro-N- [3-chloro-2,6-dinitro-4- (trifluoromethyl) phenyl] -5- (trifluoromethyl) -2-pyridinamine (The Pesticide Manual, publ. The British Crop Protection Council, 10th edition (1995), p. 474);
Fosetyl, fosetyl-aluminum, ethylphosphonate (FR 22 54 276);
Iprovaricarb, isopropyl [(1S) -2-methyl-1- (1-p-tolylethylcarbamoyl) propyl] carbamate (EP-A 472 996);
Hexachlorobenzene (CR 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);
Metraphenone, 3′-bromo-2,3,4,6′-tetramethoxy-2 ′, 6-dimethylbenzophenone (US 5 945 567);
Pencyclon, 1- (4-chlorobenzyl) -1-cyclopentyl-3-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, propyl 3- (dimethylamino) propyl carbamate (DE-A 15 67 169);
Phthalide (DE-A 16 43 347);
Tolcrophos-methyl, O-2,6-dichloro-p-tolyl O, O-dimethyl phosphorothioate (GB 14 67 561);
Kintozen, 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];
Captohol, N- (1,1,2,2-tetrachloroethylthio) cyclohex-4-ene-1,2-dicarboximide (Phytopathology, Vol. 52, p. 754 (1962));
Captan, N- (trichloromethylthio) cyclohex-4-ene-1,2-dicarboximide (US 2 553 770);
Dichlorofluanide, N-dichlorofluoromethylthio-N ′, N′-dimethyl-N-phenylsulfamide (DE-A 11 93 498);
Holpet, N- (trichloromethylthio) phthalimide (US 2 553 770);
Tolylfuranide, N-dichlorofluoromethylthio-N ′, N′-dimethyl-Np-tolylsulfamide (DE-A 11 93 498);
Dimethomorph, 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) -1-morpholin-4-yl-propenone (EP-A 120 321);
Flumetovar, 2- (3,4-dimethoxyphenyl) -N-ethyl-α, α, α-trifluoro-N-methyl-p-toluamide [AGROW no. 243, 22 (1995)];
Flumorph, 3- (4-fluorophenyl) -3- (3,4-dimethoxyphenyl) -1-morpholin-4-ylpropenone (EP-A 860 438),
N- (4′-bromobiphenyl-2-yl) -4-difluoromethyl-2-methylthiazole-5-carboxamide,
N- (4′-trifluoromethylbiphenyl-2-yl) -4-difluoromethyl-2-methylthiazole-5-carboxamide,
N- (4′-chloro-3′-fluorobiphenyl-2-yl) -4-difluoromethyl-2-methylthiazole-5-carboxamide,
N- (3 ′, 4′-dichloro-4-fluorobiphenyl-2-yl) -3-difluoromethyl-1-methylpyrazole-4-carboxamide (WO 03/66610),
N- (2-cyanophenyl) -3,4-dichloroisothiazole-5-carboxamide (WO 99/24413);
N- (2- (4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl) ethyl) -2-methane-sulfonylamino-3-methylbutyramide, N- (2- ( 4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl) ethyl) -2-ethanesulfonylamino-3-methylbutyramide (WO 04/49804);
3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] pyridine (EP-A 10 35 122);
2-butoxy-6-iodo-3-propylchromen-4-one (WO 03/14103);
N, N-dimethyl-3- (3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1,2,4] triazole-1-sulfonamide (EP-A 10 31 571);
Methyl (2-chloro-5- [1- (3-methylbenzyloxyimino) ethyl] benzyl) carbamate,
Methyl (2-chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) carbamate (EP-A 12 01 648);
Methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) -propionate (EP-A 10 28 125);
Azoxystrobin, methyl 2- {2- [6- (2-cyano-1-vinylpenta-1,3-dienyloxy) pyrimidin-4-yloxy] -phenyl} -3-methoxyacrylate (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-1,4,2-dioxazin-3- Yl) methanone O-methyl oxime (WO 97/27189);
Cresoxime-methyl, methyl (E) -methoxyimino [α- (o-tolyloxy) -o-tolyl] acetate (EP-A 253 213);
Metminostrobin, (E) -2- (methoxyimino) -N-methyl-2- (2-phenoxyphenyl) acetamide (EP-A 398 692);
Orisatrobin, (2E) -2- (methoxyimino) -2- {2-[(3E, 5E, 6E) -5- (methoxyimino) -4,6-dimethyl-2,8-dioxa-3,7- Diazanona-3,6-dien-1-yl] phenyl} -N-methylacetamide (WO 97/15552);
Picoxystrobin, methyl 3-methoxy-2- [2- (6-trifluoromethylpyridin-2-yloxymethyl) phenyl] acrylate (EP-A 278 595);
Pyraclostrobin, methyl N- {2- [1- (4-chlorophenyl) -1H-pyrazol-3-yloxymethyl] phenyl} (N-methoxy) carbamate (WO 96/01256);
Trifloxystrobin, methyl (E) -methoxyimino-{(E) -α- [1- (α, α, α-trifluoro-m-tolyl) ethylidene-aminooxy] -o-tolyl} acetate (EP -A 460 575);
Methyl 2- [ortho- (2,5-dimethylphenyloxymethylene) phenyl] -3-methoxyacrylate (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-carboxamide (WO 99/24413),
Compounds of formula III (WO 04/049804);
N- (2- (4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl) ethyl) -2-methane-sulfonylamino-3-methylbutyramide and N- (2- ( 4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl) ethyl) -2-ethanesulfonylamino-3-methylbutyramide (WO 03/66609);
2-butoxy-6-iodo-3-propylchromen-4-one of formula IV (WO 03/14103);
N, N-dimethyl-3- (3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1,2,4] triazole-1-sulfonamide of formula V (WO 03/053145);
Methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) -propionate of formula VI (EP-A 1028125).

  The object of the present invention is to reduce the total amount of active compound applied for the purpose of reducing the application rate and broadening the activity spectrum of active compounds I and II, in particular a mixture with improved activity against harmful fungi, specifically identified and indicated. Is to provide.

  As a result, we have found a mixture defined at the beginning of active compounds I and II. Furthermore, we apply at least one compound I and at least one compound II simultaneously, ie together or separately, or alternatively one or more compounds I and at least one compound I. It has been found that by sequentially applying Compound II, harmful fungi can be further controlled compared to the case where each compound can occur alone (synergistic mixture).

  Compound I can be used as a synergist against a number of different fungicidal compounds. At the same time, ie together or separately, the compound I is applied with at least one active compound II and its bactericidal activity is increased superadditively.

  Compound I may exist in various crystal modifications, and they may differ in their biological activity.

  In formula I, halogen is fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.

C ₁ -C ₄ -alkyl is methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl, preferably methyl or ethyl .

C ₁ -C ₆ -alkyl is a C ₁ -C ₄ -alkyl group as described above, or n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1- Ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1, 2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl; preferably a C ₁ -C ₄ -alkyl group as described above.

C ₁ -C ₄ -haloalkyl is a C ₁ -C ₄ -alkyl group which is partially or fully halogenated, in which case one or more halogen atoms are in particular fluorine, chlorine and / or bromine I.e., chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1- Fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro -2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, heptafluoropropyl or nonafluorobutyl, especially halomethyl Especially preferred are CH ₂ -Cl, CH (Cl) ₂ , CH ₂ -F, CH (F) ₂ , CF ₃ , CHFCl, CF ₂ Cl or CF (Cl) ₂ , especially difluoromethyl and tri Fluoromethyl.

C ₁ -C ₆ -haloalkyl is a C ₁ -C ₆ -alkyl group which is partially or fully halogenated, in which case one or more halogen atoms are in particular fluorine, chlorine and / or bromine For example a C ₁ -C ₄ -haloalkyl group as described above, or 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, 5,5,5-trichloropentyl, Undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl, 6,6,6-trichlorohexyl or dodecafluorohexyl; preferably a C ₁ -C ₄ -haloalkyl group It is.

  3,5-disubstituted N-biphenylpyrazole carboxamides of the formula I in which X is oxygen are known, for example, from WO 2005/123689, WO 2005/123690 and the earlier German application 102005007160.0, i.e. they are It can be prepared by the methods described therein.

  Compound I where X is sulfur can be prepared, for example, by sulfiding the corresponding compound I where X is oxygen (eg, D. Petrova & K. Jakobcic, Croat. Chem. Acta 48, 49 ( 1976), as well as WO 01/42223).

  Preferred among 3,5-disubstituted N-biphenylpyrazole carboxamides I are those in which X is oxygen first.

  Second, compounds I where X is sulfur are preferred.

For the mixtures according to the invention, preference is given to R ¹ and R ² being independently of one another cyano, fluorine, chlorine, methyl, methoxy or trifluoromethyl, R ³ being fluorine, chlorine, methyl or C ₁ -haloalkyl. A compound of formula I wherein R ⁴ is hydrogen or halogen;

Particularly preferred are R ¹ and R ² independently of one another cyano, fluorine, chlorine or methoxy and R ³ is fluorine, chlorine, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoro A compound of formula I which is methyl or trifluoromethyl and R ⁴ is hydrogen, fluorine or chlorine.

Particularly particularly preferred are R ¹ and R ² independently of one another fluorine or chlorine and R ³ is methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl or trifluoromethyl. A compound of formula I, wherein R ⁴ is hydrogen.

Particularly preferred are the compounds Ia listed in the table below.

table 1:
Compounds 1.1-1.20
A compound of formula I, wherein R ¹ is fluorine and R ² and R ³ in each case have the meaning given in one of the rows in table A.

Table 2:
Compounds 2.1-2.20
A compound of formula I, wherein R ¹ is chlorine and R ² and R ³ in each case have the meaning given in one of the rows in table A.

Table 3:
Compounds 3.1-3.20
A compound of formula I, wherein R ¹ is bromine and R ² and R ³ in each case have the meaning given in one of the rows in table A.

Table 4:
Compounds 4.1-4.20
A compound of formula I, wherein R ¹ is iodine and R ² and R ³ in each case have the meaning given in one of the rows in table A.

Table 5:
Compounds 5.1-5.20
A compound of formula I, wherein R ¹ is methyl and R ² and R ³ in each case have the meaning given in one of the rows in table A.

Table 6:
Compounds 6.1-6.20
A compound of formula I, wherein R ¹ is methoxy and R ² and R ³ in each case have the meaning given in one of the rows in table A.

Table 7:
Compounds 7.1-7.20
A compound of formula I, wherein R ¹ is trifluoromethyl and R ² and R ³ in each case have the meaning given in one of the rows in table A.

Table 8:
Compound 8.1-8.20
A compound of formula I, wherein R ¹ is trifluoromethoxy and R ² and R ³ in each case have the meaning given in one of the rows in table A.

Table 9:
Compound 9.1-9.20
A compound of formula I, wherein R ¹ is cyano and R ² and R ³ in each case have the meaning given in one of the rows in table A.

Table 10:
Compounds 10.1 to 10.20
A compound of formula I, wherein R ¹ is nitro and R ² and R ³ in each case have the meaning given in one of the rows in table A.

  Particularly particularly preferred compounds of the formula I are N- (3 ′, 5′-dichlorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- ( 3 ', 5'-difluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (3'-chloro-5'-fluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (3 ', 5'-bis (trifluoromethyl) biphenyl-2-yl) -1-methyl-3-trifluoromethyl -1H-pyrazole-4-carboxamide, N- (3 ', 5'-dichlorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide, N- (3', 5 '-Difluorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide, N- (3'-chloro-5'-fluorobiphenyl-2-yl) -1-methyl- 3-Difluoromethyl-1H- Pyrazole-4-carboxamide, N- (3 ′, 5′-bis (trifluoromethyl) biphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide, N- (3 ′ , 5'-Difluorobiphenyl-2-yl) -1-methyl-3-fluoromethyl-1H-pyrazole-4-carboxamide, N- (3 ', 5'-difluorobiphenyl-2-yl) -1-methyl- 3-difluoromethyl-1H-pyrazole-4-carboxamide, N- (3 ', 5'-difluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (3'-chloro-5'-fluorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide, N- (3'-chloro-5'-fluorobiphenyl-2- Yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (3′-chloro-5′-fluorobiphenyl-2-yl) -1-methyl-3-fluoromethyl-1H -Pyrazole-4-ca Ruboxamide, N- (3′-chloro-5′-fluorobiphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N- (3 ′, 5′-bis ( (Trifluoromethyl) biphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N- (3′-fluoro-5′-methylbiphenyl-2-yl) -1, 3-Dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N- (3'-cyano-5'-fluorobiphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4 -Carboxamide and N- (3 ', 5'-dimethylbiphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide.

  Preference is given to a mixture of a compound of the formula I and A) at least one active compound selected from the group of azoles.

  Preference is also given to a mixture of a compound of the formula I and at least one active compound selected from the group B) strobilurins.

  Preference is also given to mixtures of the compound of the formula I with at least one active compound selected from the group C) carboxamides.

  Further preferred is a mixture of a compound of formula I and at least one active compound selected from the group of D) heterocyclic compounds.

  Preference is furthermore given to a mixture of a compound of the formula I and at least one active compound selected from the group E) carbamates.

  Further preferred are mixtures comprising a compound of formula I and F) at least one active compound selected from the group of other fungicides.

  Further preferred are compounds of formula I and cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriahol, metconazole, microbutanyl, penconazole, propiconazole, prothioconazole, triazimephone. At least one active compound selected from the group consisting of: A, azoles, triazimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamide, benomyl, carbendazim and ethaboxam It is a mixture of

  Particularly preferred are compounds of the formula I and cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriahol, metconazole, microbutanyl, propiconazole, prothioconazole, triadimethone, triazimeme A mixture of at least one active compound selected from the group consisting of A) azoles, selected from the group consisting of nor, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamide, benomyl and carbendazim.

  Very particular preference is given to A) azoles selected from the group consisting of compounds of the formula I and epoxiconazole, fluquinconazole, flutriahol, metconazole, tebuconazole, triticonazole, prochloraz and carbendazim A mixture with at least one active compound selected from the group of classes.

  Preference is also given to a compound of formula I and azoxystrobin, dimoxystrobin, fluoxastrobin, cresoxime-methyl, orissastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin B) a mixture with at least one active compound selected from the group of B) strobilurins selected from the group.

  Particular preference is given to mixtures of compounds of the formula I with at least one active compound selected from the group of cresoxime-methyl, orisatrobin and pyraclostrobin, B) from the group of strobilurins is there.

  Particularly preferred is a mixture of the compound of formula I and pyraclostrobin.

  Also preferred are compounds of formula I and C) carboxamide selected from the group consisting of fenhexamide, metalaxyl, mefenoxam, off lars, dimethomorph, flumorph, fluopicolide (picobenzamide), zoxamide, carpropamide and mandipropamide. A mixture with at least one active compound selected from the group of classes.

  Also particularly preferred is a compound of formula I and at least one selected from the group consisting of C) carboxamides selected from the group consisting of phenhexamide, metalaxyl, mefenoxam, oflers, dimethomorph, zoxamide and carpropamide. Mixtures of seed active compounds.

  Also preferred are a compound of formula I and fluazinam, cyprodinyl, phenalimol, mepanipyrim, pyrimethanil, trifoline, fludioxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, vinclozoline, famoxadone, fenamidone, Probenazole, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl)-[1,2,4] triazolo [1,5-a] pyrimidine, Proquinazide, acibenzoral-S-methyl, captahol, holpet, phenoxanyl and quinoxyphene, especially fluazinam, cyprodinil, phenalimol, mepanipyrim, pyrimethanil, trifoline, fludioxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, At least one active compound selected from the group consisting of D) heterocyclic compounds, selected from the group consisting of nclozoline, famoxadone, fenamidone, probenazole, proquinazide, acibenzoral-S-methyl, captahol, holpet, phenoxanyl and quinoxyphene It is a mixture of

  Also particularly preferred are compounds of the formula I and pyrimethanil, dodemorph, fenpropimorph, tridemorph, iprodione, vinclozoline, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2 , 4,6-trifluorophenyl)-[1,2,4] triazolo [1,5-a] pyrimidine and quinoxyphene, especially selected from the group consisting of pyrimethanyl, dodemorph, phenpropimorph, tridemorph, iprodione, vinclozoline and quinoxyphene D) a mixture with at least one active compound selected from the group of heterocyclic compounds.

  Also preferred is a compound of formula I and at least selected from the group consisting of E) carbamates selected from the group consisting of mancozeb, methylam, propineb, thiram, iprovaricarb, fulbenecarbib and propamocarb. A mixture with one active compound.

  Also particularly preferred are mixtures of a compound of the formula I with at least one active compound selected from the group of E) carbamates selected from the group consisting of mancozeb and methylam.

  Preference is also given to compounds of the formula I and dithianon, fentin salts, such as fentin acetate, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, chlorothalonil, diclofluranide, thiophanate-methyl, copper acetate, water A mixture with at least one active compound selected from the group consisting of copper oxide, copper oxychloride, basic copper sulfate, sulfur, simoxanyl, metraphenone and spiroxamine, F) other fungicides .

  Also particularly preferred is a compound of formula I and at least one activity selected from the group consisting of phosphorous acid and its salts, chlorothalonil and metraphenone, F) other fungicides It is a mixture with a compound.

  Preference is also given to a ternary mixture of one compound of the formula I and two active compounds II described above.

  Preferred combinations of active compounds are listed in Tables 11-17 below.

Table 11
Active compound combinations of compound I with active compound II of group A):

Table 12
Active compound combinations of compound I with active compound II of group B):

Table 13
Active compound combinations of compound I with active compound II of group C):

Table 14
Active compound combinations of compound I and group D) with active compound II:

Table 15
Active compound combinations of compound I with active compound II of group E):

Table 16
Active compound combinations of compound I with active compound II of group F):

Table 17
Active compound combination of compound I and two active compounds II:

  A mixture of compound I and at least one active compound II, or at the same time, ie together with or separately, at least one active compound I and at least one active compound II is a broad range of phytopathogenic fungi In particular, it is prominent against fungi of the classes Ascomycetes, Basidiomycetes, Deuteromycetes, and Peronosporomycetes (synonymous with Oomycetes) Have a good activity. Some of them act osmotically and they can be used as foliar fungicides, seed dressing fungicides and soil fungicides in crop protection. They can also be used for seed treatment.

  These include bananas, cotton, vegetables (eg, cucumbers, beans, cucumbers, etc.), barley, pasture, oats, coffee trees, potatoes, corn, fruit trees, rice, rye, soybeans, tomatoes, vines, wheat It is particularly important in the control of various cultivated plants such as foliage plants, sugarcane, and many fungi on the seeds of these plants.

These are particularly suitable for the control of the following plant diseases. :
• Alternaria species on vegetables, rapeseed, sugar beets and fruits and rice (eg, Alternaria solani or A. alternata on potatoes and tomatoes) ),
Aphanomyces species on sugar beets and vegetables,
・ Ascochyta species on cereals and vegetables,
Bipolaris species and Drechslera species on corn, cereals, rice and lawn (e.g., D. maydis on corn),
・ Blumeria graminis (powdery mildew) on cereals,
Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and vines,
・ Bremia lactucae on lettuce,
Cercospora species on corn, soybean, rice and sugar beet,
Cochliobolus species (e.g., cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice), etc.
・ Colletotricum species on soybean and cotton,
Drechslera species, Pyrenophora species (e.g., Drechslera teres on barley, or Drexlera tritici-lepentis on wheat) on corn, cereals, rice and grass (Such as Drechslera tritici-repentis)
Phaeoacremonium chlamydosporium, Phaeoacremonium Aleophilum, and Formitipora punctata (synonyms originated from Pheninus punctat) Esca that attaches to trees
・ Exserohilum species on corn,
・ Erysiphe cichoracearum and Sphaerotheca fuliginea on cucumber,
Fusarium species and Verticillium species on various plants (e.g., Fusarium graminearum or F. culmorum on cereals or many Plants such as Fusarium oxysporum on tomatoes)
・ Geumanomyces graminis on cereals,
Gibberella species (for example, Gibberella fujikuroi for rice), cereals and rice
・ Grainstaining complex that attaches to rice,
・ Helminthosporium species on corn and rice,
・ Michrodochium nivale on cereals,
Mycosphaerella species on cereals, bananas and peanuts (for example, Mycosphaerella graminicola on wheat or M. fijiensis on bananas) Such),
Peronospora species on cabbage and bulbous plants (e.g., Peronospora brassicae on cabbage or Peronospora 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., Phytophthora capsici on peppers),
・ Plasmopara viticola on the vines,
・ Podosphaera leucotricha on the apple tree,
・ Pseudocercosporella herpotrichoides on cereals,
Pseudoperonospora on various plants (eg, P. cubensis on cucumbers or P. humili on hops),
Puccinia species on various plants (e.g., P. triticina, P. striformis, P. hordei or Pukukinia on cereals) Graminis (P. graminis, P. asparagi, etc.)
・ Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum, Entyloma oryzae and Entyloma oryzae
・ Pyricularia grisea on lawn and cereals,
・ Pythium spp. On grass, rice, corn, cotton, rapeseed, sunflower, sugar beet, vegetables and other plants (e.g. Pythium ultiumum on various plants) Pythium aphanidermatum)
Cotton, rice, potato, lawn, corn, rapeseed, sugar beet, vegetables and Rhizoctonia species on various plants (e.g. Rhizoctonia solani on sugar beet and various plants),
・ Rhynchosporium secalis on barley, rye and triticale,
・ Sclerotinia species on rapeseed and sunflower,
-Septoria tritici and Stagonospora nodorum on wheat,
・ Erichife on the vines (synonyms are Uncinula, Erysiphe necator),
Setospaeria species on corn and lawn,
・ Sphacelotheca reilinia on corn,
・ Thieveliopsis species on soybeans and cotton,
・ Tilletia species on cereals,
Ustilago species (e.g., Ustilago maydis on corn) on cereals, corn and sugarcane,
Venturia species (scab) on apple trees and pear trees (for example, V. inaequalis on apple trees).

  Furthermore, the mixtures according to the invention are also suitable for the control of harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or textiles) and in the protection of stored products. In wood protection, particular attention is paid to the following harmful fungi: Ascomycetes, for example, Ophiostoma spp., Ceratocystis spp., Aureova Aureobasidium pullulans, Sclerophoma spp., Caetomium spp., Humicola spp., Petriella spp., Tricrus Species (Trichurus spp.); Basidiomycetes, for example, Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus species ( Lentinus spp.), Pleurotus spp., Polya sp. (Poria spp.), Serpra spp. (Serpula spp.) And Tyromyces spp .; imperfect fungi, such as , Aspergillus spp., Clados Palladium species (Cladosporium spp.), Penicillium species (Penicillium spp.), Trichoderma species (Trichoderma spp.), Alternaria species (Alternaria spp.), Pesilomyces species (Paecilomyces spp.) And zygomycetes, for example, Mucor spp., And the following yeast fungi in the protection of materials: Candida spp. And Saccharomyces cerevisae.

  The mixtures according to the invention are applied by treating fungi or plants, seeds, materials or soils to be protected from fungal attack with an active compound in an amount effective as a fungicide. Application can be carried out both before and after infection of fungal material, plants or seeds.

  At least one of compound I and active compound II can be applied simultaneously, i.e. together or separately or sequentially, but in the case of separate application, the order generally depends on the result of the control treatment. It has no effect.

  In preparing the mixture, it is preferred to use pure active compounds I, II, further active compounds against harmful fungi or other pests such as insects, arachnids or nematodes, or herbicidal or growth-regulating active compounds or Fertilizer may be added as needed.

  Such mixtures of active compounds are, for example, compounds of the formula I, in particular N- (3 ′, 5′-difluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4 -Carboxamide, N- (3 ', 5'-dichlorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (3', 5'-difluorobiphenyl- 2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide or N- (3 ', 5'-dichlorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H- Pyrazole-4-carboxamide, azoles of group A), in particular epoxiconazole, metconazole, triticonazole or fluquinconazole, and insecticides, suitable insecticides are in particular fipronil and neonicotinoids, such as Acetamiprid, clothianidin, dinotefuran, imidaclop De, nitenpyram, is thiacloprid and thiamethoxam.

  Usually, a mixture of at least one compound I and at least one compound II is used. Here, a mixture of at least one compound I and two or even more kinds of active ingredients may provide special advantages.

  Suitable “further active ingredients” in the above sense are the active compounds II mentioned at the outset, in particular the preferred active compounds II mentioned above.

  Compound I and active compound II are usually applied 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, further active ingredients are added to compound I in a ratio of 20: 1 to 1:20.

  Depending on the type of compounds I and II and the desired effect, the application rate of the mixture according to the invention is 5 g / ha to 2000 g / ha, preferably 20 to 1500 g / ha, in particular 50 to 1000 g / ha, especially in the case of crop areas. ha.

  Similarly, the application rates of compound I are generally from 1 to 1000 g / ha, preferably from 1 to 900 g / ha, in particular from 20 to 750 g / ha.

  Similarly, the application rates of active compound II are generally from 1 to 2000 g / ha, preferably from 1 to 1500 g / ha, in particular from 40 to 1000 g / ha.

  In the treatment of seeds, the application rate of the mixture is generally from 1 to 1000 g, preferably from 1 to 750 g, in particular from 5 to 500 g, per 100 kg of seed.

  Methods for controlling harmful fungi include compound I and at least one active compound II, or a mixture of compound I and at least one active compound II before or after sowing, or before or after plant emergence. It is carried out by spraying or dusting seeds, plants or soils and applying them separately or together.

  The synergistic fungicide mixture according to the invention or compound I and at least one active compound II are converted into customary formulations, for example solutions, emulsions, suspensions, powders, powders, pastes or granules can do. The application form will depend on its particular intended purpose, and in each case it should be ensured 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 extending the active compound with solvents and / or carriers, if desired using emulsifiers and dispersants.

Suitable solvents / auxiliaries for this purpose are basically the following:
Water, aromatic solvents (eg Solvesso® products, xylene), paraffins (eg mineral oil fraction), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg , Cyclohexanone, γ-butyrolactone), pyrrolidone (N-methylpyrrolidone, N-octylpyrrolidone), acetate (glycol diacetate), glycols, fatty acid dimethylamide, fatty acid, and fatty acid ester (basically a solvent mixture is also used) Possible)
・ As a carrier, ground natural minerals (for example, kaolin, clay, talc, chalk) and ground synthetic minerals (for example, fine silica, silicate); As emulsifiers, nonionic emulsifiers and anionic emulsifiers (for example, polyoxyethylene fats) Alcohol ethers, alkyl sulfonates, aryl sulfonates, etc.) and dispersants include, for example, lignosulfite waste liquor and methylcellulose.

  Suitable for use as a surfactant is lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonic acid, alkylsulfuric acid ester, alkylsulfonic acid, fatty alcohol sulfuric acid ester, fatty acid, And alkali metal salts, alkaline earth metal salts and ammonium salts of sulfated fatty alcohol glycol ethers, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxy Ethylene octyl phenyl ether, ethoxylated isooctyl phenol, octyl phenol, nonyl phenol, alkylphenyl polyglycol ether, tributyl phenol Nyl polyglycol ether, tristearyl phenyl polyglycol ether, alkylaryl polyether alcohol, condensate of alcohol and fatty alcohol / ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether Acetals, sorbitol esters, lignosulfite waste liquors, and methylcellulose.

  Substances suitable for preparing directly sprayable liquids, emulsions, pastes or oil dispersions are medium to high boiling mineral oil fractions such as kerosene or diesel oil, as well as coal tar oil, and plants Or animal-derived oils, aliphatic, cyclic and aromatic hydrocarbons such as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene or derivatives thereof, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, high polarity Solvents such as dimethyl sulfoxide, N-methylpyrrolidone, and water.

  Powders, broad-spreading agents and dusting products can be produced by mixing or simultaneously grinding the active substance and at least one solid carrier.

  Granules (eg coated granule, impregnated granule, homogenous granule, etc.) are made by binding the active compound to at least one solid support. Can do. Examples of solid carriers are mineral earth (eg silica gel, silicate, talc, kaolin, attaclay, limestone, lime, chalk, red clay, ocher, clay, dolomite, diatomaceous earth, calcium sulfate, sulfuric acid Magnesium, magnesium oxide, etc.), ground synthetics, fertilizers (eg, ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, etc.), and products of plant origin (eg, flour, bark powder, wood flour, nutshell powder, etc.), cellulose Powders, as well as other solid carriers.

  In general, the formulations comprise 0.01 to 95% by weight, preferably 0.1 to 90% by weight, of Compound I and at least one active compound II or a mixture of compound I and at least one active compound II. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR or HPLC spectrum).

  The following are examples of formulations of the present invention.

1. Products diluted with water A) Water-solbule concentrates (SL)
10 parts by weight of the mixture according to the invention are dissolved in 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. The active compound dissolves upon dilution with water. A preparation having an active compound content of 10% by weight is thus obtained.

B) Dispersible concentrates (DC)
20 parts by weight of the mixture according to the invention are dissolved by adding 10 parts by weight of a dispersant (eg polyvinylpyrrolidone) to 70 parts by weight of cyclohexanone. Dilution with water gives a dispersion. The active compound content is 20% by weight.

C) Emulsifiable concentrates (EC)
15 parts by weight of the mixture of the present invention is dissolved by adding calcium dodecylbenzenesulfonate and castor oil ethoxylate (both 5 parts by weight) to 75 parts by weight of xylene. Dilution with water gives an emulsion. The active compound content of the formulation is 15% by weight.

D) Emulsions (EW, EO)
25 parts by weight of the mixture of the present invention is dissolved in 35 parts by weight of xylene by adding calcium dodecylbenzenesulfonate and castor oil ethoxylate (both 5 parts by weight). This mixture is introduced into 30 parts by weight of water using an emulsifier (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The active compound content of the formulation is 25% by weight.

E) Flowables (SC), OD
In a ball mill under stirring, 20 parts by weight of the mixture according to the invention are added with 10 parts by weight of a dispersant and a wetting agent and 70 parts by weight of water or an organic solvent and ground to give a fine suspension of the active compound. A turbid liquid is obtained. Dilution with water gives a stable suspension of the active compound. The active compound content of the formulation is 20% by weight.

F) Water-dispersible granule and water-soluble granules (WG, SG)
Add 50 parts by weight of a dispersant and wetting agent to 50 parts by weight of the active compound and pulverize it, then use a special apparatus (eg, extruder, spray tower, fluidized bed, etc.) Use water solvent. Dilution with water gives a stable dispersion or solution of the active compound. The active compound content of the formulation is 50% by weight.

G) Water-dispersible powders and water-soluble powders (WP, SP)
In a rotor-stator mill, 75 parts by weight of the inventive mixture are added with 25 parts by weight of a dispersant, a wetting agent and silica gel and ground. Dilution with water gives a stable dispersion or solution of the active compound. The active compound content of the formulation is 75% by weight.

2. Products applied without dilution H) Dustable powders (DP)
5 parts by weight of a mixture according to the invention is pulverized and mixed thoroughly with 95 parts by weight of pulverized kaolin. This gives a dustable product with an active compound content of 5% by weight.

J) Granules (GR, FG, GG, MG)
0.5 part by weight of a mixture according to the invention is comminuted and combined with 99.5 parts by weight of carrier. Current methods are extrusion, spray drying, or fluidized bed. This gives granules with an active compound content of 0.5% by weight to be applied undiluted.

K) ULV solution (UL)
10 parts by weight of the mixture according to the invention are dissolved in 90 parts by weight of an organic solvent (eg xylene). This gives a product to be applied undiluted with an active compound content of 10% by weight.

  The active compound is itself in the form of its formulation or application form prepared from its formulation by spraying, atomizing, dusting, spreading or pouring. For example, it can be used in the form of a directly sprayable solution, powder, flowable formulation or dispersion, emulsion formulation, oil dispersion, paste, dusting product, widespread product, or granule. The form of application depends solely on its intended purpose, but in each case it should ensure that the active compound is dispersed as finely as possible.

  Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsion formulations, pastes, or oil dispersions, homogenize the substance as is or dissolved in oil or solvent in water using a wetting agent, tackifier, dispersant or emulsifier. be able to. Although concentrates can be prepared consisting of the active substance, wetting agent, tackifier, dispersant or emulsifier, and optionally solvent or oil, these concentrates are suitable for dilution with water.

  The concentration of the active compound in the ready-to-use preparations can be varied within a relatively wide range. In general, they are 0.0001-10%, preferably 0.01-1%.

  The active compound can also be successfully used in the ultra-low volume (ULV) method, applying a formulation containing more than 95% by weight of the active compound or the active compound itself without additives. be able to.

  If necessary, various kinds of oils, wetting agents, adjuvants, herbicides, other agricultural chemicals, antibacterial agents and the like can be added to the active compound (tank mixing) immediately before use. These agents can be mixed with the mixture according to the invention, usually in a weight ratio of 1: 100 to 100: 1, preferably in a weight ratio of 1:10 to 10: 1.

  In this sense, suitable adjuvants are in particular: organo-modified polysiloxanes such as Break Thru S 240®; alcohol alkoxylates such as Atplus 245®, Atplus MBA 1303®, Plurafac LF 300 ( Registered trademark) and Lutensol ON 30®; ethoxy / propoxy block polymers such as Pluronic RPE 2035® and Genapol B®; alcohol ethoxylates such as Lutensol XP 80 As well as sodium dioctyl sulfosuccinate, such as Leophen RA®.

  The compounds I and II or mixtures, or the corresponding preparations, contain harmful fungi, their habitat or plants, seeds, soil, areas, raw materials or spaces that should be free of harmful fungi, In the case of application, the compounds I and II are applied by treating them in an amount effective as a fungicide. Application can be carried out before or after infection by harmful fungi.

Preparation example
1.) Synthesis of ortho- (3,5-dichlorophenyl) aniline
1.4 g of tetrakistriphenylphosphine palladium (0) in 20.47 g 2-bromoaniline, 24.98 g 3,5-dichlorophenylboronic acid and 25.23 g sodium carbonate dissolved in a mixture of 150 ml water and 450 ml ethylene glycol dimethyl ether Added to the solution. The mixture was stirred at reflux for 23 hours and then concentrated under reduced pressure. The residue was taken up in methyl tert-butyl ether, washed three times with water, dried over sodium sulfate and concentrated under reduced pressure. Purification by chromatography using a mixture of toluene and cyclohexane (1: 4) gave 13.3 g of product as a white powder.

2． ) Synthesis of 1-methyl-3-trifluoromethyl-N- (ortho- (3,5-dichlorophenyl) phenyl) -pyrazole-4-carboxamide
9.88 g 1-methyl-3-trifluoromethylpyrazole-4-carbonyl chloride, 11.07 g ortho- (3,5-dichlorophenyl) aniline, and 5.52 g pyridine were dissolved in 350 ml toluene. After stirring for 48 hours at room temperature, 400 ml of methyl tert-butyl ether were added and the mixture was washed twice with 5% strength hydrochloric acid, once with 5% strength aqueous sodium hydroxide and twice with water. The organic phase was dried over sodium sulfate and concentrated under reduced pressure. The crude product was recrystallized from diisopropyl ether and washed with n-pentane. There was thus obtained 16.94 g of product as a colorless powder. mp = 101-105 ° C.

  In addition to the compounds described above, Table 18 below provides representative examples of further 3,5-disubstituted N-biphenylpyrazolecarboxamides of formula I, which are prepared in a similar manner or can be prepared where X is oxygen. It describes as.

Table 18

Use Examples The synergistic effect of the mixtures according to the invention was demonstrated by the following tests.

  The active compounds are prepared individually or together as a stock solution containing 25 mg of active compound, and acetone and / or dimethyl sulfoxide and emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action of ethoxylated alkylphenol system) ) Was used in a solvent: emulsifier volume ratio of 99: 1 to make 10 ml. The mixture was then made up to 100 ml with water. This stock solution was diluted with the described solvent / emulsifier / water mixture in order to obtain the active compound concentrations indicated below.

  Alternatively, the active compounds epoxiconazole and pyraclostrobin were used as commercial formulations and diluted with water to the indicated active compound concentrations.

  Percent visual measurements of infected leaf area were converted to efficacy in% of untreated controls.

Efficacy (E) is Abbot's formula as follows:
E = (1−α / β) · 100
(α corresponds to the% fungal infection of the treated plant,
β corresponds to% fungal infection of untreated (control) plants)
Calculate using.

  A potency of 0 means that the infection level of the treated plant corresponds to that of the untreated control plant; a potency of 100 means that the treated plant was not infected.

  The expected potency of a mixture of active compounds is determined using the Colby formula (RS Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, 15, 20-22 (1967)) and compared to the observed potency .

Colby formula: E = x + y−x · y / 100
(Where
E is the expected potency expressed as a percentage of the untreated control when a mixture of active compounds A and B is used at concentrations a and b;
x is the potency expressed as% of untreated control when active compound A is used at concentration a,
y is the potency expressed as% of untreated control when active compound B is used at concentration b).

Use Example 1-Activity against tomato blight of tomatoes caused by Alternaria solani An aqueous suspension having the following active compound concentration was sprayed to the extent of running down on the leaves of potted tomatoes. The next day, the treated plants were inoculated with a spore suspension of Alternaria solani containing 0.17 × 10 ⁶ spores / mL in a 2% strength aqueous biomalt solution. The test plant was then placed in a steam saturation chamber at a temperature of 22-22 ° C. After 5 days, the disease in the untreated but infected control plants had progressed to a certain extent so that the infection could be visually determined in%.

Use Example 2-Activity against gray mold of pepper leaves caused by Botrytis cinerea, protected for 1 day:
An aqueous suspension having the following active compound concentration was sprayed on the pepper seedlings of the cultivar “Neusiedler Ideal Elite” after 2 to 3 leaves had grown sufficiently to the extent that it flowed down. The next day, the treated plants were inoculated with a spore suspension of Botrytis cinerea containing 1.7 × 10 ⁶ spores / mL in a 2% strength aqueous biomalt solution. The test plants were then placed in a dark climate chamber at a temperature of 22-24 ° C. and high atmospheric humidity. After 5 days, the degree of fungal infection on the leaves could be determined visually by%.

Use Example 3-Activity against powdery mildew of wheat caused by Erysiphe (synonymous with Blumeria), Graminis (forma specialis), Tritici on potted wheat seedling leaves An aqueous suspension having the following active compound concentration was sprayed to the extent that it flowed down: Suspensions or emulsions were prepared as described above. 24 hours after the spray coating dried, spores of wheat powdery mildew (Ericifer (synonymous with Blumeria), Graminis-differentiated type, Tritici) were sprinkled on the plants. The test plants were then placed in a greenhouse at a temperature of 20-24 ° C. and a relative atmospheric humidity of 60-90%. Seven days later, the degree of progression of this plague was visually determined as a percentage of the total leaf area.

Use Example 4-Protective activity against Puccinia recondita in wheat (wheat red rust)
An aqueous suspension having the following active compound concentration was sprayed on the leaves of potted wheat seedlings of the cultivar “Kanzler” to the extent that they flowed down. The next day, the treated plants were inoculated with a suspension of wheat rust spores (Pukkinia recondita). The plants were then placed in a chamber at 20-22 ° C. and high atmospheric humidity (90-95%) for 24 hours. During this period, the spores germinated and the germ tube entered the leaf tissue. The next day, the test plants were returned to the greenhouse and cultivated for an additional 7 days at a temperature of 20-22 ° C and a relative atmospheric humidity of 65-70%. Next, the degree of progress of leaf rust was determined visually.

Use Example 5-Healing Activity against Soybean Rust Caused by Phakopsora pachyrhizi Inoculated with Soybean Rust Disease Spore Suspension (Fakosora pachyrhizi) on Soybean Seedling of Potted Culture Variety `` Oxford '' did. These potted plants were then placed in a chamber at 23-27 ° C. and high atmospheric humidity (90-95%) for 24 hours. During this period, the spores germinated and the germ tube entered the leaf tissue. Two days later, the above-mentioned active compound solution having the following active compound concentration was sprayed to the infected plants to such an extent that it flowed down. After drying the spray coating, the test plants were grown for 14 days in a greenhouse at a temperature of 23-27 ° C. and a relative atmospheric humidity of 60-80%. Next, the degree of progression of rust on the leaves was determined.

Claims (13)

1) At least one formula I:

(Wherein the substituents are as defined below:
X is oxygen or sulfur;
R ¹ and R ² are independently of one another cyano, nitro, halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, methoxy, difluoromethoxy or trifluoromethoxy;
R ³ is halogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -haloalkyl;
R ⁴ is hydrogen or halogen)
3,5-disubstituted N-biphenylpyrazole carboxamide represented by:
2) The following groups A) to F):
A) Viteltanol, bromconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole, fenbuconazole, flusilazole, flutriahol, hexaconazole, imibenconazole, ipconazole, metconazole, Microbutanyl, penconazole, propiconazole, prothioconazole, cimeconazole, triadimethone, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, pefrazoate, imazalyl, triflumizole, cyazofamide, benomyl, carbendazim, thiabendazole Azoles selected from the group consisting of ethaboxam, etridiazole, and himexazole;
B) Azoxystrobin, Dimoxystrobin, Enestrobrin, Fluoxastrobin, Cresoxime-methyl, Metominostrobin, Orisatrobin, Picoxystrobin, Pyraclostrobin, Trifloxystrobin, Enestrobrin, Methyl (2-Chloro-5- [1- (3-methylbenzyloxyimino) ethyl] benzyl) carbamate, methyl (2-chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl ) Strobilurins selected from the group consisting of carbamate and methyl 2- (ortho-((2,5-dimethylphenyloxymethylene) phenyl) -3-methoxyacrylate;
C) Carboxin, Benalaxyl, Boscalid, Fenhexamide, Flutolanil, Frametopyr, Mepronil, Metalaxyl, Mefenoxam, Offras, Oxadixyl, Oxycarboxyl, Penthiopyrad, Thifluzamide, Thiazinyl, 3,4-Dichloro-N- (2-cyanophenyl) ) Isothiazole-5-carboxamide, dimethomorph, flumorph, flumethoval, fluopicolide (picobenzamide), zoxamide, carpropamide, diclosimet, mandipropamide, N- (2- (4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl) ethyl) -2-methanesulfonylamino-3-methylbutyramide, N- (2- (4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl) ethyl ) -2-ethanesulfonylamino-3-methylbutyramide, methyl 3- (4-chloro) Eniru) -3- (2-isopropoxycarbonyl-3-methyl-butyryl-amino) - propionate, formula III:

(Wherein R ⁵ is methyl or ethyl)
N- (4′-bromobiphenyl-2-yl) -4-difluoromethyl-2-methylthiazole-5-carboxamide, N- (4′-trifluoromethylbiphenyl-2-yl)- 4-difluoromethyl-2-methylthiazole-5-carboxamide, N- (4′-chloro-3′-fluorobiphenyl-2-yl) -4-difluoromethyl-2-methylthiazole-5-carboxamide, N- ( 3 ', 4'-dichloro-4-fluorobiphenyl-2-yl) -3-difluoromethyl-1-methylpyrazole-4-carboxamide and N- (2-cyanophenyl) -3,4-dichloroisothiazole-5 -Carboxamides selected from the group consisting of carboxamides;
D) Fluazinam, pyriphenox, bupirimate, cyprodinil, phenalimol, ferrimzone, mepanipyrim, nuarimol, pyrimethanyl, trifoline, fenpicuronyl, fludioxonil, aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, procymidone, vinclozoline, , Phenamidon, octyrinone, probenazole, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl)-[1,2,4] triazolo [1, 5-a] pyrimidine, anilazine, dichromedin, pyroxylone, proquinazide, tricyclazole, Formula IV:

Embedded image (2-butoxy-6-iodo-3-propylchromen-4-one), acibenzoral-S-methyl, captahol, captan, dazomet, holpet, phenoxanyl, quinoxyphene, and formula V:

N, N-dimethyl-3- (3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1,2,4] triazole-1-sulfonamide represented by A heterocyclic compound;
E) Mancozeb, Maneb, Metam, Methylam, Farbum, Propineb, Tiram, Zineb, Zillam, Dietofencarb, Iprovaricarb, Fullbenchalicarb, Propamocarb, 4-Fluorophenyl N- (1- (1- (4-Cyanophenyl) -Ethanesulfonyl) but-2-yl) carbamate, formula VI:

Methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propionate represented by the formula:

(Wherein Z is N or CH) carbamates selected from the group consisting of carbamate oxime ethers;
F) Guanidines: dodin, iminotadine, guazatine,
Antibiotics: kasugamycin, streptomycin, polyoxin, validamycin A,
Nitrophenyl derivatives: Binapacryl, Zinocup, Dinobutone,
Sulfur-containing heterocyclyl compounds: dithianone, isoprothiolane,
Organometallic compounds: fentin salts, such as fentin acetate,
Organophosphorus compounds: edifenphos, iprobenphos, fosetyl, fosetyl-aluminum, phosphorous acid and its salts, pyrazophos, tolcrophos-methyl,
Organochlorine compounds: chlorothalonil, diclofuranide, fursulfamide, hexachlorobenzene, phthalide, pencyclone, quintozene, thiophanate-methyl, tolylfuranide,
Inorganic active compounds: Bordeaux solution, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur,
Other: A fungicide mixture for controlling phytopathogenic harmful fungi, comprising a synergistically effective amount of another fungicide selected from the group consisting of cyflufenamide, simoxanyl, dimethymol, ethylimol, flaxilil, metraphenone and spiroxamine. . As component 1), R ¹ and R ² are independently of each other cyano, fluorine, chlorine, methyl, methoxy or trifluoromethoxy, R ³ is fluorine, chlorine, methyl or C ₁ -haloalkyl, and R ⁴ is The fungicide mixture according to claim 1, comprising 3,5-disubstituted N-biphenylpyrazole carboxamide of formula I, which is hydrogen or halogen. As component 1), R ¹ and R ² are independently of each other cyano, fluorine, chlorine or methoxy and R ³ is fluorine, chlorine, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoro The fungicide mixture according to claim 1, comprising a 3,5-disubstituted N-biphenylpyrazolecarboxamide of formula I, which is methyl or trifluoromethyl and R ⁴ is hydrogen, fluorine or chlorine. As component 1), R ¹ and R ² are independently of each other fluorine or chlorine, R ³ is methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl or trifluoromethyl, The fungicide mixture according to claim 1, comprising a 3,5-disubstituted N-biphenylpyrazole carboxamide of formula I, wherein R ⁴ is hydrogen.   As component 1), N- (3 ′, 5′-dichlorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (3 ′, 5′-difluoro Biphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (3′-chloro-5′-fluorobiphenyl-2-yl) -1-methyl-3- Trifluoromethyl-1H-pyrazole-4-carboxamide, N- (3 ′, 5′-bis (trifluoromethyl) biphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4- Carboxamide, N- (3 ′, 5′-dichlorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide, N- (3 ′, 5′-difluorobiphenyl-2- Yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide, N- (3'-chloro-5'-fluorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H- Pyrazole-4-carboxamide, N- (3 ', 5'-bis (trifluoromethyl) biphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide, N- (3', 5'-difluorobiphenyl-2 -Yl) -1-methyl-3-fluoromethyl-1H-pyrazole-4-carboxamide, N- (3 ′, 5′-difluorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole -4-carboxamide, N- (3 ', 5'-difluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (3'-chloro-5' -Fluorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide, N- (3'-chloro-5'-fluorobiphenyl-2-yl) -1-methyl-3 -Trifluoromethyl-1H-pyrazole-4-carboxamide, N- (3'-chloro-5'-fluorobiphenyl-2-yl) -1-methyl-3-fluoromethyl-1H-pyrazole-4-carboxamide, N -(3'-Chloro-5'-F Orobiphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N- (3 ′, 5′-bis (trifluoromethyl) biphenyl-2-yl) -1, 3-Dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N- (3'-fluoro-5'-methylbiphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4 -Carboxamide, N- (3'-cyano-5'-fluorobiphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide or N- (3 ', 5'-dimethyl The fungicide mixture according to claim 1, comprising biphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide.   6. The disinfectant mixture according to any one of claims 1 to 5, comprising component 1) and component 2) in a weight ratio of 100: 1 to 1: 100.   6. A bactericidal composition comprising the bactericidal mixture according to any one of claims 1 to 5 and at least one solid carrier or liquid carrier.   Treating plants, soil, seeds, areas, materials or spaces to be protected from harmful fungi, their habitat or fungal attack with the fungicide mixture according to any one of claims 1 to 5, A method for controlling phytopathogenic harmful fungi.   9. Process according to claim 8, wherein component 1) and component 2) according to any one of claims 1 to 5 are applied simultaneously, i.e. together or separately or sequentially.   The method according to claim 8 or 9, wherein component 1) and component 2) according to any one of claims 1 to 5 are applied in an amount of 5 g / ha to 2000 g / ha.   The method according to claim 8 or 9, wherein the components 1) and 2) according to any one of claims 1 to 5 are applied in an amount of 1 to 1000 g per 100 kg of seeds.   A seed comprising the mixture according to any one of claims 1 to 5 in an amount of 1 to 1000 g per 100 kg of seed.   Use of compounds I and II according to any one of claims 1 to 5 for preparing a composition suitable for the control of harmful fungi.