JP2009526745A - Bactericidal mixture based on 2,4-disubstituted N-biphenylpyrazolecarboxamide - Google Patents

Abstract

The present invention comprises as active components 1) at least one formula I wherein 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 halogenalkyl, methoxy, difluoromethoxy or trifluoromethoxy; R ³ is halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ halogenalkyl, R ⁴ is hydrogen or halogen A) 2,4-disubstituted pyrazolecarboxylic acid biphenylamides; and 2) groups A to F (A) azoles; B) strobilurins; C) carboxamides; D) heterocyclic compounds; E) carbamates; Pathogenicity using a mixture of a bactericide mixture comprising at least one active ingredient II selected from bactericides) in an amount having a synergistic activity, at least one compound I and at least one active ingredient II For controlling fungi The use of compounds I and an active component II for preparing the mixture of, and to agents and seeds containing said mixtures.

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 each other 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]
2,4-disubstituted N-biphenylpyrazole carboxamide, and
2) At least one active compound II selected from groups A) to F):
A) bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole ), Fenbuconazole, flusilazole, flutriazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, microbutanil, myclobutanil, Penconazole, propiconazole, prothioconazole, simeconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triconazole Triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid, benomyl, carbendazim, thiabendazole, thiabendazole an azole selected from the group consisting of fuberidazole), ethaboxam, etridiazole, and hymexazole;
B) Azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metomominostrobin, orysastrobin ), Picoxystrobin, pyraclostrobin, trifloxystrobin, enestroburin, methyl (2-chloro-5- [1- (3-methylbenzyloxyimino) ) Ethyl] benzyl) carbamate, methyl (2-chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) carbamate and methyl 2- (ortho- (2,5-dimethylphenyloxy) Strobilurin selected from the group consisting of methylene) phenyl) -3-methoxyacrylate;
C) Carboxin, benalaxyl, boscalid, fenhexamid, flutolanil, furametpyr, mepronil, metalaxyl, mefenoxam, mefenoxam Ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, 3,4-dichloro-N- (2-cyanophenyl) isothiazole- 5-Carboxamide, dimethomorph, flumorph, flumetover, fluopicolide (picobenzamid), zoxamide, carpropamid, diclocymet, mandipropamide , N- (2- (4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxypheny ) Ethyl) -2-methanesulfonylamino-3-methylbutyramide), N- (2- (4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl) ethyl) -2- Ethanesulfonylamino-3-methylbutyramide, methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) 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- Carboxamide selected from the group consisting of 5-carboxamide;
D) fluazinam, pyrifenox, bupirimate, cyprodinil, fenarimol, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil, triholine (triforine), fenpiclonil, fludioxonil, aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, proproidone procymidone), 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 ne), diclomezine, pyroquilon, proquinazid, tricyclazole, formula IV

(2-butoxy-6-iodo-3-propylchromen-4-one), acibenzolar-S-methyl, captafol, captan, dazomet, holpet (folpet), phenoxanil, quinoxyfen and formula V

A heterocycle selected from the group consisting of N, N-dimethyl-3- (3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1,2,4] triazole-1-sulfonamide Compound;
E) mancozeb, maneb, metam, metam, metiram, ferbam, propineb, thiram, zineb, ziram, diethofencarb ), Iprovalicarb, flubenthiavalicarb, propamocarb, 4-fluorophenyl N- (1- (1- (4-cyanophenyl) ethanesulfonyl) but-2-yl) carbamate, Formula VI

Of methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propanoate and formula VII

[Wherein Z is N or CH]
A carbamate selected from the group consisting of:
F) Guanidine: dodine, iminoctadine, guazatine,
Antibiotics: kasugamycin, streptomycin, polyoxins, validamycin A,
Nitrophenyl derivatives: binapacryl, dinocap, dinobuton,
Sulfur-containing heterocyclic compounds: dithianon, isoprothiolane,
Organometallic compounds: Fentine salts such as fentin acetate,
Organophosphorus compounds: edifenphos, iprobenfos, fosetyl, fosetylaluminum, phosphorous acid and its salts, pyrazophos, tolclofos-methyl,
Organochlorine compounds: Chlorothalonil, dichlofluanid, flusulfamide, hexachlorobenzene, phthalide, penencycuron, quintozene, thiophanate-methyl, tolylfluanid ( tolylfluanid),
Inorganic active compounds: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur,
Others: cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone and spiroxamine
It relates to a sterilization mixture comprising another fungicide selected from the group consisting of in a synergistic amount.

  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 said mixture, and these And a seed comprising a mixture of

  EP-A 589301 discloses, inter alia, several substituted N-biphenylpyrazole carboxamides. However, in the individual compounds disclosed, the biphenyl group is unsubstituted or only monosubstituted.

  Substituted biphenylamides in which the biphenyl group is substituted by only one substituent are also known from WO 01/42223.

  JP-A 09/132567 discloses a disubstituted biphenylamide having a phenyl group substituted with trifluoromethyl.

  WO 2005/34628 discloses, inter alia, mixtures of pyrazole carboxamide and various other compounds with bactericidal activity. The pyrazole carboxamide described in this document differs from the compound I of the present invention particularly in the substitution pattern of the biphenyl group.

  2,4-disubstituted N-biphenylpyrazole carboxamides are known from WO 2005/123689, WO 2005/123690 and the earlier German patent application No. 102005007160.0.

  However, the described N-biphenylpyrazolecarboxamides and known mixtures are not completely satisfactory, especially at low application rates.

  The active compounds II described 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 I want to be) 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);
Off-race, (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);
An aldimorph, “4-alkyl-2,5 (or 2,6) -dimethylmorpholine” comprising 65-75% 2,6-dimethylmorpholine and 25-35% 2,5-dimethylmorpholine; Contains more than 85% 4-dodecyl-2,5 (or 2,6) -dimethylmorpholine, where “alkyl” also includes octyl, decyl, tetradecyl and hexadecyl with a cis / trans ratio of 1: 1 Yes [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 industrial grade iminodi (octamethylene) diamine amidation reaction products, including 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-arabinohexopyranosyl] -D-kaileunositol [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));
Flucilazole, 1-{[bis (4-fluorophenyl) methylsilanyl] methyl} -1H- [1,2,4] triazole (Proc. Br. Crop Prot. Conf.-Pests Dis., 1, 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);
Felbum, dimethyldithiocarbamic acid / iron (3+) (US 1 972 961);
Nabum, 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, ammoniated zinc ethylenebis (dithiocarbamate) (US 3 248 400);
Propinebu, propylene bis (dithiocarbamate) zinc polymer (BE 611 960);
Polycarbamate, bis (dimethylcarbamodithioate-κS, κS ') [μ-[[1,2-ethanediylbis [carbamodithioate-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-carboxyanilide 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];
Phenamidon, (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);
Nualimol, 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-carboxyanilide [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-carboxyanilide [CAS RN 223580-51-6];
Tricyclazole, 5-methyl-1,2,4-triazolo [3,4-b] [1,3] benzothiazole [CAS RN 41814-78-2];
Triphorin, 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 x 3Cu (OH) ₂ x 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];
Dinocup, a mixture of 2,6-dinitro-4-octylphenylcrotonate and 2,4-dinitro-6-octylphenylcrotonate, where “octyl” is 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];
Nitrotal isopropyl, diisopropyl 5-nitroisophthalate (Proc. Br. Insectic. Fungic. Conf. 7., Vol. 2, p. 673 (1973));
Fenpicronyl, 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, The British Crop Protection Council Crop Protection Council), 10th edition, 1995, p. 482);
Acibenzoral-S-methyl, methyl 1,2,3-benzothiadiazole-7-carbothioate [CAS RN 135158-54-2];
Fullbench 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-methylcyclopropanecarboxamide [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 ), The British Crop Protection Council, 10th edition, (1995), p. 474);
Fosetyl, fosetyl aluminum, ethyl phosphonate (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, isopropyl 3- (dimethylamino) propylcarbamate (DE-A 15 67 169);
Phthalide (DE-A 16 43 347);
Troclofosmethyl, 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];
Captafor, 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);
Tolyl fluoride, N-dichlorofluoromethylthio-N, N-dimethyl-Np-tolylsulfamide (DE-A 11 93 498);
Dimethomorph, 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) -1-morpholin-4-ylpropenone (EP-A 120 321);
Flumetober, 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-methanesulfonylamino-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) ethylideneaminooxy] -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 IV (WO 04/049804);
N- (2- (4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl) ethyl) -2-methanesulfonylamino-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) propanoate of formula VI (EP-A 1028125).

  The object of the present invention is to improve against harmful fungi, especially certain indications, while reducing the total amount of active compound applied, with the aim of reducing the application rate and broadening the active spectrum of active compounds I and II. Is to provide a mixture having improved activity.

  We have now found a mixture of active compounds I and II as defined above. Furthermore, the inventors apply at least compound I and at least one active compound II simultaneously, ie together or separately, or apply compound I and at least one active compound II sequentially. Has found that it is possible to control harmful fungi better than the control that can be achieved using individual compounds alone (synergistic mixture).

  Compound I can be used as a synergist for a great many different fungicidal compounds. By applying compound I simultaneously with at least one active compound II, ie together or separately, the bactericidal activity is increased in an additive or more manner.

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

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

C ₁ -C ₆ - alkyl, C ₁ -C ₄ as described above - alkyl 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 are preferable, and C ₁ -C ₄ -alkyl groups as described above are preferable.

C ₁ -C ₄ -haloalkyl is a partially or fully halogenated C ₁ -C ₄ -alkyl group in which the halogen atom is in particular fluorine, chlorine and / or bromine. That is, for example, 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, particularly preferably CH ₂ -Cl, CH (Cl) ₂ , CH ₂ -F, CH (F) ₂ , CF ₃ , CHFC1, CF ₂ Cl or CF (Cl) ₂ , in particular difluoromethyl and trifluoromethyl.

C ₁ -C ₆ -haloalkyl is a partially or fully halogenated C ₁ -C ₆ -alkyl group in which the halogen atom is in particular fluorine, chlorine and / or bromine. That is, for example, C ₁ -C as described above ₄ - haloalkyl or 5-fluoro-pentyl, 5-chloropentyl, 5-bromopentyl, 5-Yodopenchiru, 5,5,5-trichloro-pentyl, undecafluoro- Pentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl, 6,6,6-trichlorohexyl or dodecafluorohexyl; preferably a C ₁ -C ₄ -haloalkyl group .

  2,4-disubstituted N-biphenylpyrazolecarboxamides of the formula I in which X is oxygen are known, for example, from WO 2005/123689, WO 2005/123690 and the earlier German patent application No. 102005007160.0, or there It can be prepared by the methods described.

  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) and WO 01/42223).

  Of the 2,5-disubstituted N-biphenylpyrazolecarboxamides I, those in which X is oxygen are preferred.

  Next, the above-mentioned compound I in which X is sulfur is preferable.

In the mixture of the present invention, R ¹ and R ² are independently of each other cyano, fluorine, chlorine, methyl, methoxy or trifluoromethyl, R ³ is fluorine, chlorine, methyl or C ₁ -haloalkyl, R Preference is given to compounds of the formula I in which ⁴ is hydrogen or halogen.

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, dichlorofluoromethyl or trimethyl. Particular preference is given to compounds of the formula I which are fluoromethyl and R ⁴ is hydrogen, fluorine or chlorine.

R ¹ and R ² are independently of each other fluorine or chlorine, R ³ is methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl or trifluoromethyl, and R ⁴ is hydrogen The compound of formula I, which is

The compounds Ia listed in the table below are particularly preferred.

table 1:
Compounds 1.1 to 1.60
A compound of formula I wherein R ¹ is fluorine and R ² and R ³ in each compound have the meanings listed in one row of Table A.

Table 2:
Compounds 2.1-2.60
A compound of formula I wherein R ¹ is chlorine and R ² and R ³ in each compound have the meanings listed in one row of Table A.

Table 3:
Compounds 3.1-3.60
A compound of formula I wherein R ¹ is bromine and R ² and R ³ in each compound have the meanings listed in one row of Table A.

Table 4:
Compounds 4.1-4.60
A compound of formula I wherein R ¹ is iodine and R ² and R ³ in each compound have the meaning described in one row of Table A.

Table 5:
Compound 5.1-5.60
A compound of formula I wherein R ¹ is methyl and R ² and R ³ in each compound have the meaning described in one row of Table A.

Table 6:
Compounds 6.1-6.60
A compound of formula I wherein R ¹ is methoxy and R ² and R ³ in each compound have the meanings listed in one row of Table A.

Table 7:
Compounds 7.1-7.60
A compound of formula I wherein R ¹ is trifluoromethyl and R ² and R ³ in each compound have the meanings listed in one row of Table A.

Table 8:
Compound 8.1-8.60
A compound of formula I wherein R ¹ is trifluoromethoxy and R ² and R ³ in each compound have the meanings listed in one row of Table A.

Table 9:
Compound 9.1-9.60
A compound of formula I wherein R ¹ is cyano and R ² and R ³ in each compound have the meanings listed in one row of Table A.

Table 10:
Compounds 10.1 to 10.60
A compound of formula I wherein R ¹ is nitro and R ² and R ³ in each compound have the meaning described in one row of Table A.

  A highly preferred compound of formula I is N- (2 ′, 4′-dichlorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (2 ′ -Fluoro-4'-chlorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazol-4-carboxamide, N- (2 ', 4'-difluorobiphenyl-2-yl)- 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (2 ', 4'-dichlorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4 -Carboxamide, N- (2 ', 4'-difluorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide and N- (2'-fluoro-4'- Chlorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide, N- (2′-methyl-4′-chlorobiphenyl-2-yl) -1-methyl-3 -Trifluoromethyl-1H-pyrazo -4-carboxamide, N- (2'-methyl-4'-fluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (2'- Fluoro-4'-methoxybiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (2'-methyl-4'-chlorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide, N- (2'-methyl-4'-fluorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole -4-carboxamide, N- (2 ', 4'-dichlorobiphenyl-2-yl) -1,3-dimethyl-5-chloro-1H-pyrazole-4-carboxamide, N- (2', 4 ' -Dichlorobiphenyl-2-yl) -1,3-dimethyl-1H-pyrazole-4-carboxamide, N- (2 ', 4'-difluorobiphenyl-2-yl) -1,3-dimethyl-1H-pyrazole -4-carboxamide, N- (2'-fluoro-4'-chlorobi Enyl-2-yl) -1,3-dimethyl-1H-pyrazole-4-carboxamide, N- (2 ', 4'-dichlorobiphenyl-2-yl) -1-methyl-3-chlorodifluoromethyl-1H -Pyrazole-4-carboxamide, N- (2 ', 4'-dichlorobiphenyl-2-yl) -1-methyl-3-chlorofluoromethyl-1H-pyrazole-4-carboxamide, N- (2', 4'-dichlorobiphenyl-2-yl) -1-methyl-3-fluoromethyl-1H-pyrazole-4-carboxamide, N- (2 ', 4'-dichlorobiphenyl-2-yl) -1-methyl- 3-dichlorofluoromethyl-1H-pyrazole-4-carboxamide, N- (2 ', 4'-dichlorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-5-fluoro-1H-pyrazole- 4-carboxamide, N- (2′-fluoro-4′-chlorobiphenyl-2-yl) -1-methyl-3-fluoromethyl-1H-pyrazole-4-carboxamide, N- (2′-fluoro- 4'-chlorobiphenyl-2-yl) -1-me 3-fluoromethyl-1H-pyrazole-4-carboxamide, N- (2 ′, 4′-difluorobiphenyl-2-yl) -1-methyl-3-fluoromethyl-1H-pyrazole-4-carboxamide N- (2′-chloro-4′-fluorobiphenyl-2-yl) -1-methyl-3-fluoromethyl-1H-pyrazole-4-carboxamide, N- (2′-fluoro-4′-chloro Biphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N- (2'-fluoro-4'-chlorobiphenyl-2-yl) -1,3-dimethyl -5-Fluoro-1H-pyrazole-4-carboxamide, N- (2'-Fluoro-4'-methoxybiphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxy Amido, N- (2'-fluoro-4'-methylbiphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N- (2'-methyl-4 ' -Chlorobiphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyra 4-carboxyamide, N- (2′-methyl-4′-fluorobiphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N- (2 '-Chloro-4'-fluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-5-fluoro-1H-pyrazole-4-carboxamide, N- (2'-methoxy-4'-fluoro Biphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide.

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

  Also preferred is a mixture of a compound of formula I and at least one active compound selected from the group B) strobilurin.

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

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

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

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

  Also, the compound of formula I and cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriahol, metconazole, microbutanyl, penconazole, propiconazole, prothioconazole, triadimethone, triadimenol, tebuconazole, Also preferred are mixtures with at least one active compound selected from the group of A) azoles selected from the group consisting of tetraconazole, triticonazole, prochloraz, cyazofamide, benomyl, carbendazim and ethaboxam.

  Also, the compound of formula I may be combined with cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriahol, metconazole, microbutanyl, propiconazole, prothioconazole, triadimethone, triadimenol, tebuconazole, tetraconazole. Particular preference is given to mixtures with at least one active compound selected from the group A) azoles selected from the group consisting of nazol, triticonazole, prochloraz, cyazofamide, benomyl and carbendazim.

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

  And B) strobilurin selected from the group consisting of the compound of formula I and azoxystrobin, dimoxystrobin, fluoxastrobin, cresoxime methyl, orisatrobin, picoxystrobin, pyraclostrobin and trifloxystrobin Preference is given to mixtures with at least one active compound selected from the group of

  Also particularly preferred are mixtures of compounds of the formula I with at least one active compound selected from the group B) strobilurin selected from the group consisting of cresoxime methyl, orisatrobin and pyraclostrobin.

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

  Also selected from the group of C) carboxyamide selected from the group consisting of a compound of formula I and fenhexamide, metalaxyl, mefenoxam, off-race, dimethomorph, flumorph, flupicoride (picobenzamide), zoxamide, carpropamide and mandipropamide. Preference is given to mixtures with at least one active compound.

  Also, a mixture of a compound of formula I with at least one active compound selected from the group of C) carboxamide selected from the group consisting of phenhexamide, metalaxyl, mefenoxam, off race, dimethomorph, zoxamide and carpropamide Is particularly preferred.

  Also, the compound of formula I and fluazinam, cyprodinyl, phenalimol, mepanipyrim, pyrimethanyl, triphorin, 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, Captaphor, holpet, phenoxanyl, quinoxifen, especially fluazinam, cyprodinil, phenalimol, mepanipyrim, pyrimethanil, triphorin, fludioxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, vinclozoline, famoxadone Fenamidone, probenazole, proquinazid, acibenzolar -S- methyl, Kaputahoru, folpet, a mixture of at least one active compound selected from the group of D) heterocyclic compounds selected from the group consisting of fenoxanil and quinoxyfen are preferred.

  Also, a compound of formula I and pyrimethanil, dodemorph, fenpropimorph, tridemorph, iprodione, vinclozolin, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluoro A mixture with at least one active compound selected from the group of D) heterocyclic compounds selected from the group consisting of (phenyl)-[1,2,4] triazolo [1,5-a] pyrimidine and quinoxyphene preferable.

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

  Also particularly preferred are mixtures of the compounds 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.

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

  Also particularly preferred are mixtures of compounds of the formula I with at least one active compound selected from the group F) other fungicides selected from the group consisting of phosphorous acid and its salts, chlorothalonil and metraphenone.

  Also preferred are ternary mixtures of one compound of formula I and two active compounds II described above.

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

  A mixture of compound I and at least one active compound II, or at least one compound I and at least one active compound II applied simultaneously, ie together or separately, is a broad spectrum of phytopathogenic fungi, In particular, it has excellent activity against fungi belonging to the classes of ascomycetes, basidiomycetes, incomplete fungi (Deuteromycetes) and oomycete (Peronosporomycetes (also known as Oomycetes)). Some of them have osmotic effects and can be used in crop protection as fungicides acting on leaves, as fungicides for seed treatment and as soil fungicides. They can also be used for treating seed.

  They are especially various cultivated plants such as wheat, rye, barley, oats, rice, corn, grass, banana, cotton, soybeans, coffee, sugarcane, grapes, fruits and ornamental plants, as well as cucumbers, beans, tomatoes, potatoes And are particularly important for the control of many fungi in vegetables such as cucurbitaceae and in the seeds of these plants.

They are particularly suitable for controlling the following plant diseases:

Vegetable, rape, sugar beet and fruit and rice species of the genus Alternaria, such as potato and tomato, A. solani or A. alternata;
・ Species of the genus Aphanomyces of sugar beet and vegetables;
-Ascochyta species of cereals and vegetables;
Corn, cereals, rice and buckwheat Bipolaris and Drechslera species, such as corn D. maydis;
-Grain Blumeria graminis (mildew);
-Botrytis cinerea (grey mold disease) of strawberries, vegetables, flowers and grapes;
-Lettuce downy mildew (Bremia lactucae);
Corn, soybean, rice and sugar beet Cercospora species;
Corn, cereals, rice species of the genus Cochliobolus, e.g., cereal spot fungus (Cochliobolus sativus), rice sesame leaf blight (Cochliobolus miyabeanus);
-Species of the genus Colletotricum of soybean and cotton;
Corn, cereals, rice and shiba species of the genus Drechslera, species of the genus Pyrenophora, for example D. teres of barley or D. tritici-repentis;
・ Peoeocremonium ・ Phaeoacremonium chlamydosporium, Pheoacremonium areofilm (Ph. Aleophilum) and Formitipora punctata (also known as Phellinus punctatus) Esca disease;
Corn species of the genus Exserohilum cucumber powdery mildew, Erysiphe cichoracearum and Sphaerotheca fuliginea;
Fusarium and Verticillium species of various plants, such as cereal red mold fungus (F. graminearum or F. culmorum), or many plant dwarf fungi (F, for example tomatoes) oxysporum);
・ Gaeumanomyces graminis of cereals;
• Cereal and rice species of the genus Gibberella (eg, Gibberella fujikuroi);
-Rice grain pollution complex;
Corn and rice species of the genus Helminthosporium;
・ Mixrodochium nivale of cereals;
Cereals, bananas and groundnuts of the genus Mycosphaerella, for example, wheat mycosferella granicola (M. graminicola) or banana black Sigatoka (M. fijiensis);
Species of the genus Peronospora of cabbage and bulbous plants, such as cabbage downy mildew (P. brassicae) or onion downy mildew (P. destructor);
-Soybean Phakopsara pachyrhizi and Phakopsara meibomiae;
• Species of the genus Phomopsis of soybean and sunflower;
-Phytophthora infestans; potato and tomatoes;
・ Species of the genus Phytophthora of various plants, for example, P. capsici
・ Glass downy mildew (Plasmopara viticola);
・ Apple powdery mildew (Podosphaera leucotricha);
-Pseudocercosporella herpotrichoides in cereals;
Various plant species of the genus Pseudoperonospora, for example, cucumber downy mildew (P. cubensis) or hop downy mildew (P. humili);
Puccinia species of various plants, e.g. cereal rust fungi (P. triticina), P. striformins, P. hordei or black rust fungi (P .graminis) or asparagus rust (P. asparagi);
Rice blast fungus (Pyricularia oryzae), blight fungus (Corticium sasakii), leaf sheath rot fungus (Sarocladium oryzae), brown rice fungus (S. attenuatum), black rot fungus (Entyloma oryzae);
・ Pyricularia grisea in barley and cereals;
・ Pythium spp. Of barley, rice, corn, cotton, oilseed rape, sunflower, sugar beet, vegetables and other plants, e.g. P. ultiumum of various plants, P. aphanidermatum;
Cotton, rice, potato, buckwheat, corn, rape, sugar beet, vegetables and various plant species of the genus Rhizoctonia, such as beet and various plant R. solani;
-Barley, rye and triticale Rhynchosporium secalis;
Rapeseed and sunflower species of the genus Sclerotinia;
-Wheat leaf blight fungus (Septoria tritici) and Stagonospora nodorum;
・ Grape powdery mildew (Erysiphe (unknown name: Uncinula) necator);
• Species of the genus Setospaeria of corn and buckwheat;
• Corn sphaceloteca reilinia;
-Species of the genus Chievariopsis of soybean and cotton;
-Cereal Tilletia species;
Cereals, corn and sugarcane species of the genus Ustilago, e.g. corn smut (U. maydis);
Apple and pear species of the genus Venturia (black scab), for example apple scab (V. inaequalis).

  The mixtures according to the invention are also suitable for the protection of harmful fungi in the protection of materials (eg wood, paper, paint dispersions, fibers or textiles) and in the protection of stored products. In the protection of wood, the following harmful fungi: Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Ascomycetes such as Trichurus spp .; Coniophora spp., Coriolus spp. , Genus Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. And Tyromyces spp. Basidiomycetes; Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Pesilomyces Genus (Paecilomyces spp.) Etc. Special attention has been given to Deuteromycetes and Zygomycetes, such as Mucor spp. And in the protection of materials the following yeasts: Candida spp. And Saccharomyces・ Cerevisiae (Saccharomyces cerevisae) requires special attention.

  Compound I and at least one active compound II can be applied at the same time, i.e. together or separately, or sequentially, in the case of separate applications, the order generally depends on the result of the control. The influence of.

  In the case of providing a mixture, it is preferred to use pure active compounds I and II, where there are other active compounds against harmful fungi or other pests such as insects, arachnids or nematodes, or herbicidal activity or Growth-regulating active compounds or fertilizers may be added.

  Such mixtures of three active compounds are, for example, compounds of the formula I, in particular N- (2 ′, 4′-difluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole -4-carboxamide, N- (2 ', 4'-dichlorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (2', 4 ' -Difluorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide or N- (2 ', 4'-dichlorobiphenyl-2-yl) -1-methyl-3- It consists of difluoromethyl-1H-pyrazole-4-carboxamide, an azole of group A), in particular epoxiconazole, metconazole, triticonazole or fluquinconazole, and an insecticide. Suitable pesticides include fipronil, as well as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam. It is a nicotinoid.

  Usually a mixture of at least one compound I and at least one active compound II is used. Here, mixtures of at least one compound I with two or more active ingredients if desired can be particularly advantageous.

  Suitable further active ingredients in this sense are, in particular, the active compounds II mentioned at the outset, in particular the abovementioned preferred active compounds II.

  Compound I and active compound 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.

  Another active ingredient is optionally added to compound I in a ratio of 20: 1 to 1:20.

  Depending on the type of compounds I and II and the required effect, the application rates of the mixtures according to the invention are 5 g / ha to 2000 g / ha, preferably 20 to 1500 g / ha, especially in the agricultural area. In particular from 50 to 1000 g / ha.

  Similarly, the application rates of compound I are generally 1-1000 g / ha, preferably 10-900 g / ha, in particular 20-750 g / ha.

  Similarly, the application rates of active compound II are generally from 1 to 2000 g / ha, preferably from 10 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 1 to 1000 g / 100 kg of seed, preferably 1 to 750 g / 100 kg, in particular 5 to 500 g / 100 kg of seed.

  A method for controlling harmful fungi comprises compound I and at least one active compound II by spraying or dusting the seed, plant or soil before or after sowing of the plant or before or after germination of the plant. Are applied separately or together or by applying a mixture of compound I and at least one active compound II.

  The synergistic germicidal mixture according to the invention, or compound I and at least one active compound II, can be converted into conventional formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes or granules. . The application form depends on the particular purpose, but in any case it must ensure the finest and even distribution of the mixture according to the invention possible.

  The formulations are prepared in a manner known per se, for example by diluting the active compounds with solvents and / or carriers, if desired using emulsifiers and dispersants. Suitable solvents / additives for this purpose are basically as follows:

-Water, aromatic solvents (eg Solvesso® products, xylene), paraffins (eg mineral oil fractions), alcohols (eg methanol, butanol, pentanol, benzyl alcohol), ketones (eg Cyclohexanone, gamma-butyrolactone), pyrrolidone (N-methylpyrrolidone, N-octylpyrrolidone), acetate (glycol diacetate), glycol, fatty acid dimethylamide, fatty acid and fatty acid ester. In principle, solvent mixtures can also be used.

-Carriers such as ground natural minerals (eg kaolin, clay, talc, chalk) and ground synthetic minerals (eg finely ground silica, silicates); nonionic and anionic emulsifiers (eg polyoxyethylene) Emulsifiers such as fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignosulfite waste liquors and methylcellulose.

  Suitable surfactants include lignosulfonic acid, naphthalene sulfonic acid, phenol sulfonic acid, dibutyl naphthalene sulfonic acid, alkyl aryl sulfonate, alkyl sulfate, alkyl sulfonate, fatty alcohol sulfate, fatty acid and sulfated fatty alcohol glycol ether alkali. Metal salts, alkaline earth metal salts and ammonium salts. In addition, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl poly Glycol ether, tristearyl phenyl polyglycol ether, alkylaryl polyether alcohol, alcohol and fatty alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester , Roh is a sulfite waste liquors and methylcellulose.

  Suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are medium to high boiling mineral oil fractions such as kerosene or diesel oil, as well as coal tar oils and oils of vegetable or animal origin, Aliphatic, cyclic and aromatic hydrocarbons such as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene or derivatives thereof, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents such as , Dimethyl sulfoxide, N-methylpyrrolidone, and water.

  Powders, dusting materials and dusting products can be prepared by mixing or simultaneously grinding the active substance with at least one solid carrier.

  Granules such as coated granules, impregnated granules and uniform granules can be prepared by binding the active compound to at least one solid carrier. Examples of solid carriers are silica gel, silicate, talc, kaolin, activated clay, limestone, lime, chalk, red clay, ocher, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide and other minerals, grinding Synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and plant-derived products such as grain coarse flour, bark coarse flour, wood coarse flour and nut nut coarse flour, Cellulose powder and other solid carriers.

  In general, the formulations comprise 0.01-95% by weight, preferably 0.1-90% 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 compound is used in a purity of 90-100%, preferably 95-100% (according to NMR or HPLC spectrum).

  Examples of the formulation of the present invention are described below.

1. Products diluted with water
A) Water-soluble concentrate (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 additives are added. The active compound dissolves when diluted with water. This gives a formulation having an active compound content of 10% by weight.

B) Dispersible concentrate (DC)
20 parts by weight of the mixture according to the invention are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion. The active compound content is 20% by weight.

C) Emulsifiable concentrate (EC)
15 parts by weight of the mixture according to the invention are dissolved in 75 parts by weight of xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylated (5 parts by weight each). Dilution with water gives an emulsion. The formulation has an active compound content of 15% by weight.

D) Emulsion (EW, EO)
25 parts by weight of the mixture according to the invention are dissolved in 35 parts by weight of xylene with the addition of calcium dodecylbenzenesulfonate and ethoxylated castor oil (5 parts each). This mixture is introduced into 30 parts by weight of water using an emulsifier (eg Ultraturrax) to make a uniform emulsion. Dilution with water gives an emulsion. The formulation has an active compound content of 25% by weight.

E) Suspension (SC, OD)
In a stirred ball mill, 20 parts by weight of a mixture according to the invention are ground by adding 10 parts by weight of a dispersant and a wetting agent and 70 parts by weight of water or an organic solvent to give a fine active compound suspension. obtain. Dilution with water gives a stable suspension of the active compound. The active compound content in the formulation is 20% by weight.

F) Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of a mixture according to the invention are finely ground with addition of 50 parts by weight of a dispersant and a wetting agent and are water-dispersible or water-soluble using technical equipment (eg injection machines, spray towers, fluidized beds) Prepare granules. Dilution with water gives a stable dispersion or solution of the active compound. The formulation has an active compound content of 50% by weight.

G) Water-dispersible powder and water-soluble powder (WP, SP)
75 parts by weight of the inventive mixture are ground in a rotor-stator mill with the addition of 25 parts by weight of a dispersant, a wetting agent and silica gel. 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) Powder for dusting (DP)
5 parts by weight of the mixture according to the invention are finely ground and intimately mixed with 95 parts by weight of finely ground kaolin. This gives a dusting product having an active compound content of 5% by weight.

J) Granules (GR, FG, GG, MG)
0.5 part by weight of the mixture according to the invention is finely ground and combined with 99.5 parts by weight of support. The latest methods are injection, spray drying or fluidized bed. This gives granules to be applied undiluted having an active compound content of 0.5% by weight.

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, for example xylene. This gives a product to be applied undiluted having an active compound content of 10% by weight.

  The active compounds can be used as such, in the form of their preparations or in the use forms prepared from such preparations, for example solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts that can be sprayed directly Can be used by spraying, spraying, dusting, spraying or pouring in the form of a product, spraying material, or granule. The use forms depend entirely on the intended purpose, but in each case they are intended to ensure the finest possible distribution of the active compounds.

  Aqueous use forms can be prepared by adding water to the concentrated emulsion, paste or wettable powder (sprayable powder, oil dispersion). To prepare an emulsion, paste or oil dispersion, the material can be homogenized in water as it is or dissolved in an oil or solvent using a wetting agent, tackifier, dispersant or emulsifier. . Alternatively, it is possible to prepare concentrates containing active substances, wetting agents, tackifiers, dispersants or emulsifiers and, where appropriate, solvents or oils, such concentrates being suitable for dilution with water. ing.

  The active ingredient concentration in ready-to-use formulations can vary within a relatively wide range. In general, the concentration is from 0.0001 to 10%, preferably from 0.01 to 1%.

  The active compounds can also be used effectively in microdispersion methods (ULV), whereby a formulation containing 95% or more by weight of the active compound can be applied, or an active compound containing no additives can be applied. You can even do it.

  Various types of oils, wetting agents, adjuvants, herbicides, other insecticides, or bactericides can be added to the active compounds (tank mix) just before use if desired. These agents are usually mixed in the mixture according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.

  Adjuvants suitable in this sense are in particular organically modified polysiloxanes such as Break Thru S 240®; alkoxylated alcohols such as Atplus 245®, Atplus MBA 1303® ), Plurafac LF 300® and Lutensol® ON 30; EO / PO block polymers such as Pluronic® RPE 2035 and Genapol® B; alcohol ethoxylates such as Lutensol® Trademark) XP 80; and sodium dioctyl sulfosuccinate, such as Leophen® RA.

  Compounds I and II or mixtures or corresponding preparations can be used to remove harmful fungi, their growing environment or plants, seeds, soils, areas, materials or spaces that are to be prevented from infection, In the case of application, it is applied by treating with compounds I and II. Application can be carried out before or after infection by harmful fungi.

Preparation example
1.) Synthesis of ortho- (2,4-dichlorophenyl) aniline
0.14 g tetrakistriphenylphosphine palladium (0), 20.47 g 2-bromoaniline, 24.98 g 2,4-dichlorophenylboronic acid and 25.23 g sodium carbonate in 150 ml water and 450 ml ethylene glycol dimethyl ether Added to the solution in the mixture. The mixture was refluxed and stirred for 48 hours. The mixture 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. Purification by chromatography using a mixture of toluene and cyclohexane (1: 2) gave 15.5 g of product as a pale yellow powder.

2.) Synthesis of 1-methyl-3-trifluoromethyl-N- (ortho- (2,4-dichlorophenyl) phenyl) -pyrazole-4-carboxamide
0.32 g 1-methyl-3-trifluoromethylpyrazole-4-carbonyl chloride, 0.36 g ortho- (2,4-dichlorophenyl) aniline and 0.23 g triethylamine were dissolved in 10 ml toluene. After stirring the mixture for 4 hours at room temperature and adding 20 ml of methyl tert-butyl ether, the mixture is washed twice with 5% strength hydrochloric acid, twice with 5% strength aqueous sodium hydroxide solution and once with aqueous sodium chloride solution. Washed twice. The organic phase was dried over sodium sulfate and concentrated under reduced pressure. Purification by chromatography using a mixture of toluene and methyl tert-butyl ether gave 0.32 g of product as a colorless powder. mp = 136-140 ° C.

In addition to the above compounds, other 2,4-disubstituted N-biphenylpyrazole carboxamides of formula I prepared or prepared by similar methods are listed in Table 18 as examples.

Examples of use The synergism of the mixtures according to the invention was demonstrated by the following tests.

  The active compounds, separately or together, in a mixture of acetone and / or dimethyl sulfoxide and the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenol) (solvent / emulsifier volume ratio) = 99: 1) was used to prepare a 10 ml stock solution containing 25 mg of active compound. Next, water was added to the mixture to make 100 ml. This stock solution was diluted with the described solvent / emulsifier / water mixture to give the active compound concentrations below. Alternatively, the active compounds epoxiconazole and pyraclostrobin were used as commercial formulations and diluted to the stated active compound concentrations with water.

  The visually measured percentage of infected leaf area was converted to an effect expressed as a percentage of the untreated control.

  The effect (E) is calculated as follows using the Abbot equation.

E = (1 − α / β) ・ 100
α is the fungal infection of the treated plant expressed in%,
β is the fungal infection of untreated (control) plants expressed in%.

  Effect 0 means that the level of infection of the treated plant is consistent with the untreated control plant, and effect 100 means that the treated plant was not infected.

The expected effect of a mixture of active compounds is described by Colby's formula (RS Colby, `` Calculating synergistic and antagonistic responses of herbicide combinations '', Weeds 15 , 20 -22 (1967)) and compared with the observed effects.

Colby's formula: E = x + y − x · y / 100
E The expected effect, expressed as a percentage of the untreated control, when using a mixture of active compounds A and B at concentrations a and b;
x the effect in% of active compound A with concentration a relative to the untreated control;
y Effect expressed as% of untreated control when active compound B at concentration b is used.

Use Example 1-Activity against ring rot of tomato caused by Alternaria solani A leaf of potted tomato plant was sprayed with an aqueous suspension having the following active compound concentration to the pour point. The next day, the leaves were infected with an aqueous spore suspension of Alternaria solani in 2% biomalt having a concentration of 0.17 × 10 ⁶ spores / ml. The plants were then placed in a room saturated with water vapor at a temperature of 20-22 ° C. After 5 days, the disease in the untreated, infected control plants had developed to such an extent that the infection could be measured visually.

Use Case 2-Activity against gray mold disease of pepper leaf caused by Botrytis cinerea, daily protective application 2 to 3 leaves are good for pepper seedlings of variety "Neusiedler Ideal Elite" After development, an aqueous suspension having the following active compound concentrations was sprayed to the pour point. 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 control room with 22-24 ° C. and high atmospheric humidity. After 5 days, the extent of fungal infection of the leaves could be visually measured in%.

Use Example 3-Curing activity of wheat against red rust caused by Puccinia recondita A spore suspension of red rust fungus (Pukkinia recondita) was applied to the leaves of wheat seedlings of the variety "Kanzler" grown in flower pot Vaccinated. The flower pots were then placed in a room at high atmospheric humidity (90-95%) and 20-22 ° C. for 24 hours. Within this time, the spores germinated and the germ tube penetrated into the leaf tissue. The next day, the infected plants were sprayed to the pour point with a solution of the active compound having the following active compound concentration: After the spray coating had dried, the test plants were grown for 7 days in a greenhouse at a temperature of 20-22 ° C. and a relative atmospheric humidity of 65-70%. Next, the degree of development of rust disease in the leaves was measured.

Use Case 4-Protective activity against Puccinia recondita (wheat red rust) in wheat Aqueous suspension with the following active compound concentration is applied to the leaves of wheat seedlings of the potted variety "Kanzler" Until sprayed. The next day, the treated plants were inoculated with a spore suspension of wheat red rust fungus (Pukukinia recondita). The plants were then placed in a room at high atmospheric humidity (90-95%) and 20-22 ° C. for 24 hours. Within this time, the spores germinated and the germ tube penetrated into 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 development of rust disease in the leaves was measured visually.

Use Case 5-Activity against barley net blotch caused by Pyrenophora teres, one day of protective application An aqueous suspension with the following active compound concentration flows out into the leaves of potted barley seedlings Sprayed to point. Twenty-four hours after the spray coating had dried, the test plants were inoculated with an aqueous spore suspension of Pyrenophora (Drechslera) teres, the pathogen of net blotch disease. The test plants were then placed in a greenhouse at a temperature of 20-24 ° C. and a relative atmospheric humidity of 95-100%. After 6 days, the extent of disease development was measured visually as a percentage of infection relative to the total leaf area.

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 each other 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]
2,4-disubstituted N-biphenylpyrazole carboxamide, and
2) At least one active compound II selected from groups A) to F):
A) bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fluquinconazole ), Fenbuconazole, flusilazole, flutriazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, microbutanil, myclobutanil, Penconazole, propiconazole, prothioconazole, simeconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triconazole Triticonazole, prochloraz, pefurazoate, imazalil, triflumizole, cyazofamid, benomyl, carbendazim, thiabendazole, thiabendazole an azole selected from the group consisting of fuberidazole), ethaboxam, etridiazole, and hymexazole;
B) Azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metomominostrobin, orysastrobin ), Picoxystrobin, pyraclostrobin, trifloxystrobin, enestroburin, methyl (2-chloro-5- [1- (3-methylbenzyloxyimino) ) Ethyl] benzyl) carbamate, methyl (2-chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) carbamate and methyl 2- (ortho- (2,5-dimethylphenyloxy) Strobilurin selected from the group consisting of methylene) phenyl) -3-methoxyacrylate;
C) Carboxin, benalaxyl, boscalid, fenhexamid, flutolanil, furametpyr, mepronil, metalaxyl, mefenoxam, mefenoxam Ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, 3,4-dichloro-N- (2-cyanophenyl) isothiazole- 5-Carboxamide, dimethomorph, flumorph, flumetover, fluopicolide (picobenzamid), zoxamide, carpropamid, diclocymet, mandipropamide , N- (2- (4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxypheny ) Ethyl) -2-methanesulfonylamino-3-methylbutyramide), N- (2- (4- [3- (4-chlorophenyl) prop-2-ynyloxy] -3-methoxyphenyl) ethyl) -2- Ethanesulfonylamino-3-methylbutyramide, methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) 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- Carboxamide selected from the group consisting of 5-carboxamide;
D) fluazinam, pyrifenox, bupirimate, cyprodinil, fenarimol, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil, triholine (triforine), fenpiclonil, fludioxonil, aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, proproidone procymidone), 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 ne), diclomezine, pyroquilon, proquinazid, tricyclazole, formula IV

(2-butoxy-6-iodo-3-propylchromen-4-one), acibenzolar-S-methyl, captafol, captan, dazomet, holpet (folpet), phenoxanil, quinoxyfen and formula V

A heterocycle selected from the group consisting of N, N-dimethyl-3- (3-bromo-6-fluoro-2-methylindole-1-sulfonyl)-[1,2,4] triazole-1-sulfonamide Compound;
E) mancozeb, maneb, metam, metam, metiram, ferbam, propineb, thiram, zineb, ziram, diethofencarb ), Iprovalicarb, flubenthiavalicarb, propamocarb, 4-fluorophenyl N- (1- (1- (4-cyanophenyl) ethanesulfonyl) but-2-yl) carbamate, Formula VI

Of methyl 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methylbutyrylamino) propanoate and formula VII

[Wherein Z is N or CH]
A carbamate selected from the group consisting of:
F) Guanidine: dodine, iminoctadine, guazatine,
Antibiotics: kasugamycin, streptomycin, polyoxins, validamycin A,
Nitrophenyl derivatives: binapacryl, dinocap, dinobuton,
Sulfur-containing heterocyclic compounds: dithianon, isoprothiolane,
Organometallic compounds: Fentine salts such as fentin acetate,
Organophosphorus compounds: edifenphos, iprobenfos, fosetyl, fosetylaluminum, phosphorous acid and its salts, pyrazophos, tolclofos-methyl,
Organochlorine compounds: Chlorothalonil, dichlofluanid, flusulfamide, hexachlorobenzene, phthalide, penencycuron, quintozene, thiophanate-methyl, tolylfluanid ( tolylfluanid),
Inorganic active compounds: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur,
Others: cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone and spiroxamine
A sterilizing mixture for controlling phytopathogenic harmful fungi, comprising a synergistic amount of another fungicide selected from the group consisting of: As component 1), R ¹ and R ² are independently of each other cyano, fluorine, chlorine, methyl, methoxy or trifluoromethyl, R ³ is fluorine, chlorine, methyl or C ₁ -haloalkyl and R ⁴ is The sterilizing mixture of claim 1, comprising a 2,4-disubstituted N-biphenylpyrazolecarboxamide 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 methyl or trifluoromethyl, R ⁴ is hydrogen, fluorine or chlorine, including 2,4-disubstituted N- biphenyl pyrazole carboxamides of formula I, fungicidal mixture according to claim 1. 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 sterilizing mixture of claim 1, comprising a 2,4-disubstituted N-biphenylpyrazole carboxamide of formula I, wherein R ⁴ is hydrogen.   As component 1) at least one of the following compounds: N- (2 ′, 4′-dichlorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N -(2'-Fluoro-4'-chlorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (2 ', 4'-difluorobiphenyl-2 -Yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (2 ′, 4′-dichlorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H -Pyrazole-4-carboxamide, N- (2 ', 4'-difluorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide and N- (2'-fluoro -4'-chlorobiphenyl-2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide, N- (2'-methyl-4'-chlorobiphenyl-2-yl) -1 -Methyl-3-trifluoromethyl -1H-pyrazole-4-carboxamide, N- (2'-methyl-4'-fluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (2'-Fluoro-4'-methoxybiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N- (2'-methyl-4'-chlorobiphenyl- 2-yl) -1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide, N- (2'-methyl-4'-fluorobiphenyl-2-yl) -1-methyl-3-difluoromethyl -1H-pyrazole-4-carboxamide, N- (2 ', 4'-dichlorobiphenyl-2-yl) -1,3-dimethyl-5-chloro-1H-pyrazole-4-carboxamide, N- (2 ', 4'-dichlorobiphenyl-2-yl) -1,3-dimethyl-1H-pyrazole-4-carboxamide, N- (2', 4'-difluorobiphenyl-2-yl) -1,3-dimethyl -1H-pyrazole-4-carboxamide, N- (2'-fluoro -4'-chlorobiphenyl-2-yl) -1,3-dimethyl-1H-pyrazole-4-carboxamide, N- (2 ', 4'-dichlorobiphenyl-2-yl) -1-methyl-3- Chlorodifluoromethyl-1H-pyrazole-4-carboxamide, N- (2 ′, 4′-dichlorobiphenyl-2-yl) -1-methyl-3-chlorofluoromethyl-1H-pyrazole-4-carboxamide, N -(2 ', 4'-dichlorobiphenyl-2-yl) -1-methyl-3-fluoromethyl-1H-pyrazole-4-carboxamide, N- (2', 4'-dichlorobiphenyl-2-yl) -1-methyl-3-dichlorofluoromethyl-1H-pyrazole-4-carboxamide, N- (2 ', 4'-dichlorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-5-fluoro -1H-pyrazole-4-carboxamide, N- (2'-fluoro-4'-chlorobiphenyl-2-yl) -1-methyl-3-fluoromethyl-1H-pyrazole-4-carboxamide, N- ( 2'-Fluoro-4'-chlorobiphenyl -2-yl) -1-methyl-3-fluoromethyl-1H-pyrazole-4-carboxamide, N- (2 ′, 4′-difluorobiphenyl-2-yl) -1-methyl-3-fluoromethyl- 1H-pyrazole-4-carboxamide, N- (2′-chloro-4′-fluorobiphenyl-2-yl) -1-methyl-3-fluoromethyl-1H-pyrazole-4-carboxamide, N- (2 '-Fluoro-4'-chlorobiphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N- (2'-fluoro-4'-chlorobiphenyl-2- Yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N- (2'-fluoro-4'-methoxybiphenyl-2-yl) -1,3-dimethyl-5-fluoro -1H-pyrazole-4-carboxamide, N- (2'-fluoro-4'-methylbiphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N- (2'-Methyl-4'-chlorobiphenyl-2-yl) -1,3-dimethyl-5-fur Oro-1H-pyrazole-4-carboxamide, N- (2′-methyl-4′-fluorobiphenyl-2-yl) -1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N -(2'-chloro-4'-fluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-5-fluoro-1H-pyrazole-4-carboxamide, N- (2'-methoxy-4 2. The sterilizing mixture of claim 1 comprising '-fluorobiphenyl-2-yl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide.   6. The sterilizing mixture according to any one of claims 1 to 5, comprising components 1) and 2) in a weight ratio of 100: 1 to 1: 100.   6. A sterilizing composition comprising the sterilizing mixture according to any one of claims 1 to 5 and at least one solid or liquid carrier.   A plant pathogen that treats a harmful fungus, its growing environment, or a plant, soil, seed, region, material or space to be protected from fungal infection with the sterilizing mixture according to any one of claims 1 to 5. To control harmful harmful fungi.   9. Process according to claim 8, wherein components 1) and 2) according to any one of claims 1 to 5 are applied simultaneously, i.e. together or separately or sequentially.   10. Process 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 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 g to 1000 g / 100 kg of seed.   Seeds comprising the mixture according to any one of claims 1 to 5 in an amount of 1 g to 1000 g / 100 kg of seeds.   Use of compounds I and II according to any one of claims 1 to 5 for preparing a composition suitable for controlling harmful fungi.