WO2010139653A1 - Fungicidal mixtures comprising heteraromatic sulfonamides - Google Patents

Fungicidal mixtures comprising heteraromatic sulfonamides Download PDF

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WO2010139653A1
WO2010139653A1 PCT/EP2010/057514 EP2010057514W WO2010139653A1 WO 2010139653 A1 WO2010139653 A1 WO 2010139653A1 EP 2010057514 W EP2010057514 W EP 2010057514W WO 2010139653 A1 WO2010139653 A1 WO 2010139653A1
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methyl
phenyl
alkyl
chloro
compound
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PCT/EP2010/057514
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French (fr)
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Marianna Vrettou-Schultes
Jan Klaas Lohmann
Jurith Montag
Wassilios Grammenos
Bernd Müller
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Basf Se
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

Definitions

  • Fungicidal mixtures comprising heteraromatic sulfonamides
  • the present invention relates to mixtures comprising, as active components
  • X is N or CH or C-R 1 ;
  • n indicates the number of substituents R 1 on the pyridine or pyrimidine ring and n is 0, 1 , 2 or 3;
  • R 1 is halogen, CN, NO 2 , OH, SH, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, Ci-C 4 -alkylthio, Ci-C 4 -haloalkylthio, Ci-C 4 -alkylsulfinyl, Ci-C 4 -haloalkylsulfinyl, Ci-C 4 -alkylsulfonyl, Ci-C 4 -haloalkylsulfonyl, amino, Ci-C 4 -alkylamino, di(Ci-C 4 -alkyl)amino, Ci-C 4 -alkoxy-Ci-C 4 -alkyl, C2-C 4 -alk- enyl, C2-C 4 -alkynyl, Cs-Cs-cycloalkyl or Ci-C 4 -al
  • R 1 that are bound to adjacent carbon atoms of the pyridine or pyrimine ring may form together with said carbon atoms a fused benzene ring, a fused saturated or partially unsaturated 5-, 6-, or 7-membered carbocycle or a fused 5-, 6-, or 7-membered heterocycle containing 1 , 2, or
  • heteroatoms selected from the group consisting of 2 nitrogen, 1 oxygen and 1 sulfur atoms as ring members, it being possible for the fused ring to carry 1 or 2 radicals selected from the group consisting of halogen, Ci-C 4 -alkyl, halomethyl, Ci-C 4 -alkoxy or halomethoxy,
  • n 2, 3 or 4 that R 1 are identical or different;
  • R 2 is hydrogen, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, C2-C 4 -alkenyl, C2-C 4 -alkynyl,
  • Het is a 5- or 6-membered heteroaromatic radical, wherein the ring member atoms of the heteroaromatic radical include, besides carbon atoms 1 , 2, 3 or 4 nitrogen atoms, or 1 oxygen atom and 0, 1 or 2 nitrogen atoms or 1 sulfur atom and 0, 1 or 2 nitrogen atoms and wherein the heteroaromatic radical is unsubstituted or carries 1 , 2, 3 or 4 identical or different substituents R a , wherein two radicals R a that are bound to adjacent ring member atoms may form a fused 5- or 6-membered carbocycle or heterocycle, wherein the fused carbocycle or heterocycle is unsubstituted or carries 1 , 2, 3 or 4 identical or different substituents R b ;
  • R a is halogen, CN, NO 2 , Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, Ci-C 4 -alkylthio,
  • Ci-C 4 -alkyl Ci-C 4 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl or Ci-C 4 -alkoxy-Ci-C 4 -alkyl,
  • R b and R c independently of each other are selected from halogen, CN, NO2, OH, SH, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy and Ci-C 4 -halo- alkoxy;
  • - carboxanilides benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, flutolanil, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carbox- amide (penflufen), penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4-methyl-thiazole-5-carboxanilide, 2-chloro-N-(1 ,1
  • - benzoic acid amides flumetover, fluopicolide, fluopyram, zoxamide, N-(3-ethyl- 3,5,5-trimethyl-cyclohexyl)-3-formylamino-2-hydroxy-benzamide;
  • - other carboxamides carpropamid, dicyclomet, mandiproamid, oxytetracyclin, silthiofarm and N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide;
  • - triazoles azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-(4-chloro- phenyl)-2-([1 ,2,4]triazol-1 -yl)-cycloheptanol;
  • - pyridines fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin- 3-yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 2,3,5,6-tetra-chloro-4-methanesulfonyl-pyridine, 3,4,5-trichloropyridine-2,6-di- carbonitrile, N-(1 -( ⁇ -bromo-S-chloro-pyridin ⁇ -y ⁇ -ethyQ ⁇ -dichloronicotinamide,
  • pyrimidines bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, mepani- pyrim, nitrapyrin, nuarimol, pyrimethanil;
  • piperazines triforine;
  • - pyrroles fenpiclonil, fludioxonil;
  • morpholines aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph;
  • dicarboximides fluoroimid, iprodione, procymidone, vinclozolin;
  • non-aromatic 5-membered heterocycles famoxadone, fenamidone, flutianil, octhilinone, probenazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydro- pyrazole-1-carbothioic acid S-allyl ester;
  • acibenzolar-S-methyl acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S, captafol, captan, chinomethionat, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, fenoxanil, Folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quinoxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo-3- propylchromen-4-one, 5-chloro-1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H- benzoimidazole, 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine and
  • guanidines guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate); - antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, polyoxine, validamycin A; nitrophenyl derivates: binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecnazen, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;
  • organophosphorus compounds edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl;
  • organochlorine compounds chlorothalonil, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pencycuron, pentachlorphenole and its salts, phthalide, quintozene, thiophanate-methyl, tolylfluanid, N-(4-chloro-2-nitro- phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
  • - inorganic active substances Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
  • acetochlor alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;
  • - aryloxyphenoxypropionates clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
  • - (thio)carbamates asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate;
  • - dinitroanilines benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin; - diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen; hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil; imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr; - phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-
  • - pyridines aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr; - sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfos
  • - triazines ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam; ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron,tebuthiuron;
  • acetolactate synthase inhibitors bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho- sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam;
  • organo(thio)phosphates acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
  • - carbamates alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate;
  • pyrethroids allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin,
  • - insect growth regulators a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat; - nicotinic receptor agonists/antagonists compounds: clothi
  • - macrocyclic lactone insecticides abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram; - mitochondrial electron transport inhibitor (METI)
  • I acaricides fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
  • oxidative phosphorylation inhibitors cyhexatin, diafenthiuron, fenbutatin oxide, propargite; moulting disruptor compounds: cryomazine; mixed function oxidase inhibitors: piperonyl butoxide;
  • the invention also relates to a method for controlling phytopathogenic harmful fungi using mixtures of a compound I and and a compound Il at least one active compound III and to the use of compound I and compounds Il and compounds III for preparing such mixtures, and to compositions and seed comprising these mixtures.
  • the invention relates to binary mixtures comprising as active ingredients one compound I and one compound Il as defined herein in a synergistically effective amount.
  • the binary mixtures comprise a compound I and a compound Il in a weight ratio of from 100:1 to 1 :100.
  • the invention relates to binary mixtures comprising as active ingredients a compound I as defined herein and N-methyl-2- ⁇ 1-[(5-methyl-3-trifluoromethyl-1 H-pyr- azol-1 -yl)-acetyl]-piperidin-4-yl ⁇ -N-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1 -yl]-4-thiazole- carboxamide.
  • a compound I as defined herein and N-methyl-2- ⁇ 1-[(5-methyl-3-trifluoromethyl-1 H-pyr- azol-1 -yl)-acetyl]-piperidin-4-yl ⁇ -N-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1 -yl]-4-thiazole- carboxamide.
  • compositions comprising compound I and compound and at least one compound III.
  • Compounds I and/or the compounds Il and/or compounds III can be present in different crystal modifications, which may differ in biological activity.
  • WO 05/033081 describes 4-pyridylmethyl sulfonamide compounds of formula
  • X inter alia may represent an unsubstituted or substituted biphenyl ether, and the use of such compounds against plant pathogenic fungi.
  • WO 08/06201 1 describes pyrimidin-4-ylmethyl sulfonamide compounds of formula
  • the compounds I differ from those kown from the abovementioned publications by the combination of the heteroarylmethyl group with the specific sulfonic acid substituent Phenyl-Y-Het.
  • Compounds I and their preparation have been described in the international non- published applications PCT/EP2008/065958, PCT/EP2008/065961 , PCT/EP2009/051500 and PCTEP2009/051501.
  • 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 1 1 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); cycloheximid, 4- ⁇ (2R)-2-[(1 S,3S,5S)-3,5-dimethyl-2-oxocyclohexyl]-2-hydroxyethyl
  • enilconazole imazalil
  • 1-[2-(2,4-dichlorphenyl)-2-(2-propenyloxy)ethyl]-1 H-imidazole Fruits 28, p.
  • fluquinconazole 3-(2,4-dichlorophenyl)-6-fluoro-2-[1 ,2,4]-triazol-1-yl-3H-quin- azolin-4-one (Proc. Br. Crop Prot. Conf.-Pests Dis., 5-3, 411 (1992)); flusilazole, 1- ⁇ [bis-(4-fluorophenyl)methylsilanyl]methyl ⁇ -1 H-[1 ,2,4]triazole (Proc. Br. Crop Prot.
  • N-methyl-2- ⁇ 1-[(5-methyl-3-trifluorometh- yl-1 H-pyrazol-1 -yl)-acetyl]-piperidin-4-yl ⁇ -N-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1 -yl]- 4-thiazolecarboxamide has been described in WO 2007/014290.
  • C n -Cm indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.
  • halogen refers to fluorine, chlorine, bromine and iodine.
  • Ci-C4-alkyl refers to a straight-chained or branched saturated hydrocarbon group having 1 to 4 carbon atoms, for example methyl, ethyl, propyl, 1-methyl- ethyl, butyl, 1-methylpropyl, 2-methylpropyl, and 1 ,1-dimethylethyl.
  • Ci-C4-haloalkyl refers to a straight-chained or branched alkyl group having 1 to 4 carbon atoms, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoro- methyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chlo- ro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloro-
  • Ci-C4-alkoxy refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms which is bonded via an oxygen, at any position in the alkyl group, e.g. methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1 -methyhpropoxy, 2-methyl- propoxy or 1 ,1-dimethylethoxy.
  • Ci-C4-haloalkoxy refers to a Ci-C4-alkoxy radical as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, e.g., OCH 2 F, OCHF 2 , OCF 3 , OCH 2 CI, OCHCI 2 , OCCb, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoro- ethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-tri- fluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoro- ethoxy, 2,2,2-trichloro->ethoxy, OC 2 F 5 , 2-fluoropropoxy
  • Ci-C4-alkoxy- Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms, wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C4-alkoxy group.
  • Ci-C4-alkoxy- Ci-C4-alkoxy refers to an Ci-C4-alkoxy- Ci-C4-alkyl group, which is bonded via an oxygen atom to the remainder of the molecule.
  • Ci-C4-alkylthio refers to straight-chain or branched alkyl groups having 1 to 4 carbon atoms bonded through a sulfur atom, at any position in the alkyl group, for example methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.
  • Ci-C4-haloalkylthio refers to straight-chain or branched haloalkyl groups having 1 to 4 carbon atoms bonded through a sulfur atom, at any position in the haloalkyl group.
  • Ci-C4-alkylamino refers to an amino radical carrying one Ci-C4-alkyl group as substituent, for example methylamino, ethylamino, propylamino, 1-methyl- ethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1 ,1-dimethylethyl- amino and the like.
  • di(Ci-C4-alkyl)amino refers to an amino radical carrying two identical or different Ci-C4-alkyl groups as substituents, for example dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, N-ethyl-N-methylamino, N-(n-propyl)-N-methyl- amino, N-isopropyl-N methylamino, N-(n-butyl)-N-methylamino, N-(n-pentyl)-N-methyl- amino, N-(2-butyl)-N methylamino, N-isobutyl-N-methylamino, and the like.
  • Ci-C4-alkoxycarbonyl refers to a Ci-C4-alkoxy radical which is attached via a carbonyl group.
  • di(Ci-C4-alkyl)aminocarbonyl refers to a di(Ci-C4)alkylamino radical which is attached via a carbonyl group.
  • C2-C4-alkenyl refers to a branched or unbranched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl (allyl), 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl- 2-propenyl.
  • C2-C4-alkynyl refers to a branched or unbranched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and containing at least one triple bond, such as ethynyl, 1-propynyl, 2-propynyl (propargyl), 1-butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2-propynyl.
  • Cs-Cs-cycloalkyl refers to monocyclic saturated hydrocarbon radicals having 3 to 8 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • Ci-C4-alkyl-C3-C8-cycloalkyl refers to a cycloalkyl radical having 3 to 8 carbon atoms, wherein one hydrogen atom of the cycloalkyl radical is replaced by a Ci-C4-alkyl group.
  • 5-, 6- or 7-membered carbocycle is to be understood as meaning both saturated and partially unsaturated carbocycles having 5, 6 or 7 ring members as well as phenyl.
  • non-aromatic rings include cyclopentyl, cyclopentenyl, cyclo- pentadienyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cycloheptenyl, cycloheptadienyl and the like.
  • 5-, 6-, or 7-membered heterocycle which contains one, two, three or four heteroatoms from the group consisting of O, N and S, is to be understood as meaning both saturated and partially unsaturated as well as aromatic heterocycles having 5, 6 or 7 ring atoms. Examples include:
  • heterocycyl (heteroaromatic radical) which contains 1 , 2, 3 or 4 nitrogen atoms: 6 membered heteroaryl groups which, in addition to carbon atoms, may contain 1 , 2, 3 or 4 nitrogen atoms as ring members, for example 2-pyridinyl, 3-pyridin- yl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.
  • heteroaryl groups which, in addition to carbon atoms, may contain 1 , 2, 3 or 4 nitrogen atoms as ring members, for example 2-pyridinyl, 3-pyridin- yl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.
  • Ci-C4-alkanediyl refers to a divalent, branched or straight-chain saturated hydrocarbon radical having 1 to 4 carbon atoms, derived from a Ci-C4-alkyl group (as defined above) that has two points of attachment.
  • two radicals R 1 that are bound to adjacent carbon atoms of the pyridine ring may form together with said carbon atoms a fused ring refers to a bicyclic ring system, wherein pyridin-4-yl carries a fused-on 5-, 6- or 7-membered carbocyclic or heterocyclic ring.
  • fused bicyclic ring systems include benzo[b]py- ridine (quinoline), pyrido[2,3-b]pyridine (1 ,8-naphthyridine), pyrido[3,4-b]pyridine (1 ,7-naphthyridine), pyrido[4,3-b]pyridine (1 ,6-naphthyridine), pyrido[3,2-b]pyridine (1 ,5-naphthyridine), pyrido[2,3-d]pyrimidine, pyrido[3,2-d]pyrimidine, pyrido[2,3-b]fu- rane, pyrido[3,2-b]furane, pyrido[2,3-c]furane, pyrido[2,3-d]thiazole, pyrido[3,2-d]thia- zole, pyrido[2,3-d]isoxazo
  • the fused-on ring can be unsubstituted or substituted by 1 , 2, 3 radicals substituents selected, independently from one another, from the group consisting of halogen, Ci-C4-alkyl, halomethyl, Ci-C4-alkoxy and halomethoxy.
  • two radicals R a that are bound to adjacent carbon atoms of the Het group may form together with said carbon atoms a fused ring refers to a bicyclic ring system, wherein Het, carries a fused-on 5-, 6- or 7-membered carbocyclic or heterocyclic ring.
  • fused bicyclic rings examples include quinoline, quinazoline, benzofurane, isobenzofurane, phthalazine, cinnoline, quinoxaline, benzothiazole, benzoisothiazole, benzoxazole, benzoisoxazole, 1 ,5-naphthyridine, 1 ,6-naphthyridine, 1 ,7-naphthyridine, 1 ,8-naphthyridine, 2,6-naphtyridine, 2,7-naphtyridine, pyrido[2,3-d]pyrimidine, pyrido[3,2-d]pyrimidine, pyrido[3,4-d]pyrimidine, pyrido[4,3-d]pyrimidine, pyrido[2,3-b]- furane, pyrido[3,2-b]furane, pyrido[2,
  • the fused-on ring can be unsubstituted or substituted by 1 , 2, 3 or 4 radicals substituents selected, independently from one another, from the group consisting of halogen, cyano, nitro, OH, SH, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
  • Agriculturally acceptable salts of the compounds I encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds I.
  • Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry 1 to 4 Ci-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethyl- ammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphoni- um ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogen- phosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluoro- phosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting a compound I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • One embodiment of the invention relates to mixtures comprising compounds I, wherein X is N. Another embodiment relates to mixtures comprising compounds I, wherein X is CH or C-R 1 .
  • One embodiment relates to mixtures comprising compounds I, wherein n is 0, 1 or 2, in particular n is 1.
  • a further embodiment relates to mixtures comprising compounds
  • a further embodiment relates to mixtures comprising compounds I, wherein n is 0.
  • One embodiment relates to mixtures comprising compounds I, wherein m is 0, 1 or
  • m is 0 or 1 , in particular m is 0.
  • a further embodiment relates to mixtures comprising compounds I, wherein m is 1.
  • R 1 is selected from halogen, CN, NO2, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-halo- alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylsulfinyl, Ci-C4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, Ci-C4-alkoxy-Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Cs-Cs-cycloalkyl and Ci-C4-alk- yl-C3-C8-cycl
  • a further embodiment relates to mixtures comprising compounds I, wherein R 1 is selected from methyl, ethyl, n-propyl and i-propyl, more preferably R 1 is methyl.
  • a further embodiment relates to mixtures comprising compounds I, wherein R 1 is selected from methoxy, ethoxy, n-propoxy and i-propoxy, in particular R 1 is methoxy.
  • One embodiment relates to mixtures comprising compounds I, wherein R 2 is selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl and C3-C8-cycloalkyl, more preferably selected from hydrogen and Ci-C4-alkyl, and in particlar R 2 is hydrogen.
  • R 2 is CH3.
  • One embodiment relates to mixtures comprising compounds I, wherein R 3 is selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl and Ci-C4-alkoxy, more preferably selected from halogen, Ci-C4-alkyl and Ci-C4-alkoxy, and even more selected preferably from F, Cl, Br, I, CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 and CH(CH 3 ) 2 , in particular R 3 is F.
  • Another embodiment relates to mixtures comprising compounds I, wherein R 3 is Cl.
  • a further embodiment relates to mixtures comprising compounds I, wherein R 3 is CH 3 .
  • mixtures comprising compounds I wherein the moiety Het-Y is located on the phenyl ring in the meta- or para-position with respect to the sulfonyl group, in particular in the para-position.
  • mixtures comprising compounds I wherein the moiety Het-Y is located on the phenyl ring in the meta-position with respect to the sulfonyl group.
  • Another embodiment relates to mixtures comprising compounds I, wherein Y is -S-.
  • One embodiment relates to mixtures comprising compounds I, wherein Het is selected from pyridinyl, pyrimidinyl, thiophenyl, pyrazolyl, isoxazoyl, isothiazolyl, thiazolyl, imidazolyl and oxazolyl, more preferably selected from pyridinyl, pyrimidinyl, thiophenyl and pyrazolyl, and in particular Het is pyridinyl.
  • Another embodiment relates to mixtures comprising compounds I, wherein Het is pyrazolyl.
  • Another embodiment relates to mixtures comprising compounds I, wherein Het is pyrimidyl.
  • a further preferred embodiment relates to mixtures comprising compounds I, wherein Het is selected from pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridin-5-yl, pyridin-6-yl, pyrimidin- 2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrimidin-6-yl, thiophen-2-yl, thiophen-3-yl, thiophen- 4-yl, thiophen-5-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl and pyrazol-5-yl, and more preferably selected from pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridin-5-yl, pyridin-6-yl, pyrimidn-2-yl, pyrazol-1-yl, pyrazol-3-yl,
  • One embodiment relates to mixtures comprising compounds I, wherein Het carries 1 , 2 or 3 radicals R a , more preferably 1 or 2 radicals R a , and in particular Het carries 1 radical R a .
  • Another embodiment relates to mixtures comprising compounds I, wherein Het carries 2 radicals R a .
  • Another preferred embodiment relates to mixtures comprising compounds I, wherein R a is selected from F, Cl, Br, CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 , CH(CH 3 ) 2 , CF 3 , CF 2 CHF 2 and CF 2 CF 3 , more preferably selected from F, Cl, Br, CH 3 and CF 3 .
  • One embodiment relates to mixtures comprising compounds I, wherein R b and R c are independently of each other selected from halogen, Ci-C4-alkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, more preferably these radicals are selected from F, Cl, CH 3 , OCH 3 and CF 3 .
  • the mixtures comprise compounds I, wherein X is N or CH, n is 0, 1 or 2, R 1 is CH 3 or OCH 3 , R 2 is hydrogen, the moiety Het- Y is located on the phenyl ring in the para-position with respect to the sulfonyl group, Y is -O-, m is 0 or 1 , R 3 is CH 3 or F, Het is selected from pyridin-2-yl, pyridin-4-yl and pyrimidin-2-yl, wherein the aforementioned 3 heteroaromatic radicals carry 1 or 2 radicals R a selected from Cl, Br, CH 3 , SCH 3 , OCHF 2 and CF 3 , which compounds I are of formula 1.1 :
  • component 1 With respect to their use as component 1 ) in the inventive mixtures, particular preference is given to the compounds I which are of subformula 1.1 compiled in the Table A below.
  • the groups mentioned in the Tables for a substituent are furthermore, independently of the combination wherein they are mentioned, a particularly preferred embodiment of the substituent in question.
  • Table A Compounds I of subformula 1.1 , wherein m, n, R 1 , R 3 and the meaning of Het for each individual compound corresponds in each case to one line.
  • the mixtures comprise compounds I, wherein X is N or CH, n is O, 1 or 2, R 1 is CH 3 or OCH 3 , R 2 is hydrogen, the moiety Het- Y is located on the phenyl ring in the para-position with respect to the sulfonyl group, Y is -S-, m is O or 1 , R 3 is CH 3 or F, Het is selected from pyridin-2-yl, pyridin-4-yl and pyrimidin-2-yl, wherein the aforementioned 3 heteroaromatic radicals carry 1 or 2 radicals R a selected from Cl, Br, CH 3 and CF 3 , which compounds I are of formula 1.2:
  • component 1 With respect to their use as component 1 ) in the inventive mixtures, particular preference is given to the compounds I which are of subformula 1.2 compiled in the Table D below.
  • the groups mentioned in the Tables for a substituent are furthermore, independently of the combination wherein they are mentioned, a particularly preferred embodiment of the substituent in question.
  • Table D Compounds I of subformula 1.2, wherein m, n, R 1 , R 3 and the meaning of Het for each individual compound corresponds in each case to one line.
  • the mixtures comprise compounds I, wherein X is N or CH, n is O, 1 or 2, R 1 is CH 3 or OCH 3 , R 2 is hydrogen, the moiety Het- Y is located on the phenyl ring in the meta-position with respect to the sulfonyl group, Y is -O-, m is 0 or 1 , R 3 is CH3 or F, Het is selected from pyridin-2-yl, pyridin-4-yl and pyrimidin-2-yl, wherein the aforementioned 3 heteroaromatic radicals carry 1 or 2 radicals R a selected from Cl, Br, CH3 and CF3, which compounds I are of formula 1.3:
  • component 1 With respect to their use as component 1 ) in the inventive mixtures, particular preference is given to the compounds I which are of subformula 1.3 compiled in the Table E below.
  • the groups mentioned in the Tables for a substituent are furthermore, independently of the combination wherein they are mentioned, a particularly preferred embodiment of the substituent in question.
  • Table E Compounds I of subformula 1.3, wherein m, n, R 1 , R 3 and the meaning of Het for each individual compound corresponds in each case to one line.
  • the mixtures comprise compounds I, wherein X is N or CH, n is O, 1 or 2, R 1 is CH 3 or OCH 3 , R 2 is hydrogen, the moiety Het- Y is located on the phenyl ring in the para-position with respect to the sulfonyl group, Y is -O-CH2-, m is O or 1 , R 3 is CH 3 or F, Het is selected from pyridin-2-yl, pyridin-4-yl and pyrimidin-2-yl, wherein the aforementioned 3 heteroaromatic radicals carry 1 or 2 radicals R a selected from Cl, Br, CH 3 and CF 3 , which compounds I are of formula 1.4:
  • component 1 With respect to their use as component 1 ) in the inventive mixtures, particular preference is given to the compounds I which are of subformula 1.4 compiled in the Table F below.
  • the groups mentioned in the Tables for a substituent are furthermore, independently of the combination wherein they are mentioned, a particularly preferred embodiment of the substituent in question.
  • Table F Compounds I of subformula 1.4, wherein m, n, R 1 , R 3 and the meaning of Het for each individual compound corresponds in each case to one line.
  • the mixtures comprise compounds I, wherein X is N or CH, n is 0, 1 or 2, R 1 is CH 3 or OCH 3 , R 2 is methyl, the moiety Het-Y is located on the phenyl ring in the para-position with respect to the sulfonyl group, Y is -0-, m is O or 1 , R 3 is CH 3 or F, Het is selected from pyridin-2-yl, pyridin-4-yl and pyrimidin-2-yl, wherein the aforementioned 3 heteroaromatic radicals carry 1 or 2 radicals R a selected from Cl, Br, CH3 and CF3, which compounds I are of formula 1.5:
  • component 1 With respect to their use as component 1 ) in the inventive mixtures, particular preference is given to the compounds I which are of subformula 1.5 compiled in the Table G below.
  • the groups mentioned in the Tables for a substituent are furthermore, independently of the combination wherein they are mentioned, a particularly preferred embodiment of the substituent in question.
  • Table G Compounds I of subformula 1.5, wherein m, n, R 1 , R 3 and the meaning of Het for each individual compound corresponds in each case to one line.
  • the mixtures comprise compound I, compounds Il and compounds III in a synergistically effective amount. It is also preferred, that the binary mixtures comprise a compound I and a compound Il in as synergistically effective amount. Another embodiment relates to mixtures wherein compound Il selected from groups A) to I) is different from compound III selected from groups A) to I).
  • the mixtures comprise as compounds Il and compounds III fungicidal compounds that are independently of each other selected from the groups A), B), C), D), E) and F). It may also be preferred that the binary mixtures comprise as compound Il a fungicidal compound that is selected from the groups A), B), C), D), E) and F).
  • mixtures comprise as compound
  • Ili a herbicidal compound that is selected from the group H).
  • mixtures comprise as compound III an insecticidal compound that is selected from the group I).
  • mixtures comprising at least one compound selected from the strobilurines of group A) and particularly selected from azoxystrobin, dimoxy- strobin, enestroburin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb and trifloxystrobin.
  • mixtures comprising at least one active substance selected from the carboxamides of group B) and particularly selected from bixafen, boscalid, fluopyram, isopyrazam, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-
  • 5-fluoro-1 H-pyrazole-4-carboxamide penflufen
  • penthiopyrad penthiopyrad, sedaxane, fenhexamid, metalaxyl, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolid (picobenzamid), fluopram, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-car- boxamide (penflufen), penthiopyrad, zoxamide, carpropamid, mandipropamid and N- (3',4',5'-trifluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide.
  • mixtures comprising at least one compound selected from the azoles of group C) and particularly selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamid, benomyl and ethaboxam.
  • mixtures comprising at least one compound selected from the heterocyclic compounds of group D) and particularly selected from fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforine, fludioxonil, dodemorph, fen- propimorph, tridemorph, fenpropidin, iprodione, vinclozolin, famoxadone, fenamidone, probenazole, proquinazid, acibenzolar-S-methyl, captafol, folpet, fenoxanil, quinoxyfen and 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine.
  • mixtures comprising at least one compound selected from the carbamates of group E) and particularly selected from mancozeb, metiram, propineb, thiram, iprovalicarb, benthiavalicarb and propamocarb.
  • mixtures comprising at least one compound selected from the fungicides given in group F) and particularly selected from dithianon, fentin salts, such as fentin acetate, fosetyl, fosetyl-aluminium, H3PO3 and salts thereof, chlorothalonil, dichlofluanid, thiophanat-methyl, copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, cymoxanil, metrafenone, spiroxamine and N-methyl-2- ⁇ 1 -[(5-methyl-3-trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin-4-yl ⁇ - N-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1 -yl]-4-thiazolecarboxamide.
  • fentin salts such as fentin acetate, fosetyl, fosetyl-aluminium
  • mixtures comprising as compound Il one compound selected from the strobilurines of group A) and particularly selected from azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, orysa- strobin, picoxystrobin, pyraclostrobin, pyribencarb and trifloxystrobin, and as compound III at least one compound selected from the carboxamides of group B) and particularly selected from bixafen, boscalid, fluopyram, isopyrazam, N-(2-(1 ,3-dimethyl-butyl)- phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide (penflufen), penthiopyrad, sedaxane, fenhexamid, metalaxyl, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolid (pico
  • mixtures comprising as compound Il one active substance selected from the strobilurines of group A) and particularly selected from azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb and trifloxystrobin, and as compound III at least one compound selected from the azoles of group C) and particularly selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamid, benomyl, carbend
  • mixtures comprising as compound Il one compound selected from the azoles of group C) and particularly selected from cypro- conazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, met- conazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamid, beno- myl, carbendazim and ethaboxam, and as compound III at least one compound selected from the carboxamides of group B) and particularly selected from bixafen, boscalid, fluopyram, isopyrazam, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-flu
  • mixtures comprising as compound Il one active substance selected from the strobilurines of group A) and particularly selected from azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb and trifloxystrobin, and as compound III at least one compound selected from the heterocyclic compounds of group D) and particularly selected from fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforine, fludioxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, vinclozolin, famoxadone, fenamidone, probenazole, proquinazid, acibenz- olar-S-methyl, captafol, folpet, fenoxan
  • mixtures comprising as compound Il one compound selected from the heterocyclic compounds of group D) and particularly selected from fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforine, fludioxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, vinclozolin, famoxadone, fenamidone, probenazole, proquinazid, acibenzolar-S-methyl, captafol, folpet, fenoxanil, quinoxyfen and 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine- 7-ylamine, and as compound III at least one compound selected from the carbox- amides of group B) and particularly selected from bixafen, boscalid, fluopyram, isopyrazam
  • mixtures comprising as compound Il one compound selected from the strobilurines of group A) and particularly selected from azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, orysa- strobin, picoxystrobin, pyraclostrobin, pyribencarb and trifloxystrobin, and as compound III at least one compound selected from the fungicides given in group F) and particularly selected from dithianon, fentin salts, such as fentin acetate, fosetyl, fosetyl- aluminium, H3PO3 and salts thereof, chlorthalonil, dichlofluanid, thiophanate-methyl, copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, cymox- anil, metrafenone, spiroxamine and N-methyl-2- ⁇ 1-[(5-methyl-3-trifluoro
  • mixtures comprising as compound Il one compound selected from the fungicides given in group F) and particularly selected from dithianon, fentin salts, such as fentin acetate, fosetyl, fosetyl-aluminium, H3PO3 and salts thereof, chlorthalonil, dichlofluanid, thiophanat-methyl, copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, cymoxanil, metrafenone, spirox- amine and N-methyl-2- ⁇ 1 -[(5-methyl-3-trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin- 4-yl ⁇ -N-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide, and as compound III at least one compound selected from the carboxamides of group B) and particularly selected from bixa
  • mixtures comprising as components 2) and 3) at least two compounds selected from epoxiconazole, metconazole, tebuconazole, triticonazole, prothioconazole, difenoconazole, cyproconazole, kresoxim-methyl, pyraclostrobin, azoxystrobin, trifloxystrobin, dimoxystrobin, orysastrobin, fluoxastrobin, dimethomorph, 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, pyrimethanil, metalaxyl, fenpropimorph, mancozeb, metiram, thiophanate-methyl, chlorothalonil, Metrafenon, bixafen, boscalid, N-(3',4',5'-trifluorobiphenyl-2-yl)-3-d
  • binary mixtures comprising as components 2) one compound selected from epoxiconazole, metconazole, tebuconazole, triticonazole, prothioconazole, difenoconazole, cyproconazole, kresoxim-methyl, pyraclostrobin, azoxystrobin, trifloxystrobin, dimoxystrobin, orysastrobin, fluoxastrobin, dimethomorph, 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, pyrimethanil, metalaxyl, fenpropimorph, mancozeb, metiram, thiophanate-methyl, chlorothalonil, Metrafenon, bixafen, boscalid, N-(3',4',5'-trifluorobiphenyl-2-yl)-3-difluoro
  • compenent 3 (Co. 3) in the inventive ternary mixtures, preference is given to the compounds III which are compiled in the Table C below.
  • Table C Preferred com ounds III for use as component 3) (Co. 3).
  • the present invention furthermore to the mixtures M-1 to M-123970 as defined in Tables 1 to 23, where a row corresponds in each case to a fungicidal composition
  • a row corresponds in each case to a fungicidal composition
  • the compositions described comprise the active substances in synergistically effective amounts.
  • Table 1 Mixtures M-1 to M-5390 comprising one compound I as defined and numbered in Tables A, D, E , F and G as component 1 ) (Co. 1 ) and one compound Il from groups A) to F) as defined and numbered in Table B as component 2) (Co. 2) and one compound III from groups A) to F) as defined and numbered in Table C as component 3) (Co. 3).
  • Table 2 Mixtures M-5391 to M-10780 as defined in Table 1 wherein component 2 (Co.
  • component 3 (Co. 3) is compound 111-1 instead of III-2.
  • component 3 (Co. 2) is compound 11— 3 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-3.
  • component 3 (Co. 2) is compound II-4 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-4.
  • component 3 (Co. 2) is compound II-6 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-6.
  • Table 7 Mixtures M-32341 to M-37730 as defined in Table 1 wherein component 2 (Co. 2) is compound II-7 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-7.
  • Table 8 Mixtures M-37731 to M-43120 as defined in Table 1 wherein component 2
  • component 3 (Co. 2) is compound II-9 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-9.
  • component 3 (Co. 2) is compound 11-10 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of 111-10.
  • Table 12 Mixtures M-59291 to M-64680 as defined in Table 1 wherein component 2 (Co. 2) is compound 11-12 instead of 11-1 and wherein, if applicable, component 3 (Co.
  • component 3 (Co. 2) is compound 11-15 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of 111-15.
  • Table 16 Mixtures M-80851 to M-86240 as defined in Table 1 wherein component 2
  • Table 17 Mixtures M-86241 to M-91630 as defined in Table 1 wherein component 2 (Co. 2) is compound 11-17 instead of 11-1 and wherein, if applicable, component 3 (Co.
  • Table 18 Mixtures M-91631 to M-97020 as defined in Table 1 wherein component 2
  • Table 21 Mixtures M-107801 to M-1 13190 as defined in Table 1 wherein component 2 (Co. 2) is compound 11-21 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of 111-21.
  • Table 22 Mixtures M-1 13191 to M-1 18580 as defined in Table 1 wherein component 3 (Co. 3) is compound III-22 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-22.
  • Table 23 Mixtures M-1 18581 to M-123970 as defined in Table 1 wherein component 3 (Co. 3) is compound III-23 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-23.
  • Table 22 Binary Mixtures B-1 to B-5635 comprising as active ingredients one compound I as defined and numbered in Table A as component 1 ) (Co. 1 ) and one compound Il from groups A) to F) as defined and numbered in Table B as component 2) (Co. 2).
  • inventive mixtures are binary mixtures comprising as component 2) a compound selected from pyraclostrobin, boscalid fluoxapyroxad, chlorothalonil, metiram, ametoctradin, epoxiconazole and dimethomorph.
  • the mixtures and compositions according to the invention are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn.
  • Oomyce- tes Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti).
  • Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
  • the mixtures and compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g.
  • cereals e. g. wheat, rye, barley, triticale, oats or rice
  • beet e. g. sugar beet or fodder beet
  • fruits such as pomes, stone fruits or soft fruits, e. g.
  • the inventive mixtures and compositions are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant.
  • treatment of plant propagation materials with the inventive combination of compound I and compounds Il and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
  • cultiva plants is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://www.bio.org/speeches/pubs/er/agrLproducts.asp).
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted post-transtional modification of protein(s), oligo- or polypeptides e. g.
  • HPPD hydroxyphenylpyruvate dioxygenase
  • ALS acetolactate synthase
  • EPSPS enolpyruvylshikimate-3-phosphate synthase
  • GS glutamine synthetase
  • EP-A 242 236, EP-A 242 246) or oxynil herbicides see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering.
  • Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield ® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as ⁇ -endotoxins, e. g.
  • VIP vegetative insecticidal proteins
  • VIP1 e.g. VIP1 , VIP2, VIP3 or VIP3A
  • insecticidal proteins of bacteria colonizing nematodes e. g. Photorhabdus spp.
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize- RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxy- steroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase
  • ion channel blockers such as blockers of sodium
  • these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ).
  • Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g.
  • insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of athropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).
  • Genetically modified plants capable to synthesize one or more insecticidal proteins are, e.
  • WO 03/018810 MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CryiAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, e. g.
  • EP-A 392 225 plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora).
  • T4-lysozym e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g.
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health- promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera ® rape, DOW Agro Sciences, Canada).
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
  • inventive mixtures and compositions are particularly suitable for controlling the following plant diseases:
  • Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alternata), tomatoes (e. g. A. solani or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A.
  • Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.) on corn (e. g. D. maydis), cereals (e. g. B. sorokiniana: spot blotch), rice (e. g. B. oryzae) and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce;
  • Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn, rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C.
  • herbarum black ear
  • Claviceps purpurea ergot
  • Cochliobolus anamorph: Helminthosporium of Bipolaris
  • spp. leaf spots
  • corn C. carbonum
  • cereals e. g. C. sativus, anamorph: B. sorokiniana
  • rice e. g. C. miyabeanus, anamorph: H. oryzae
  • spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C.
  • Cylindrocarpon spp. e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.
  • vines e. g. C. liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease
  • Dematophora teleomorph: Rosellinia necatrix (root and stem rot) on soybeans
  • Diaporthe spp. e. g. D. phaseolorum (damping off) on soybeans
  • Drechslera syn.
  • sabinae rust on pears
  • Helminthosporium spp. syn. Drechslera, teleomorph: Cochliobolus
  • Hemileia spp. e. g. H. vastatrix (coffee leaf rust) on coffee
  • lsariopsis clavispora syn. Cladosporium vitis
  • Macrophomina phaseolina syn. phaseoli
  • root and stem rot on soybeans and cotton
  • Microdochium syn. Fusarium
  • nivale pink snow mold
  • Microsphaera diffusa (powdery mildew) on soybeans
  • Monilinia spp. e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants
  • Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas
  • Peronospora spp. downy mildew) on cabbage (e. g. P.
  • brassicae brassicae
  • rape e. g. P. parasitica
  • onions e. g. P. destructor
  • tobacco P. tabacina
  • soybeans e. g. P. manshurica
  • Phakopsora pachyrhizi and P. meibomiae staybean rust
  • Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P.
  • betae root rot, leaf spot and damping-off on sugar beets
  • Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P.
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers
  • Plasmopara spp. e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers
  • Podosphaera spp. powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples
  • Polymyxa spp. e. g. on cereals, such as barley and wheat (P.
  • Pseudocercosporella herpotrichoides eyespot, teleo- morph: Tapesia yallundae
  • Pseudoperonospora downy mildew
  • Pseudopezicula tracheiphila red fire disease or .rotbrenner', anamorph: Phialophora) on vines
  • Puccinia spp. rusts
  • oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphani- dermatum); Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp.
  • R. solani root and stem rot
  • S. solani silk and stem rot
  • S. solani silk and stem rot
  • S. solani silk blight
  • R. cerealis Rhizoctonia spring blight
  • Rhizopus stolonifer black mold, soft rot
  • Rhynchosporium secalis scald
  • Sarocladium oryzae and S. attenuatum sheath rot) on rice
  • Sclerotinia spp e. g.
  • R. solani root and stem rot
  • S. solani silk blight
  • R. cerealis Rhizoctonia spring blight
  • Rhizopus stolonifer black mold, soft rot
  • Rhynchosporium secalis scald
  • Sarocladium oryzae and S. attenuatum sheath rot
  • Sclerotinia spp Sclerotinia spp.
  • seed rot or white mold on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn.
  • Erysiphe) necator prowdery mildew, anamorph: Oidium tuckeri
  • Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp.
  • S. nodorum Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum
  • wheat Synchytrium endobioticum on potatoes (potato wart disease)
  • Taphrina spp. e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums
  • Thielaviopsis spp. black root rot
  • tobacco, pome fruits, vegetables, soybeans and cotton e. g. T. basicola (syn. Chalara elegans); Tilletia spp.
  • protection of materials is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, colling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria.
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp.
  • Tyromyces spp. Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichorma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
  • mixtures and compositions of the present invention are effective against plant pathogens in speciality crops such as vine, fruits, hop, vegetables and tabacco - see the above list.
  • Plant propagation materials may be treated with the mixtures and compositions of the invention prophylactically either at or before planting or transplanting.
  • the present invention also relates to a pesticidal agent comprising at least one solid or liquid carrier and a composition as described herein.
  • the compound I and compounds II, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • agrochemical compositions e. g. solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the composition type depends on the particular intended purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention.
  • composition types are suspensions (SC, OD, FS), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, DP, DS) or granules (GR, FG, GG, MG), which can be water-soluble or wettable, as well as gel formulations for the treatment of plant propagation materials such as seeds (GF).
  • composition types e. g. SC, OD, FS, WG, SG, WP, SP, SS, WS, GF
  • composition types such as DP, DS, GR, FG, GG and MG are usually used undiluted.
  • compositions are prepared in a known manner (cf. US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, S. 8-57 und ff. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: Weed Control as a Science (J.
  • the agrochemical compositions may also comprise auxiliaries which are customary in agrochemical compositions.
  • auxiliaries depend on the particular application form and active substance, respectively.
  • auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents, anti- foaming agents, if appropriate colorants and tackifiers or binders (e. g. for seed treatment formulations).
  • Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e. g.
  • Solid carriers are mineral earths such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • mineral earths such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium sulfate, ammonium phosphat
  • Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsoulfonic acid (Borresperse ® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Morwet ® types, Akzo Nobel, U.S.A.), dibutylnaphthalene- sulfonic acid (Nekal ® types, BASF, Germany), and fatty acids, alkylsulfonates, alkyl- arylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers,
  • aromatic sulfonic acids such as ligninsoulfonic acid (Borresperse
  • methylcellulose g. methylcellulose
  • hydrophobically modified starches polyvinyl alcohols (Mowiol ® types, Clariant, Switzer- land), polycarboxylates (Sokolan ® types, BASF, Germany), polyalkoxylates, polyvinyl- amines (Lupasol ® types, BASF, Germany), polyvinylpyrrolidone and the copolymers therof.
  • thickeners i. e. compounds that impart a modified flowability to compositions, i. e. high viscosity under static conditions and low viscosity during agitation
  • thickeners are polysaccharides and organic and anorganic clays such as Xanthan gum (Kelzan ® , CP Kelco, U.S.A.), Rhodopol ® 23 (Rhodia, France), Veegum ® (RT. Vanderbilt, U.S.A.) or Attaclay ® (Engelhard Corp., NJ, USA).
  • Bactericides may be added for preservation and stabilization of the composition.
  • suitable bactericides are those based on dichlorophene and benzyl- alcohol hemi formal (Proxel ® from ICI or Acticide ® RS from Thor Chemie and Kathon ® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide ® MBS from Thor Chemie).
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • anti-foaming agents are silicone emulsions (such as e. g. Silikon ®
  • Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples to be mentioned und the designations rhodamin B, C. I. pigment red 1 12, C. I. solvent red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
  • tackifiers or binders examples include polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose ® , Shin-Etsu, Japan).
  • Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the compound I and compounds Il with at least one solid carrier.
  • Granules e. g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers.
  • solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.
  • composition types are:
  • composition types for dilution with water i) Water-soluble concentrates (SL, LS)
  • Emulsions (EW, EO, ES)
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • Water-soluble concentrates (LS), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES) emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • These compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted.
  • the compositions in question give, after two-to- tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before sowing.
  • Methods for applying or treating agrochemical compounds and compositions thereof, respectively, on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting, dusting and soaking application methods of the propagation material.
  • the compounds or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • a suspension-type (FS) composition is used for seed treatment.
  • a FS composition may comprise 1-800 g/l of active substance, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
  • the active substances can be used as such or in the form of their compositions, e. g. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading, brushing, immersing or pouring.
  • the application forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active substances according to the invention.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
  • emulsions, pastes or oil dispersions the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier.
  • concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil and such concentrates are suitable for dilution with water.
  • the active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1 % by weight of active substance.
  • the active substances may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives.
  • UUV ultra-low-volume process
  • the amounts applied are, depending on the kind of effect desired, between 0.01 and 2.0 kg of active substance per ha.
  • active substance In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 1 to 1000 g, preferably from 5 to 100 g, per 100 kilogram of seed are generally required.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are, e. g., 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, herbicides, bactericides, other fungicides and/or pesticides may be added to the active substances or the compositions comprising them, if appropriate not until immediately prior to use (tank mix).
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • Adjuvants which can be used are in particular organic modified polysiloxanes such as Break Thru S 240 ® ; alcohol alkoxylates such as Atplus 245 ® , Atplus MBA 1303 ® , Plurafac LF 300 ® and Lutensol ON 30 ® ; EO/PO block polymers, e. g. Pluronic RPE 2035 ® and Genapol B ® ; alcohol ethoxylates such as Lutensol XP 80 ® ; and dioctyl sulfosuccinate sodium such as Leophen RA ® .
  • organic modified polysiloxanes such as Break Thru S 240 ®
  • alcohol alkoxylates such as Atplus 245 ® , Atplus MBA 1303 ® , Plurafac LF 300 ® and Lutensol ON 30 ®
  • EO/PO block polymers e. g. Pluronic RPE 2035 ® and Genapol B ®
  • compositions according to the invention can, in the use form as fungicides, also be present together with other active substances, e. g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers, as pre-mix or, if appropriate, not until immeadiately prior to use (tank mix).
  • active substances e. g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers, as pre-mix or, if appropriate, not until immeadiately prior to use (tank mix).
  • a compound I and at least one compound Il occur simultaneously at the site of action (i.e. the harmful fungi to be controlled or their habitats such as infected plants, plant propagation materials, particularly seeds, surfaces, materials or the soil as well as plants, plant propagation materials, particularly seeds, soil, surfaces, materials or rooms to be protected from fungal attack) in an effective amount.
  • This can be obtained by applying compound I and compound Il simultaneously, either jointly (e. g. as tank-mix) or separately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s).
  • the order of application is not essential for working of the present invention.
  • the weight ratio of compound I and compound Il generally depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4: 1.
  • any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the compound I.
  • the weight ratio of component 1 ) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4:1 , and the weight ratio of component 1 ) and component 3) usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of the range of from 1 :4 to 4:1 , and the weight ratio of component 1 ) and component 3) usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the
  • the compound I/compound ll/compound III ratio is advantageously chosen so as to produce a synergistic effect.
  • the term "synergistic effect” is also understood to refer to that defined by application of the Tammes method, (Tammes, P. M. L., "Isoboles, a graphic representation of synergism in pesticides", Netherl. J. Plant Pathol. 70, 1964).
  • the components can be used individually or already partially or completely mixed with one another to prepare the composition according to the invention. It is also possible for them to be packaged and used as combination such as a kit of parts.
  • kits may include one or more, including all, components that may be used to prepare a subject agrochemical composition.
  • kits may include one or more fungicide component(s) and/or an adjuvant component and/or a insecticide component and/or a growth regulator component and/or a herbicde.
  • One or more of the components may already be combined together or pre- formulated. In those embodiments where more than two components are provided in a kit, the components may already be combined together and as such are packaged in a single container such as a vial, bottle, can, pouch, bag or canister. In other embodiments, two or more components of a kit may be packaged separately, i. e., not pre-formulated.
  • kits may include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical composition.
  • a component of the kit may be applied separately from or together with the further components or as a component of a combination composition according to the invention for preparing the composition according to the invention.
  • the user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank or a spray plane.
  • the agrochemical composition is made up with water and/or buffer to the desired application concentration, it being possible, if appropriate, to add further auxiliaries, and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 50 to 500 liters of the ready-to-use spray liquor are applied per hectare of agricultural useful area, preferably 100 to 400 liters.
  • composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate (tank mix).
  • either individual components of the composition according to the invention or partially premixed components may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate (tank mix).
  • either individual components of the composition according to the invention or partially premixed components can be applied jointly (e. .g. after tankmix) or consecutively.
  • compositions according to the invention can be shown by the tests described below.
  • the active compounds are prepared as a stock solution comprising 25 mg of active compound which is made up to 10 ml using a mixture of acetone and/or DMSO and the emulsifier Uniperol ® EL (wetting agent having an emulsifying and dispersing action based on ethoxylated alkylphenols) in a ratio by volume of solvent/emulsifier of 99:1.
  • the mixture is then made up to 100 ml with water.
  • This stock solution is diluted with the solvent/em ulsifier/water mixture described to give the concentration of active compound stated below.
  • E (1 - ⁇ / ⁇ ) - 100 ⁇ corresponds to the fungicidal infection of the treated plants in % and ⁇ corresponds to the fungicidal infection of the untreated (control) plants in %
  • An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected.
  • E expected efficacy expressed in % of the untreated control, when using the mixture of the active compounds A and B at the concentrations a and b x efficacy, expressed in % of the untreated control, when using the active compound A at the concentration a y efficacy, expressed in % of the untreated control, when using the active compound B at the concentration b.
  • the active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
  • the product orysastrobin was used as commercial finished formulation and diluted with water to the stated concentration of the active compound.
  • the stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.
  • MTP micro titer plate
  • a spore suspension of the respective pathogen in the respective nutrient medium was then added.
  • the plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
  • the measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. These percentages were converted into efficacies. The expected efficacies of active compound mixtures were determined using

Abstract

The present invention relates to fungicidal mixtures, comprising at least one hetero- aromatic sulfonamide compound and one active compound Il selected from groups A) to I) and at least one active compound III selected from groups A) to I) as defined in the description, and to compositions comprising these mixtures.

Description

Fungicidal mixtures comprising heteraromatic sulfonamides
Description
The present invention relates to mixtures comprising, as active components
1 ) at least one heteroaromatic sulfonamide compound of the formula I
Figure imgf000002_0001
where:
X is N or CH or C-R1;
n indicates the number of substituents R1 on the pyridine or pyrimidine ring and n is 0, 1 , 2 or 3;
R1 is halogen, CN, NO2, OH, SH, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylsulfinyl, Ci-C4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, amino, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, Ci-C4-alkoxy-Ci-C4-alkyl, C2-C4-alk- enyl, C2-C4-alkynyl, Cs-Cs-cycloalkyl or Ci-C4-alkyl-C3-C8-cycloalkyl; and/or
two radicals R1 that are bound to adjacent carbon atoms of the pyridine or pyrimine ring may form together with said carbon atoms a fused benzene ring, a fused saturated or partially unsaturated 5-, 6-, or 7-membered carbocycle or a fused 5-, 6-, or 7-membered heterocycle containing 1 , 2, or
3 heteroatoms selected from the group consisting of 2 nitrogen, 1 oxygen and 1 sulfur atoms as ring members, it being possible for the fused ring to carry 1 or 2 radicals selected from the group consisting of halogen, Ci-C4-alkyl, halomethyl, Ci-C4-alkoxy or halomethoxy,
it being possible for n = 2, 3 or 4 that R1 are identical or different;
R2 is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl,
Cs-Cs-cycloalkyl, Ci-C4-alkyl-C3-C8-cycloalkyl or benzyl wherein the phenyl moiety of benzyl is unsubstituted or carries 1 , 2, 3, 4, or 5 substituents selected from the group consisting of CN, halogen, Ci-C4-alkyl, Ci-C4-halo- alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, (Ci-C4-alkoxy)carbonyl and di(Ci-C4- alkyl)aminocarbonyl; m indicates the number of substituents R3 on the phenyl ring and m is 0, 1 , 2, 3 or 4;
R3 is halogen, CN, NO2, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy, it being possible for m = 2, 3 or 4 that R3 are identical or different;
Y is a divalent group selected from -O-, Ci-C4-alkanediyl, -O-CH2-, -CH2-O-, -C(NOR")-, -S-, -S(=0)-, -S(=0)2- and -N(Rn)-, wherein Rn is hydrogen or Ci-C4-alkyl and wherein the Ci-C4-alkanediyl moiety is unsubstituted or carries 1 or 2 substituents selected from the group consisting of oxo, CN, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy;
Het is a 5- or 6-membered heteroaromatic radical, wherein the ring member atoms of the heteroaromatic radical include, besides carbon atoms 1 , 2, 3 or 4 nitrogen atoms, or 1 oxygen atom and 0, 1 or 2 nitrogen atoms or 1 sulfur atom and 0, 1 or 2 nitrogen atoms and wherein the heteroaromatic radical is unsubstituted or carries 1 , 2, 3 or 4 identical or different substituents Ra, wherein two radicals Ra that are bound to adjacent ring member atoms may form a fused 5- or 6-membered carbocycle or heterocycle, wherein the fused carbocycle or heterocycle is unsubstituted or carries 1 , 2, 3 or 4 identical or different substituents Rb;
Ra is halogen, CN, NO2, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio,
Ci-C4-haloalkylthio, Ci-C4-alkylsulfinyl, Ci-C4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, amino, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, Ci-C4-alkoxy-Ci-C4-alkyl,
a radical C(=O)R, wherein R is H, Ci-C4-alkyl, Ci-C4-haloalkyl,
C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-alkoxy, Ci-C4-alkoxy- Ci-C4-alkoxy, Ci-C4-haloalkoxy, amino, Ci-C4-alkylamino or di(Ci-C4-alkyl)amino,
a radical CR'(=NOR"), wherein R' is H or Ci-C4-alkyl, and R" is
Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl or Ci-C4-alkoxy-Ci-C4-alkyl,
phenyl, pyridinyl, pyrimidinyl, phenoxy or phenoxyalkyl, where the five last mentioned radicals are unsubstituted or carry 1 , 2, 3 or 4 identical or different substituents Rc; Rb and Rc independently of each other are selected from halogen, CN, NO2, OH, SH, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-halo- alkoxy;
and the N-oxides and the agriculturally acceptable salts of the compounds of the formula I;
and
2) one active compound Il selected from groups A) to I):
A) strobilurins azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, meto- minostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb, trifloxystrobin, 2-(2-(6-(3-chloro-2-methyl-phenoxy)-5-fluoro-pyrimidin-4-yloxy)- phenyl)-2-methoxyimino-N-methyl-acetamide, 3-methoxy-2-(2-(N-(4-methoxy- phenyl)-cyclopropane-carboximidoylsulfanylmethyl)-phenyl)-acrylic acid methyl ester, methyl (2-chloro-5-[1 -(3-methylbenzyloxyimino)ethyl]benzyl)carbamate and 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2- methoxyimino-N-methyl-acetamide;
B) carboxamides
- carboxanilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, flutolanil, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carbox- amide (penflufen), penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4-methyl-thiazole-5-carboxanilide, 2-chloro-N-(1 ,1 ,3-trimethyl-indan- 4-yl)-nicotinamide, N-(3',4',5'-trifluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)-3-difluoro- methyl-1-methyl-1 H-pyrazole-4-carboxamide and N-(2-(1 ,3,3-trimethyl-butyl)- phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide;
- carboxylic morpholides: dimethomorph, flumorph, pyrimorph;
- benzoic acid amides: flumetover, fluopicolide, fluopyram, zoxamide, N-(3-ethyl- 3,5,5-trimethyl-cyclohexyl)-3-formylamino-2-hydroxy-benzamide; - other carboxamides: carpropamid, dicyclomet, mandiproamid, oxytetracyclin, silthiofarm and N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide;
C) azoles
- triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-(4-chloro- phenyl)-2-([1 ,2,4]triazol-1 -yl)-cycloheptanol;
- imidazoles: cyazofamid, imazalil, pefurazoate, prochloraz, triflumizol;
- benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;
- others: ethaboxam, etridiazole, hymexazole and 2-(4-chloro-phenyl)-N-[4-(3,4- dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;
D) heterocyclic compounds
- pyridines: fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin- 3-yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 2,3,5,6-tetra-chloro-4-methanesulfonyl-pyridine, 3,4,5-trichloropyridine-2,6-di- carbonitrile, N-(1 -(δ-bromo-S-chloro-pyridin^-y^-ethyQ^^-dichloronicotinamide,
N-[(5-bromo-3-chloro-pyridin-2-yl)-methyl]-2,4-dichloro-nicotinamide; pyrimidines: bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, mepani- pyrim, nitrapyrin, nuarimol, pyrimethanil; piperazines: triforine; - pyrroles: fenpiclonil, fludioxonil; morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph;
- piperidines: fenpropidin;
- dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin; - non-aromatic 5-membered heterocycles: famoxadone, fenamidone, flutianil, octhilinone, probenazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydro- pyrazole-1-carbothioic acid S-allyl ester;
- others: acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S, captafol, captan, chinomethionat, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, fenoxanil, Folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quinoxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo-3- propylchromen-4-one, 5-chloro-1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H- benzoimidazole, 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine and 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyri- midine-7-ylamine;
E) carbamates
- thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, propineb, thiram, zineb, ziram;
- carbamates: benthiavalicarb, diethofencarb, iprovalicarb, propamocarb, propamocarb hydrochlorid, valiphenal and N-(1-(1-(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
F) other active substances
- guanidines: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate); - antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, polyoxine, validamycin A; nitrophenyl derivates: binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecnazen, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;
- sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane;
- organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, iprobenfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl;
- organochlorine compounds: chlorothalonil, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pencycuron, pentachlorphenole and its salts, phthalide, quintozene, thiophanate-methyl, tolylfluanid, N-(4-chloro-2-nitro- phenyl)-N-ethyl-4-methyl-benzenesulfonamide; - inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
- others: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamin, metrafenone, mildiomycin, oxin-copper, prohexadione-calcium, spiroxamine, tolylfluanid, N- (cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2- phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl- phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro-3-trifluoromethyl- phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5- trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)- phenyl)-N-ethyl-N-methyl formamidine,
2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazole-1-yl)-acetyl]-piperidin-4-yl}-thiazole- 4-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1-yl)-amide, 2-{1-[2-(5- methyl-S-trifluoromethyl-pyrazole-i-yO-acetyO-piperidin^-ylJ-thiazole^-carbox- ylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide, acetic acid 6-tert- butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester, methoxy-acetic acid 6-tert-butyl-8- fluoro-2,3-dimethyl-quinolin-4-yl ester and N-Methyl-2-{1-[(5-methyl-3-trifluoro- methyl-1 H-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-N-[(1 R)-1 ,2,3,4-tetrahydro- naphthalen-1-yl]-4-thiazolecarboxamide. G) growth regulators abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dike- gulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthi- acet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N- 6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid , trinexapac-ethyl and uniconazole; H) herbicides
- acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;
- amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate;
- aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
- Bipyridyls: diquat, paraquat;
- (thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate;
- cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim;
- dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin; - diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen; hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil; imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr; - phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-
DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
- pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;
- pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr; - sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1-((2-chloro-6-propyl-imidazo[1 ,2-b]pyridazin-3- yl)sulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea;
- triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam; ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron,tebuthiuron;
- other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho- sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam;
- others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone,benfluresate, benzofenap, bentazone, benzobicyclon, bromacil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethlyl, chlorthal, cinmethylin, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, 4-hydroxy-3-[2-(2-methoxy-ethoxymethyl)-6-tri- fluoromethyl-pyridine-3-carbonyl]-bicyclo[3.2.1]oct-3-en-2-one, (3-[2-chloro-4- fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-2H-pyπmidin-1-yl)- phenoxy]-pyridin-2-yloxy)-acetic acid ethyl ester, 6-amino-5-chloro-2- cyclopropyl-pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2-cyclopropyl-
6-methyl-phenoxy)-pyridazin-4-ol, 4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro- pyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy- phenyl)-pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4- chloro-S-dimethylamino^-fluoro-pheny^-pyridine^-carboxylic acid methyl ester. I) insecticides
- organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
- carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate; pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin;
- insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat; - nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1-(2-chloro- thiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1 ,3,5]triazinane; GABA antagonist compounds: endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, 5-amino-1 -(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl- 1 H-pyrazole-3-carbothioic acid amide;
- macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram; - mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
- METI Il and III compounds: acequinocyl, fluacyprim, hydramethylnon;
- Uncouplers: chlorfenapyr;
- oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide, propargite; moulting disruptor compounds: cryomazine; mixed function oxidase inhibitors: piperonyl butoxide;
- sodium channel blockers: indoxacarb, metaflumizone;
- others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thiocyclam, flubendiamide, chlorantraniliprole, cyazypyr (HGW86), cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, and pyrifluquinazon;
and
3) at least one further active compound III selected from groups A) to I) as defined above.
The invention also relates to a method for controlling phytopathogenic harmful fungi using mixtures of a compound I and and a compound Il at least one active compound III and to the use of compound I and compounds Il and compounds III for preparing such mixtures, and to compositions and seed comprising these mixtures.
Moreover, the invention relates to binary mixtures comprising as active ingredients one compound I and one compound Il as defined herein in a synergistically effective amount. Preferable, the binary mixtures comprise a compound I and a compound Il in a weight ratio of from 100:1 to 1 :100.
Moreover, the invention relates to binary mixtures comprising as active ingredients a compound I as defined herein and N-methyl-2-{1-[(5-methyl-3-trifluoromethyl-1 H-pyr- azol-1 -yl)-acetyl]-piperidin-4-yl}-N-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1 -yl]-4-thiazole- carboxamide. Practical agricultural experience has shown that the repeated and exclusive application of an individual active compound in the control of harmful fungi leads in many cases to a rapid selection of those fungus strains which have developed natural or adapted resistance against the active compound in question. Effective control of these fungi with the active compound in question is then no longer possible. To reduce the risk of the selection of resistant fungus strains, mixtures of different active compounds are nowadays conventionally employed for controlling harmful fungi. By combining active compounds having different mechanisms of action, it is possible to ensure successful control over a relatively long period of time. It is an object of the present invention to provide, with a view to effective resistance management and effective control of phytopathogenic harmful fungi, at application rates which are as low as possible, compositions which, at a reduced total amount of active compounds applied, have improved activity against the harmful fungi (synergistic mixtures) and a broadened activty spectrum, in particular for certain indications.
We have accordingly found that this object is achieved by the compositions, defined herein, comprising compound I and compound and at least one compound III.
Moreover, we have found that simultaneous, that is joint or separate, application of compound I and compound Il and at least one compound III or successive application of a compound I and of compound Il and of a compound III allows better control of harmful fungi than is possible with the individual compounds alone (synergistic mixtures). Furthermore, synergistic effects in relation with the insecticidal and/or herbicidal action has been found with the inventive mixtures.
Compounds I and/or the compounds Il and/or compounds III can be present in different crystal modifications, which may differ in biological activity.
WO 05/033081 describes 4-pyridylmethyl sulfonamide compounds of formula
Figure imgf000010_0001
wherein X inter alia may represent an unsubstituted or substituted biphenyl ether, and the use of such compounds against plant pathogenic fungi. WO 08/06201 1 describes pyrimidin-4-ylmethyl sulfonamide compounds of formula
Figure imgf000010_0002
and their use as crop protection agents. Compounds in which A is phenylene or a 5- or 6-membered heteroarendiyl and R3 is a 5- or 6-membered heteroaryloxy or heteroarylthio are generally covered by this patent application. However, there is no single compound disclosed in which A is phenylene or a 5- or 6-membered heteroarenediyl and R3 is a 5- or 6-membered heteroaryloxy or heteroarylthio.
The compounds I differ from those kown from the abovementioned publications by the combination of the heteroarylmethyl group with the specific sulfonic acid substituent Phenyl-Y-Het. Compounds I and their preparation have been described in the international non- published applications PCT/EP2008/065958, PCT/EP2008/065961 , PCT/EP2009/051500 and PCTEP2009/051501.
The compounds II, their preparation and their activity against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available and known, for example, from the references below: benalaxyl, methyl N-(phenylacetyl)-N-(2,6-xylyl)-DL-alaninate (DE 29 03 612); meta- laxyl, methyl N-(methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate (GB 15 00 581 ); ofurace, (RS)-α-(2-chloro-N-2,6-xylylacetamido)-γ-butyrolactone [CAS RN 58810-48-3]; oxadix- yl; 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", comprising 65-75% of 2,6-di- methylmorpholine and 25-35% of 2,5-dimethylmorpholine, comprising more than 85% of 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 [CAS RN 91315-15-0]; dodine, 1-dodecylguanidinium acetate (Plant Dis. Rep., Vol. 41 , p.1029 (1957)); dodemorph, 4-cyclododecyl-2,6-dimethylmorpholine (DE 1198125); fenpropimorph, (RS)-cis-4-[3-(4- tert-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine (DE 27 52 096); fenpropidin, (RS)-I -[3-(4-tert-butylphenyl)-2-methylpropyl]piperidine (DE 27 52 096); guazatine, mixture of the reaction products from the amidation of technical grade iminodi(octa- methylene)diamine, comprising various guanidines and polyamines [CAS RN 108173- 90-6]; iminoctadine, 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 1 1 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); cycloheximid, 4-{(2R)-2-[(1 S,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[benzo- furan-2(3H),1 '-cyclohex-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-chiro-inositol [CAS RN 6980-18-3]; natamycin, (8E,14E,16E,18E,20E)-(1 R,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-6,1 1 , 28-trioxatricyclo[22.3.1.05,7]octacosa-8, 14, 16,18,20- pentaene-25-carboxylic acid [CAS RN 7681-93-8]; polyoxin, 5-(2-amino-5-O-carbamo- yl-2-deoxy-L-xylonamido)-1 -(5-carboxy-1 ,2,3,4-tetrahydro-2,4-dioxopyrimidin-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-trihydroxycyclohex-1 ,3-ylene}diguanidine (J. Am. Chem. Soc. 69, p.1234 (1947)); bitertanol, β-([1 ,1 '-biphenyl]-4-yloxy)-α-(1 ,1-dimethylethyl)-1 H- 1 ,2,4-triazole-1-ethanol (DE 23 24 020); bromuconazole, 1-[[4-bromo-2-(2,4-dichloro- phenyl)tetrahydro-2-furanyl]methyl]-1 H-1 ,2,4-triazole (Proc. Br. Crop. Prot. Conf. 1990 - 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); difenoconazole, 1-{2-[2-chloro-4-(4-chloro- phenoxy)phenyl]-4-methyl-[1 ,3]dioxolan-2-ylmethyl}-1 H-[1 ,2,4]triazole (GB-A 2 098 607); diniconazole, (βE)-β-[(2,4-dichlorophenyl)methylene]-α-(1 ,1-dimethylethyl)-1 H- 1 ,2,4-triazole-1-ethanol (Noyaku Kagaku, 1983, Vol. 8, p. 575); enilconazole (imazalil), 1-[2-(2,4-dichlorphenyl)-2-(2-propenyloxy)ethyl]-1 H-imidazole (Fruits 28, p. 545, 1973); epoxiconazole, (2RS,3SR)-1 -[3-(2-chlorophenyl)-2,3-epoxy-2-(4-fluorophenyl)propyl]- 1 H-1 ,2,4-triazole (EP-A 196 038); fenbuconazole, α-[2-(4-chlorophenyl)ethyl]-α-phenyl- 1 H-1 ,2,4-triazole-1-propanenitrile (Proc. Br. Crop Prot. Conf. 1988 - Pests Dis. Vol. 1 , p. 33); fluquinconazole, 3-(2,4-dichlorophenyl)-6-fluoro-2-[1 ,2,4]-triazol-1-yl-3H-quin- azolin-4-one (Proc. Br. Crop Prot. Conf.-Pests Dis., 5-3, 411 (1992)); flusilazole, 1-{[bis-(4-fluorophenyl)methylsilanyl]methyl}-1 H-[1 ,2,4]triazole (Proc. Br. Crop Prot. Conf.-Pests Dis., 1 , 413 (1984)); flutriafol, α-(2-fluorophenyl)-α-(4-fluorophenyl)- 1 H-1 ,2,4-triazole-1-ethanol (EP 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-(1 H-1 ,2,4-triazol-1-ylmethyl)cyclopentanol (EP 267 778), metconazole, 5-(4-chlorobenzyl)-2,2-dimethyl-1 -[1 ,2,4]triazol-1 -ylmethylcyclopentanol (GB 857 383); myclobutanil, 2-(4-chlorophenyl)-2-[1 ,2,4]triazol-1-ylmethylpentanenitrile (CAS RN 88671-89-0); penconazole, 1-[2-(2,4-dichlorophenyl)pentyl]-1 H-[1 ,2,4]tri- azole (Pesticide Manual, 12th Ed. (2000), S.712); propiconazole, 1-[[2-(2,4-dichloro- phenyl)-4-propyl-1 ,3-dioxolan-2-yl]methyl]-1 H-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); simeconazole, α-(4-fluorophenyl)-α- [(trimethylsilyl)methyl]-1 H-1 ,2,4-triazole-1 -ethanol [CAS RN 149508-90-7]; tebucon- azole, 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]-1 H- 1 ,2,4-triazole (EP 234 242); triadimefon, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1 H-1 ,2,4- triazol-1-yl)-2-butanone (BE 793 867); triadimenol, β-(4-chlorophenoxy)-α-(1 ,1-dimeth- ylethyl)-1 H-1 ,2,4-triazole-1 -ethanol (DE 23 24 010); triflumizol, (4-chloro-2-trifluoro- methylphenyl)-(2-propoxy-1-[1 ,2,4]triazol-1-ylethyliden)-amine (JP-A 79/119 462); triticonazole, (5E)-5-[(4-chlorophenyl)methylene]-2,2-dimethyl-1 -(1 H-1 ,2,4-triazol-1 -yl- methyl)cyclopentanol (FR 26 41 277); iprodione, N-isopropyl-3-(3,5-dichlorophenyl)- 2,4-dioxoimidazolidine-1-carboxamide (GB 13 12 536); myclozolin, (RS)-3-(3,5- dichlorophenyl)-5-methoxymethyl-5-methyl-1 ,3-oxazolidine-2,4-dione [CAS RN 54864- 61-8]; procymidone, N-(3,5-dichlorophenyl)-1 ,2-dimethylcyclopropane-1 ,2-dicarbox- imide (US 3 903 090); vinclozolin, 3-(3,5-dichlorophenyl)-5-methyl-5-vinyloxazolidine- 2,4-dione (DE-A 22 07 576); ferbam, iron(3+) dimethyldithiocarbamate (US 1 972 961); nabam, disodium ethylenebis(dithiocarbamate) (US 2 317 765); maneb, manganese ethylenebis(dithiocarbamate) (US 2 504 404); mancozeb, manganese ethylenebis- (dithiocarbamate) polymer complex zinc salt (GB 996 264); metam, methyldithiocar- baminic acid (US 2 791 605); metiram, zinc ammoniate ethylenebis(dithiocarbamate) (US 3 248 400); propineb, zinc propylenebis(dithiocarbamate) polymer (BE 611 960); polycarbamate, bis(dimethylcarbamodithioato-S,S')[μ-[[1 ,2-ethanediylbis[carbamodi- thioato-S,S']](2-)]]di[zinc] [CAS RN 64440-88-6]; thiram, bis(dimethylthiocarbamoyl) disulfide (DE 642 532); ziram, dimethyldithiocarbamate [CAS RN 137-30-4]; zineb, zinc ethylenebis(dithiocarbamate) (US 2 457 674); anilazine, 4,6-dichloro-N-(2-chloro- phenyl)-1 ,3,5-triazine-2-amine (US 2 720 480); benomyl, N-butyl-2-acetylaminobenzo- imidazole-1-carboxamide (US 3 631 176); boscalid, 2-chloro-N-(4'-chlorobiphenyl-2-yl)- nicotinamide (EP-A 545 099); carbendazim, methyl (1 H-benzoimidazol-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-di- oxide (US 3 399 214); cyazofamid, 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)- 1 H-imidazole-1 -sulfonamide (CAS RN 1201 16-88-3]; dazomet, 3,5-dimethyl-1 ,3,5-thia- diazinane-2-thione (Bull. Soc. Chim. Fr. 15, p. 891 (1897)); dithianon, 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]; fenamidone, (S)-1-anilino-4-methyl-2-methylthio-4-phenylimidazolin-5-one [CAS RN 161326-34-7]; fenarimol, α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol (GB 12 18 623); fuberidazole, 2-(2-furanyl)-1 H-benzimidazole (DE 12 09 799); fluto- lanil, α,α,α-trifluoro-3'-isopropoxy-o-toluanilide (JP 1 104514); furametpyr, 5-chloro-N- (1 ,3-dihydro-1 ,1 ,3-trimethyl-4-isobenzofuranyl)-1 , 3-d im ethyl- 1 H-pyrazole-4-carbox- amide [CAS RN 123572-88-3]; isoprothiolane, diisopropyl 1 ,3-dithiolan-2-ylidene- malonate (Proc. Insectic. Fungic. Conf. 8. Vol. 2, p. 715 (1975)); mepronil, 3'-isoprop- oxy-o-toluanilide (US 3 937 840); nuarimol, α-(2-chlorophenyl)-α-(4-fluorophenyl)-5-py- rimidinemethanol (GB 12 18 623); fluopicolide (picobenzamid), 2,6-dichloro-N-(3-chlo- ro-5-trifluoromethylpyridin-2-ylmethyl)benzamide (WO 99/42447); probenazole, 3-allyl- oxy-1 ,2-benzothiazole 1 ,1 -dioxide (Agric. Biol. Chem. 37, p. 737 (1973)); proquinazid, 6-iodo-2-propoxy-3-propylquinazolin-4(3H)-one (WO 97/48684); pyrifenox, 2',4'-di- chloro-2-(3-pyridyl)acetophenone (EZ)-O-methyloxime (EP 49 854); pyroquilon, 1 ,2,5,6-tetrahydropyrrolo[3,2,1-ij]quinolin-4-one (GB 139 43 373) quinoxyfen, 5,7-di- chloro-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); thifluzamide, 2',6'-dibromo-2-methyl-4'-tri- fluormethoxy-4-trifluormethyl-1 ,3-thiazole-5-carboxanilide [CAS RN 130000-40-7]; thiophanate-methyl, 1 ,2-phenylenebis(iminocarbonothioyl)bis(dimethylcarbamate) (DE-A 19 30 540); tiadinil, 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]; triforine, N,N'-{piperazine-1 ,4-diylbis[(trichlormethyl)methyl- ene]}diformamide (DE 19 01 421 ); Bordeaux mixture, mixture of CuSO4 x 3Cu(OH)2 x 3CaSO4 [CAS RN 8011-63-0]; copper acetate, Cu(OCOCHs)2 [CAS RN 801 1-63-0]; copper oxychloride, Cu2CI(OH)3 [CAS RN 1332-40-7]; basic copper sulfate, CuSO4 [CAS RN 1344-73-6]; binapacryl, (RS)-2-sec-butyl-4,6-dinitrophenyl 3-methylcrotonate [CAS RN 485-31-4]; dinocap, mixture of 2,6-dinitro-4-octylphenylcrotonate and 2,4- dinitro-6-octylphenylcrotonate, where "octyl" is a mixture of 1-methylheptyl, 1-ethylhexyl and 1-propylpentyl (US 2 526 660); dinobuton, (RS)-2-sec-butyl-4,6-dinitrophenyl iso- propyl carbonate [CAS RN 973-21-7]; nitrothal-isopropyl, diisopropyl 5-nitroisophthalate (Proc. Br. Insectic. Fungic. Conf. 7., Vol. 2, p. 673 (1973)); fenpiclonil, 4-(2,3-dichloro- phenyl)-1 H-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)-1 H-pyrrole-3-carbonitrile (The Pesticide Manual, publ. The British Crop Protection Council, 10th ed. (1995), p. 482); acibenzolar-S-methyl, methyl 1 ,2,3-benzothiadiazol-7-carbothioate [CAS RN 135158- 54-2]; flubenthiavalicarb (benthiavalicarb), isopropyl {(S)-1-[(1 R)-1-(6-fluorobenzo- thiazol-2-yl)-ethylcarbamoyl]-2-methylpropyl}carbamate (JP-A 09/323 984); carprop- amid, 2,2-dichloro-N-[1-(4-chlorophenyl)ethyl]-1-ethyl-3-methylcyclopropanecarbox- amide [CAS RN 104030-54-8]; chlorothalonil, 2,4,5,6-tetrachloroisophthalonitrile (US 3 290 353); cyflufenamid, (Z)-N-[α-(cyclopropylmethoxyimino)-2,3-difluoro-6-(trifluoro- methyl)benzyl]-2-phenylacetamide (WO 96/19442); cymoxanil, 1 -(2-cyano-2-methoxy- iminoacetyl)-3-ethylurea (US 3 957 847); diclomezine, 6-(3,5-dichlorophenyl-p-tolyl)- pyridazin-3(2H)-one (US 4 052 395) diclocymet, (RS)-2-cyano-N-[(R)-1-(2,4-dichloro- phenyl)ethyl]-3,3-dimethylbutyramide [CAS RN 139920-32-4]; diethofencarb, isopropyl 3,4-diethoxycarbanilate (EP 78 663); edifenphos, O-ethyl S,S-diphenyl phosphoro- dithioate (DE 14 93 736) ethaboxam, N-(cyano-2-thienylmethyl)-4-ethyl-2-(ethylamino)- 5-thiazolecarboxamide (EP-A 639 574); fenhexamid, N-(2,3-dichloro-4-hydroxyphenyl)- 1-methylcyclohexanecarboxamide (Proc. Br. Crop Prot. Conf. - Pests Dis., 1998, Vol. 2, p. 327); fentin acetate, triphenyltin (US 3 499 086); fenoxanil, N-(1-cyano-1 ,2-di- methylpropyl)-2-(2,4-dichlorophenoxy)propanamide (EP 262 393); ferimzone, mepani- pyrim, (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-(tri- fluoromethyl)-2-pyridinamine (The Pesticide Manual, publ. The British Crop Protection Council, 10th ed. (1995), p. 474); fosetyl, fosetyl-aluminum, ethylphosphonate (FR 22 54 276); iprovalicarb, isopropyl [(1S)-2-methyl-1-(1-p-tolylethylcarbamoyl)propyl]- carbamate (EP-A 472 996); hexachlorbenzene (C. R. Seances Acad. Agric. Fr. 31 , p. 24, 1945); metrafenon, 3'-bromo-2,3,4,6'-tetramethoxy-2',6-dimethylbenzophenone (US 5 945 567); pencycuron, 1-(4-chlorobenzyl)-1-cyclopentyl-3-phenylurea (DE 27 32 257); penthiopyrad, (RS)-N-[2-(1 ,3-dimethylbutyl)-3-thienyl]-1-methyl-3-(trifluorometh- yl)-1 H-pyrazole-4-carboxamide (JP 10130268); propamocarb, propyl 3-(dimethyl- amino)propylcarbamate (DE 15 67 169); phthalide (DE 16 43 347); toloclofos-methyl, 0-2,6-dichloro-p-tolyl O,O-dimethyl phosphorothioate (GB 14 67 561); quintozene, pentachlornitrobenzene (DE 682 048); zoxamide, (RS)-3,5-dichloro-N-(3-chloro-1-eth- yl-1-methyl-2-oxopropyl)-p-toluamide [CAS RN 156052-68-5]; azoxystrobin, methyl 2-{2-[6-(2-cyano-1 -vinyl penta-1 , 3-dienyloxy)pyrimidin-4-yloxy]phenyl}-3-methoxy- acrylate (EP 382 375), dimoxystrobin, (E)-2-(methoxyimino)-N-methyl-2-[α-(2,5-xylyl- oxy)-o-tolyl]acetamide (EP 477 631 ); enestroburin, methyl 2-{2-[3-(4-chlorophenyl)- 1-methylallylideneaminooxymethyl]phenyl}-3-methoxyacrylate (EP 936 213); fluoxastrobin, (E)-{2-[6-(2-chlorophenoxy)-5-fluoropyrimidin-4-yloxy]phenyl}(5,6- dihydro-1 ,4,2-dioxazin-3-yl)methanone O-methyloxime (WO 97/27189); kresoxim- methyl, methyl (E)-methoxyimino[α-(o-tolyloxy)-o-tolyl]acetate (EP 253 213); met- ominostrobin, (E)-2-(methoxyimino)-N-methyl-2-(2-phenoxyphenyl)acetamide (EP 398 692); orysastrobin, (2E)-2-(methoxyimino)-2-{2-[(3E,5E,6E)-5-(methoxyimino)-4,6-di- methyl-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-yloxy- methyl)phenyl]acrylate (EP 278 595); pyraclostrobin, methyl N-{2-[1-(4-chlorophenyl)- 1 H-pyrazol-3-yloxymethyl]phenyl}(N-methoxy)carbamate (WO 96/01256); trifloxy- strobin, methyl (E)-methoxyimino-{(E)-α-[1 -(α,α,α-trifluoro-m-tolyl)ethylideneaminooxy]- o-tolyl}acetate (EP 460 575); captafol, N-(1 ,1 ,2,2-tetrachloroethylthio)cyclohex-4-ene- 1 ,2-dicarboximide (Phytopathology, Vol. 52, p. 754 (1962)); captan, N-(trichloromethyl- thio)cyclohex-4-ene-1 ,2-dicarboximide (US 2 553 770); dichlofluanid, N-dichlorofluoro- methylthio-N',N'-dimethyl-N-phenylsulfamide (DE 1 1 93 498); folpet, N-(trichlormethyl- thio)phthalimide (US 2 553 770); tolylfluanid, N-dichlorofluoromethylthio-N',N'-dimethyl- N-p-tolylsulfamide (DE 11 93 498); dimethomorph, 3-(4-chlorophenyl)-3-(3,4-dimeth- oxyphenyl)-1-morpholin-4-yl-propenone (EP 120 321 ); flumetover, 2-(3,4-dimethoxy- phenyl)-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 860 438); δ-Amino^-isopropyl-S-oxo^-o-tolyl^^-dihydro-pyrazole-i-carbothioic acid S-allyl ester (CN 1939128).
The compounds described by IUPAC nomenclature, their preparation and their fungicidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031 ; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941 ; EP- A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501 ; WO 01/56358; WO 02/22583; WO 02/40431 ; WO 03/10149; WO 03/11853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491 ; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721 ; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624). N-methyl-2-{1-[(5-methyl-3-trifluorometh- yl-1 H-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}-N-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1 -yl]- 4-thiazolecarboxamide has been described in WO 2007/014290.
In the definitions of the variables given above, collective terms are used which are generally representative for the substituents in question. The term Cn-Cm indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.
The term "halogen" refers to fluorine, chlorine, bromine and iodine. The term "oxo" refers to a double-bonded oxygen atom (=0). The term "Ci-C4-alkyl" refers to a straight-chained or branched saturated hydrocarbon group having 1 to 4 carbon atoms, for example methyl, ethyl, propyl, 1-methyl- ethyl, butyl, 1-methylpropyl, 2-methylpropyl, and 1 ,1-dimethylethyl.
The term " Ci-C4-haloalkyl" refers to a straight-chained or branched alkyl group having 1 to 4 carbon atoms, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoro- methyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chlo- ro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloro- ethyl and pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-di- fluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bro- mopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, CH2-C2F5, CF2-C2F5, CF(CFs)2, 1 -fluoromethyl-2-fluoroethyl, 1 -(chloromethyl)-2-chloroethyl, 1 -bromomethyl-2-bromo- ethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl, and the like. The term " Ci-C4-alkoxy" refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms which is bonded via an oxygen, at any position in the alkyl group, e.g. methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1 -methyhpropoxy, 2-methyl- propoxy or 1 ,1-dimethylethoxy.
The term "Ci-C4-haloalkoxy" refers to a Ci-C4-alkoxy radical as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, e.g., OCH2F, OCHF2, OCF3, OCH2CI, OCHCI2, OCCb, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoro- ethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-tri- fluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoro- ethoxy, 2,2,2-trichloro->ethoxy, OC2F5, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoro- propoxy, 2,3-difluoro->propoxy, 2 chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromo-"propoxy, 3 bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2Fs, OCF2-C2Fs, 1-fluoromethyl-2-fluoroethoxy, i-chloromethyl-2-chloroethoxy, 1-bromomethyl-2-bromo~iethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy.
The term " Ci-C4-alkoxy- Ci-C4-alkyl" refers to alkyl having 1 to 4 carbon atoms, wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C4-alkoxy group.
The term " Ci-C4-alkoxy- Ci-C4-alkoxy" refers to an Ci-C4-alkoxy- Ci-C4-alkyl group, which is bonded via an oxygen atom to the remainder of the molecule. The term " Ci-C4-alkylthio" as used herein refers to straight-chain or branched alkyl groups having 1 to 4 carbon atoms bonded through a sulfur atom, at any position in the alkyl group, for example methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.
Accordingly, the term " Ci-C4-haloalkylthio" as used herein refers to straight-chain or branched haloalkyl groups having 1 to 4 carbon atoms bonded through a sulfur atom, at any position in the haloalkyl group.
The term " Ci-C4-alkylsulfinyl" refers to straight-chain or branched alkyl group having 1 to 4 carbon atoms bonded through a -S(=0)- moiety, at any position in the alkyl group, for example methylsulfinyl and the like.
Accordingly, the term " Ci-C4-haloalkylsulfinyl" refers to straight-chain or branched haloalkyl group having 1 to 4 carbon atoms bonded through a -S(=0)- moiety, at any position in the haloalkyl group.
The term " Ci-C4-alkylsulfonyl" refers to straight-chain or branched alkyl group having 1 to 4 carbon atoms bonded through a -S(=0)2- moiety, at any position in the alkyl group, for example methylsulfonyl. Accordingly, the term " Ci-C4-haloalkylsulfonyl" refers to straight-chain or branched haloalkyl group having 1 to 4 carbon atoms bonded through a -S(=0)2- moiety, at any position in the haloalkyl group.
The term " Ci-C4-alkylamino" refers to an amino radical carrying one Ci-C4-alkyl group as substituent, for example methylamino, ethylamino, propylamino, 1-methyl- ethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1 ,1-dimethylethyl- amino and the like.
The term "di(Ci-C4-alkyl)amino" refers to an amino radical carrying two identical or different Ci-C4-alkyl groups as substituents, for example dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, N-ethyl-N-methylamino, N-(n-propyl)-N-methyl- amino, N-isopropyl-N methylamino, N-(n-butyl)-N-methylamino, N-(n-pentyl)-N-methyl- amino, N-(2-butyl)-N methylamino, N-isobutyl-N-methylamino, and the like.
The term "( Ci-C4-alkoxy)carbonyl" refers to a Ci-C4-alkoxy radical which is attached via a carbonyl group.
The term "di(Ci-C4-alkyl)aminocarbonyl" refers to a di(Ci-C4)alkylamino radical which is attached via a carbonyl group.
The term "C2-C4-alkenyl" refers to a branched or unbranched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl (allyl), 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl- 2-propenyl.
The term "C2-C4-alkynyl" refers to a branched or unbranched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and containing at least one triple bond, such as ethynyl, 1-propynyl, 2-propynyl (propargyl), 1-butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2-propynyl.
The term "Cs-Cs-cycloalkyl" refers to monocyclic saturated hydrocarbon radicals having 3 to 8 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. The term " Ci-C4-alkyl-C3-C8-cycloalkyl" refers to a cycloalkyl radical having 3 to 8 carbon atoms, wherein one hydrogen atom of the cycloalkyl radical is replaced by a Ci-C4-alkyl group.
The term "5-, 6- or 7-membered carbocycle" is to be understood as meaning both saturated and partially unsaturated carbocycles having 5, 6 or 7 ring members as well as phenyl. Examples for non-aromatic rings include cyclopentyl, cyclopentenyl, cyclo- pentadienyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cycloheptenyl, cycloheptadienyl and the like.
The term "5-, 6-, or 7-membered heterocycle" which contains one, two, three or four heteroatoms from the group consisting of O, N and S, is to be understood as meaning both saturated and partially unsaturated as well as aromatic heterocycles having 5, 6 or 7 ring atoms. Examples include:
- saturated and partially unsaturated 5-, 6-, or 7-membered heterocycle which contains 1 , 2 or 3 nitrogen atoms and/or one oxygen or sulfur atom or 1 or 2 oxygen and/or sulfur atoms, and which is saturated or partially unsaturated, for example 2- tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl,
2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothi- azolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyr- azolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrro- lin-2-yl, 3-pyrrolin-3-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1 ,3-dioxan-5-yl, 2-tetra- hydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3 hexahydropyridazinyl, 4-hexa- hydropyridazinyl, 2-hexahydropyrimidinyl, 4 hexahydropyrimidinyl, 5-hexahydropyri- midinyl and 2-piperazinyl; - 5-membered aromatic heterocyclyl (heteroaromatic radical) which contains 1 , 2, 3 or 4 nitrogen atoms or 1 , 2 or 3 nitrogen atoms and one sulfur or oxygen atom: 5-membered heteroaryl groups which, in addition to carbon atoms, may contain 1 to 4 nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members, for example 2-thienyl, 3-thienyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-ox- azolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl and 1 ,3,4-triazol-2-yl;
- 6-membered heterocycyl (heteroaromatic radical) which contains 1 , 2, 3 or 4 nitrogen atoms: 6 membered heteroaryl groups which, in addition to carbon atoms, may contain 1 , 2, 3 or 4 nitrogen atoms as ring members, for example 2-pyridinyl, 3-pyridin- yl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.
The term " Ci-C4-alkanediyl" refers to a divalent, branched or straight-chain saturated hydrocarbon radical having 1 to 4 carbon atoms, derived from a Ci-C4-alkyl group (as defined above) that has two points of attachment.
The term "two radicals R1 that are bound to adjacent carbon atoms of the pyridine ring may form together with said carbon atoms a fused ring" refers to a bicyclic ring system, wherein pyridin-4-yl carries a fused-on 5-, 6- or 7-membered carbocyclic or heterocyclic ring. Examples of such fused bicyclic ring systems include benzo[b]py- ridine (quinoline), pyrido[2,3-b]pyridine (1 ,8-naphthyridine), pyrido[3,4-b]pyridine (1 ,7-naphthyridine), pyrido[4,3-b]pyridine (1 ,6-naphthyridine), pyrido[3,2-b]pyridine (1 ,5-naphthyridine), pyrido[2,3-d]pyrimidine, pyrido[3,2-d]pyrimidine, pyrido[2,3-b]fu- rane, pyrido[3,2-b]furane, pyrido[2,3-c]furane, pyrido[2,3-d]thiazole, pyrido[3,2-d]thia- zole, pyrido[2,3-d]isoxazole, pyrido[3,2-d]isoxazole, pyrido[2,3-c]isoxazole and pyrido[3,2-c]isoxazole. The fused-on ring can be unsubstituted or substituted by 1 , 2, 3 radicals substituents selected, independently from one another, from the group consisting of halogen, Ci-C4-alkyl, halomethyl, Ci-C4-alkoxy and halomethoxy.
The term "two radicals Ra that are bound to adjacent carbon atoms of the Het group may form together with said carbon atoms a fused ring" refers to a bicyclic ring system, wherein Het, carries a fused-on 5-, 6- or 7-membered carbocyclic or heterocyclic ring. Examples of such fused bicyclic rings include quinoline, quinazoline, benzofurane, isobenzofurane, phthalazine, cinnoline, quinoxaline, benzothiazole, benzoisothiazole, benzoxazole, benzoisoxazole, 1 ,5-naphthyridine, 1 ,6-naphthyridine, 1 ,7-naphthyridine, 1 ,8-naphthyridine, 2,6-naphtyridine, 2,7-naphtyridine, pyrido[2,3-d]pyrimidine, pyrido[3,2-d]pyrimidine, pyrido[3,4-d]pyrimidine, pyrido[4,3-d]pyrimidine, pyrido[2,3-b]- furane, pyrido[3,2-b]furane, pyrido[2,3-c]furane, pyrido[3,4-b]furane, pyrido[4,3-b]- furane, pyrido[3,4-c]furane, pyrido[2,3-d]thiazole, pyrido[3,2-d]thiazole, pyrido[3,4-d]- thiazole, pyrido[4,3-d]thiazole, pyrido[2,3-d]isoxazole, pyrido[3,2-d]isoxazole, pyri- do[2,3-c]isoxazole, pyrido[3,2-c]isoxazole, pyrido[3,4-d]isoxazole, pyrido[4,3-d]isoxa- zole, pyrido[3,4-c]isoxazole, pyrido[4,3-c]isoxazole and the like. The fused-on ring can be unsubstituted or substituted by 1 , 2, 3 or 4 radicals substituents selected, independently from one another, from the group consisting of halogen, cyano, nitro, OH, SH, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy. Agriculturally acceptable salts of the compounds I encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds I. Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry 1 to 4 Ci-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethyl- ammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphoni- um ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogen- phosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluoro- phosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting a compound I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
In the inventive mixtures (e.g. binary and ternary mixtures), as compound I, the following compounds are preferred: Preference is given to those compounds of formula I (compounds I) and of subformula 1.1 (compounds 1.1 ), wherein the substituents and variables X, n, m, Y, R1, R2, R3, Ra, Rb, Rc, R and Het have independently of each other or more preferably in combination the following meanings:
One embodiment of the invention relates to mixtures comprising compounds I, wherein X is N. Another embodiment relates to mixtures comprising compounds I, wherein X is CH or C-R1.
One embodiment relates to mixtures comprising compounds I, wherein n is 0, 1 or 2, in particular n is 1. A further embodiment relates to mixtures comprising compounds
1, wherein n is 2. A further embodiment relates to mixtures comprising compounds I, wherein n is 0.
One embodiment relates to mixtures comprising compounds I, wherein m is 0, 1 or
2, preferably m is 0 or 1 , in particular m is 0. A further embodiment relates to mixtures comprising compounds I, wherein m is 1.
One embodiment relates to mixtures comprising compounds I, wherein R1 is selected from halogen, CN, NO2, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-halo- alkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylsulfinyl, Ci-C4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, Ci-C4-alkoxy-Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Cs-Cs-cycloalkyl and Ci-C4-alk- yl-C3-C8-cycloalkyl; more preferably from CN, , Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alk- oxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkoxy-Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Cs-Cs-cycloalkyl and Ci-C4-alkyl-C3-Cs-cycloalkyl, even more preferably from Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkylthio and Cs-Cs-cycloalkyl, and in particular selected from Ci-C4-alkyl and Ci-C4-alkoxy. A further embodiment relates to mixtures comprising compounds I, wherein R1 is selected from methyl, ethyl, n-propyl and i-propyl, more preferably R1 is methyl. A further embodiment relates to mixtures comprising compounds I, wherein R1 is selected from methoxy, ethoxy, n-propoxy and i-propoxy, in particular R1 is methoxy. One embodiment relates to mixtures comprising compounds I, wherein R2 is selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl and C3-C8-cycloalkyl, more preferably selected from hydrogen and Ci-C4-alkyl, and in particlar R2 is hydrogen. Another embodiment relates to mixtures comprising compounds I, wherein R2 is CH3. One embodiment relates to mixtures comprising compounds I, wherein R3 is selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl and Ci-C4-alkoxy, more preferably selected from halogen, Ci-C4-alkyl and Ci-C4-alkoxy, and even more selected preferably from F, Cl, Br, I, CH3, CH2CH3, CH2CH2CH3 and CH(CH3)2, in particular R3 is F. Another embodiment relates to mixtures comprising compounds I, wherein R3 is Cl. A further embodiment relates to mixtures comprising compounds I, wherein R3 is CH3.
Preference is also given to mixtures comprising compounds I, wherein the moiety Het-Y is located on the phenyl ring in the meta- or para-position with respect to the sulfonyl group, in particular in the para-position. Particular preference is also given to mixtures comprising compounds I, wherein the moiety Het-Y is located on the phenyl ring in the meta-position with respect to the sulfonyl group.
One embodiment relates to mixtures comprising compounds I, wherein Y is selected from -O-, Ci-C4-alkanediyl, -0-CH2-, -CH2-O-, -C(NOR")-, -S-, -S(=0)-, -S(=O)2- and -N(R")-, wherein Rn is hydrogen or Ci-C4-alkyl, more preferably selected from -0-, Ci-C4-alkanediyl, -0-CH2-, -CH2-O- and -S-, and in particular Y is -0-. Another embodiment relates to mixtures comprising compounds I, wherein Y is -S-.
One embodiment relates to mixtures comprising compounds I, wherein Het is selected from pyridinyl, pyrimidinyl, thiophenyl, pyrazolyl, isoxazoyl, isothiazolyl, thiazolyl, imidazolyl and oxazolyl, more preferably selected from pyridinyl, pyrimidinyl, thiophenyl and pyrazolyl, and in particular Het is pyridinyl. Another embodiment relates to mixtures comprising compounds I, wherein Het is pyrazolyl. Another embodiment relates to mixtures comprising compounds I, wherein Het is pyrimidyl. A further preferred embodiment relates to mixtures comprising compounds I, wherein Het is selected from pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridin-5-yl, pyridin-6-yl, pyrimidin- 2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrimidin-6-yl, thiophen-2-yl, thiophen-3-yl, thiophen- 4-yl, thiophen-5-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl and pyrazol-5-yl, and more preferably selected from pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridin-5-yl, pyridin-6-yl, pyrimidn-2-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl and pyrazol-5-yl.
One embodiment relates to mixtures comprising compounds I, wherein Het carries 1 , 2 or 3 radicals Ra, more preferably 1 or 2 radicals Ra, and in particular Het carries 1 radical Ra. Another embodiment relates to mixtures comprising compounds I, wherein Het carries 2 radicals Ra.
One embodiment relates to mixtures comprising compounds I, wherein Ra is selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-halo- alkoxy, Ci-C4-alkylthio and C(=O)R, wherein R is Ci-C4-alkoxy, more preferably selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl and Ci-C4-alkoxy. Another preferred embodiment relates to mixtures comprising compounds I, wherein Ra is selected from F, Cl, Br, CH3, CH2CH3, CH2CH2CH3, CH(CH3)2, CF3, CF2CHF2 and CF2CF3, more preferably selected from F, Cl, Br, CH3 and CF3.
One embodiment relates to mixtures comprising compounds I, wherein Rb and Rc are independently of each other selected from halogen, Ci-C4-alkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, more preferably these radicals are selected from F, Cl, CH3, OCH3 and CF3.
According to a further preferred embodiment, the mixtures comprise compounds I, wherein X is N or CH, n is 0, 1 or 2, R1 is CH3 or OCH3, R2 is hydrogen, the moiety Het- Y is located on the phenyl ring in the para-position with respect to the sulfonyl group, Y is -O-, m is 0 or 1 , R3 is CH3 or F, Het is selected from pyridin-2-yl, pyridin-4-yl and pyrimidin-2-yl, wherein the aforementioned 3 heteroaromatic radicals carry 1 or 2 radicals Ra selected from Cl, Br, CH3, SCH3, OCHF2 and CF3, which compounds I are of formula 1.1 :
Figure imgf000021_0001
With respect to their use as component 1 ) in the inventive mixtures, particular preference is given to the compounds I which are of subformula 1.1 compiled in the Table A below. Here, the groups mentioned in the Tables for a substituent are furthermore, independently of the combination wherein they are mentioned, a particularly preferred embodiment of the substituent in question.
Table A: Compounds I of subformula 1.1 , wherein m, n, R1, R3 and the meaning of Het for each individual compound corresponds in each case to one line.
Figure imgf000021_0002
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0002
"-" when referring to (R1)n or (R3)m means that n or m is zero.
According to a further preferred embodiment, the mixtures comprise compounds I, wherein X is N or CH, n is O, 1 or 2, R1 is CH3 or OCH3, R2 is hydrogen, the moiety Het- Y is located on the phenyl ring in the para-position with respect to the sulfonyl group, Y is -S-, m is O or 1 , R3 is CH3 or F, Het is selected from pyridin-2-yl, pyridin-4-yl and pyrimidin-2-yl, wherein the aforementioned 3 heteroaromatic radicals carry 1 or 2 radicals Ra selected from Cl, Br, CH3 and CF3, which compounds I are of formula 1.2:
Figure imgf000028_0001
With respect to their use as component 1 ) in the inventive mixtures, particular preference is given to the compounds I which are of subformula 1.2 compiled in the Table D below. Here, the groups mentioned in the Tables for a substituent are furthermore, independently of the combination wherein they are mentioned, a particularly preferred embodiment of the substituent in question.
Table D: Compounds I of subformula 1.2, wherein m, n, R1, R3 and the meaning of Het for each individual compound corresponds in each case to one line.
Figure imgf000028_0003
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
"-" when referring to (R1)n or (R3)m means that n or m is zero.
According to a further preferred embodiment, the mixtures comprise compounds I, wherein X is N or CH, n is O, 1 or 2, R1 is CH3 or OCH3, R2 is hydrogen, the moiety Het- Y is located on the phenyl ring in the meta-position with respect to the sulfonyl group, Y is -O-, m is 0 or 1 , R3 is CH3 or F, Het is selected from pyridin-2-yl, pyridin-4-yl and pyrimidin-2-yl, wherein the aforementioned 3 heteroaromatic radicals carry 1 or 2 radicals Ra selected from Cl, Br, CH3 and CF3, which compounds I are of formula 1.3:
Figure imgf000035_0001
With respect to their use as component 1 ) in the inventive mixtures, particular preference is given to the compounds I which are of subformula 1.3 compiled in the Table E below. Here, the groups mentioned in the Tables for a substituent are furthermore, independently of the combination wherein they are mentioned, a particularly preferred embodiment of the substituent in question.
Table E: Compounds I of subformula 1.3, wherein m, n, R1, R3 and the meaning of Het for each individual compound corresponds in each case to one line.
Figure imgf000035_0002
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0002
"-" when referring to (R1)n or (R3)m means that n or m is zero.
According to a further preferred embodiment, the mixtures comprise compounds I, wherein X is N or CH, n is O, 1 or 2, R1 is CH3 or OCH3, R2 is hydrogen, the moiety Het- Y is located on the phenyl ring in the para-position with respect to the sulfonyl group, Y is -O-CH2-, m is O or 1 , R3 is CH3 or F, Het is selected from pyridin-2-yl, pyridin-4-yl and pyrimidin-2-yl, wherein the aforementioned 3 heteroaromatic radicals carry 1 or 2 radicals Ra selected from Cl, Br, CH3 and CF3, which compounds I are of formula 1.4:
Figure imgf000041_0001
With respect to their use as component 1 ) in the inventive mixtures, particular preference is given to the compounds I which are of subformula 1.4 compiled in the Table F below. Here, the groups mentioned in the Tables for a substituent are furthermore, independently of the combination wherein they are mentioned, a particularly preferred embodiment of the substituent in question.
Table F: Compounds I of subformula 1.4, wherein m, n, R1, R3 and the meaning of Het for each individual compound corresponds in each case to one line.
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
"-" when referring to (R1)n or (R3)m means that n or m is zero.
According to a further preferred embodiment, the mixtures comprise compounds I, wherein X is N or CH, n is 0, 1 or 2, R1 is CH3 or OCH3, R2 is methyl, the moiety Het-Y is located on the phenyl ring in the para-position with respect to the sulfonyl group, Y is -0-, m is O or 1 , R3 is CH3 or F, Het is selected from pyridin-2-yl, pyridin-4-yl and pyrimidin-2-yl, wherein the aforementioned 3 heteroaromatic radicals carry 1 or 2 radicals Ra selected from Cl, Br, CH3 and CF3, which compounds I are of formula 1.5:
Figure imgf000048_0001
With respect to their use as component 1 ) in the inventive mixtures, particular preference is given to the compounds I which are of subformula 1.5 compiled in the Table G below. Here, the groups mentioned in the Tables for a substituent are furthermore, independently of the combination wherein they are mentioned, a particularly preferred embodiment of the substituent in question.
Table G: Compounds I of subformula 1.5, wherein m, n, R1, R3 and the meaning of Het for each individual compound corresponds in each case to one line.
Figure imgf000048_0002
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
"-" when referring to (R1)n or (R3)m means that n or m is zero.
According to the present invention, it may be preferred that the mixtures comprise compound I, compounds Il and compounds III in a synergistically effective amount. It is also preferred, that the binary mixtures comprise a compound I and a compound Il in as synergistically effective amount. Another embodiment relates to mixtures wherein compound Il selected from groups A) to I) is different from compound III selected from groups A) to I).
It may also be preferred that the mixtures comprise as compounds Il and compounds III fungicidal compounds that are independently of each other selected from the groups A), B), C), D), E) and F). It may also be preferred that the binary mixtures comprise as compound Il a fungicidal compound that is selected from the groups A), B), C), D), E) and F).
According to another embodiment of the invention, mixtures comprise as compound
Ili a herbicidal compound that is selected from the group H).
According to a further embodiment, mixtures comprise as compound III an insecticidal compound that is selected from the group I).
Preference is also given to mixtures comprising at least one compound selected from the strobilurines of group A) and particularly selected from azoxystrobin, dimoxy- strobin, enestroburin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb and trifloxystrobin.
Preference is also given to mixtures comprising at least one active substance selected from the carboxamides of group B) and particularly selected from bixafen, boscalid, fluopyram, isopyrazam, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-
5-fluoro-1 H-pyrazole-4-carboxamide (penflufen), penthiopyrad, sedaxane, fenhexamid, metalaxyl, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolid (picobenzamid), fluopram, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-car- boxamide (penflufen), penthiopyrad, zoxamide, carpropamid, mandipropamid and N- (3',4',5'-trifluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide. Preference is given to mixtures comprising at least one compound selected from the azoles of group C) and particularly selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamid, benomyl and ethaboxam.
Preference is also given to mixtures comprising at least one compound selected from the heterocyclic compounds of group D) and particularly selected from fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforine, fludioxonil, dodemorph, fen- propimorph, tridemorph, fenpropidin, iprodione, vinclozolin, famoxadone, fenamidone, probenazole, proquinazid, acibenzolar-S-methyl, captafol, folpet, fenoxanil, quinoxyfen and 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine.
Preference is also given to mixtures comprising at least one compound selected from the carbamates of group E) and particularly selected from mancozeb, metiram, propineb, thiram, iprovalicarb, benthiavalicarb and propamocarb. Preference is also given to mixtures comprising at least one compound selected from the fungicides given in group F) and particularly selected from dithianon, fentin salts, such as fentin acetate, fosetyl, fosetyl-aluminium, H3PO3 and salts thereof, chlorothalonil, dichlofluanid, thiophanat-methyl, copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, cymoxanil, metrafenone, spiroxamine and N-methyl-2-{1 -[(5-methyl-3-trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}- N-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1 -yl]-4-thiazolecarboxamide.
Particular preference is also given to mixtures comprising as compound Il one compound selected from the strobilurines of group A) and particularly selected from azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, orysa- strobin, picoxystrobin, pyraclostrobin, pyribencarb and trifloxystrobin, and as compound III at least one compound selected from the carboxamides of group B) and particularly selected from bixafen, boscalid, fluopyram, isopyrazam, N-(2-(1 ,3-dimethyl-butyl)- phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide (penflufen), penthiopyrad, sedaxane, fenhexamid, metalaxyl, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolid (picobenzamid), fluopram, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl- 5-fluoro-1 H-pyrazole-4-carboxamide (penflufen), penthiopyrad, zoxamide, carprop- amid, mandipropamid and N-(3',4',5'-trifluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxamide.
Particular preference is also given to mixtures comprising as compound Il one active substance selected from the strobilurines of group A) and particularly selected from azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb and trifloxystrobin, and as compound III at least one compound selected from the azoles of group C) and particularly selected from cyproconazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamid, benomyl, carbendazim and ethaboxam.
Particular preference is also given to mixtures comprising as compound Il one compound selected from the azoles of group C) and particularly selected from cypro- conazole, difenoconazole, epoxiconazole, fluquinconazole, flusilazole, flutriafol, met- conazole, myclobutanil, penconazole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, cyazofamid, beno- myl, carbendazim and ethaboxam, and as compound III at least one compound selected from the carboxamides of group B) and particularly selected from bixafen, boscalid, fluopyram, isopyrazam, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyr- azole-4-carboxamide (penflufen), penthiopyrad, sedaxane, fenhexamid, metalaxyl, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolid (picobenzamid), fluopyram, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide (penflufen), penthiopyrad, zoxamide, carpropamid, mandipropamid and N-(3',4',5'-tri- fluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxamide.
Particular preference is also given to mixtures comprising as compound Il one active substance selected from the strobilurines of group A) and particularly selected from azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb and trifloxystrobin, and as compound III at least one compound selected from the heterocyclic compounds of group D) and particularly selected from fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforine, fludioxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, vinclozolin, famoxadone, fenamidone, probenazole, proquinazid, acibenz- olar-S-methyl, captafol, folpet, fenoxanil, quinoxyfen and 5-ethyl-6-octyl-[1 ,2,4]triazolo- [1 ,5-a]pyrimidine-7-ylamine.
Particular preference is also given to mixtures comprising as compound Il one compound selected from the heterocyclic compounds of group D) and particularly selected from fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforine, fludioxonil, dodemorph, fenpropimorph, tridemorph, fenpropidin, iprodione, vinclozolin, famoxadone, fenamidone, probenazole, proquinazid, acibenzolar-S-methyl, captafol, folpet, fenoxanil, quinoxyfen and 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine- 7-ylamine, and as compound III at least one compound selected from the carbox- amides of group B) and particularly selected from bixafen, boscalid, fluopyram, isopyrazam, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-car- boxamide (penflufen), penthiopyrad, sedaxane, fenhexamid, metalaxyl, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolid (picobenzamid), fluopram, N-(2-(1 ,3-di- methyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide (penflufen), penthiopyrad, zoxamide, carpropamid, mandipropamid and N-(3',4',5'-trifluorobiphenyl- 2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide.
Particular preference is also given to mixtures comprising as compound Il one compound selected from the strobilurines of group A) and particularly selected from azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, orysa- strobin, picoxystrobin, pyraclostrobin, pyribencarb and trifloxystrobin, and as compound III at least one compound selected from the fungicides given in group F) and particularly selected from dithianon, fentin salts, such as fentin acetate, fosetyl, fosetyl- aluminium, H3PO3 and salts thereof, chlorthalonil, dichlofluanid, thiophanate-methyl, copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, cymox- anil, metrafenone, spiroxamine and N-methyl-2-{1-[(5-methyl-3-trifluoromethyl- 1 H-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-N-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1-yl]- 4-thiazolecarboxamide. Particular preference is also given to mixtures comprising as compound Il one compound selected from the fungicides given in group F) and particularly selected from dithianon, fentin salts, such as fentin acetate, fosetyl, fosetyl-aluminium, H3PO3 and salts thereof, chlorthalonil, dichlofluanid, thiophanat-methyl, copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, cymoxanil, metrafenone, spirox- amine and N-methyl-2-{1 -[(5-methyl-3-trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin- 4-yl}-N-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide, and as compound III at least one compound selected from the carboxamides of group B) and particularly selected from bixafen, boscalid, fluopyram, isopyrazam, N-(2-(1 ,3-dimethyl- butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide (penflufen), penthio- pyrad, sedaxane, fenhexamid, metalaxyl, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolid (picobenzamid), zoxamide, carpropamid, mandipropamid and N-(3', 4', 5'-trifluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxamide. Particular preference is also given to mixtures, comprising as components 2) and 3) at least two compounds selected from epoxiconazole, metconazole, tebuconazole, triticonazole, prothioconazole, difenoconazole, cyproconazole, kresoxim-methyl, pyraclostrobin, azoxystrobin, trifloxystrobin, dimoxystrobin, orysastrobin, fluoxastrobin, dimethomorph, 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, pyrimethanil, metalaxyl, fenpropimorph, mancozeb, metiram, thiophanate-methyl, chlorothalonil, Metrafenon, bixafen, boscalid, N-(3',4',5'-trifluorobiphenyl-2-yl)-3-difluoromethyl-1- methyl-1 H-pyrazole-4-carboxamide, isopyrazam, fluopyram, N-(2-(1 ,3-dimethyl-butyl)- phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide (penflufen), penthiopyrad, sedaxane, N-Methyl-2-{1 -[(5-methyl-3-trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin- 4-yl}-N-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide, mandi- propamide, iprovalicarb, benthiovalicarb, copper salts, sulphur and dithianon. Particular preference is also given to binary mixtures, comprising as components 2) one compound selected from epoxiconazole, metconazole, tebuconazole, triticonazole, prothioconazole, difenoconazole, cyproconazole, kresoxim-methyl, pyraclostrobin, azoxystrobin, trifloxystrobin, dimoxystrobin, orysastrobin, fluoxastrobin, dimethomorph, 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine, pyrimethanil, metalaxyl, fenpropimorph, mancozeb, metiram, thiophanate-methyl, chlorothalonil, Metrafenon, bixafen, boscalid, N-(3',4',5'-trifluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H- pyrazole-4-carboxamide, isopyrazam, fluopyram, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3- dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide (penflufen), penthiopyrad, sedaxane, N- Methyl-2-{1 -[(5-methyl-3-trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}-N-[(1 R)- 1 ,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide, mandipropamide, iprovalicarb, benthiovalicarb, copper salts, sulphur and dithianon.
With respect to their use as compenent 2) (Co. 2) in the inventive mixtures, preference is given to the compounds Il which are compiled in the Table B below. Table B: Preferred compounds Il for use as component 2) (Co. 2).
Figure imgf000058_0002
Figure imgf000058_0001
With respect to their use as compenent 3) (Co. 3) in the inventive ternary mixtures, preference is given to the compounds III which are compiled in the Table C below. Table C: Preferred com ounds III for use as component 3) (Co. 3).
Figure imgf000058_0004
Figure imgf000058_0003
Accordingly, the present invention furthermore to the mixtures M-1 to M-123970 as defined in Tables 1 to 23, where a row corresponds in each case to a fungicidal composition comprising as component 1 ) one of the in Tables A, D, E, F and G defined compounds I (Co. 1 ), and as component 2) the respective compound Il from groups A) to F) (Co. 2), and as component 3) the respective compound III from groups A) to F) (Co. 3) stated in the row in question. Preferably, the compositions described comprise the active substances in synergistically effective amounts.
Table 1 : Mixtures M-1 to M-5390 comprising one compound I as defined and numbered in Tables A, D, E , F and G as component 1 ) (Co. 1 ) and one compound Il from groups A) to F) as defined and numbered in Table B as component 2) (Co. 2) and one compound III from groups A) to F) as defined and numbered in Table C as component 3) (Co. 3).
Figure imgf000059_0001
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Table 2: Mixtures M-5391 to M-10780 as defined in Table 1 wherein component 2 (Co.
2) is compound II-2 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-2.
Table 3: Mixtures M-10781 to M-16170 as defined in Table 1 wherein component 2
(Co. 2) is compound 11— 3 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-3.
Table 4: Mixtures M-16171 to M-21560 as defined in Table 1 wherein component 2
(Co. 2) is compound II-4 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-4.
Table 5: Mixtures M-21561 to M-26950 as defined in Table 1 wherein component 2
(Co. 2) is compound II-5 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-5. Table 6: Mixtures M-26951 to M-32340 as defined in Table 1 wherein component 2
(Co. 2) is compound II-6 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-6.
Table 7: Mixtures M-32341 to M-37730 as defined in Table 1 wherein component 2 (Co. 2) is compound II-7 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-7.
Table 8: Mixtures M-37731 to M-43120 as defined in Table 1 wherein component 2
(Co. 2) is compound II-8 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-8. Table 9: Mixtures M-43121 to M-48510 as defined in Table 1 wherein component 2
(Co. 2) is compound II-9 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-9.
Table 10: Mixtures M-4851 1 to M-53900 as defined in Table 1 wherein component 2
(Co. 2) is compound 11-10 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of 111-10.
Table 11 : Mixtures M-53901 to M-59290 as defined in Table 1 wherein component 2
(Co. 2) is compound 11-11 instead of 11-1 and wherein, if applicable, component 3 (Co.
3) is compound 111-1 instead of 111-11.
Table 12: Mixtures M-59291 to M-64680 as defined in Table 1 wherein component 2 (Co. 2) is compound 11-12 instead of 11-1 and wherein, if applicable, component 3 (Co.
3) is compound 111-1 instead of 111-12.
Table 13: Mixtures M-64681 to M-70070 as defined in Table 1 wherein component 2
(Co. 2) is compound 11-13 instead of 11-1 and wherein, if applicable, component 3 (Co.
3) is compound 111-1 instead of 111-13. Table 14: Mixtures M-70071 to M-75460 as defined in Table 1 wherein component 2
(Co. 2) is compound 11-14 instead of 11-1 and wherein, if applicable, component 3 (Co.
3) is compound 111-1 instead of 111-14.
Table 15: Mixtures M-75461 to M-80850 as defined in Table 1 wherein component 2
(Co. 2) is compound 11-15 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of 111-15.
Table 16: Mixtures M-80851 to M-86240 as defined in Table 1 wherein component 2
(Co. 2) is compound 11-16 instead of 11-1 and wherein, if applicable, component 3 (Co.
3) is compound 111-1 instead of 111-16.
Table 17: Mixtures M-86241 to M-91630 as defined in Table 1 wherein component 2 (Co. 2) is compound 11-17 instead of 11-1 and wherein, if applicable, component 3 (Co.
3) is compound 111-1 instead of 111-17.
Table 18: Mixtures M-91631 to M-97020 as defined in Table 1 wherein component 2
(Co. 2) is compound 11-18 instead of 11-1 and wherein, if applicable, component 3 (Co.
3) is compound 111-1 instead of 111-18. Table 19: Mixtures M-97021 to M-102410 as defined in Table 1 wherein component 2
(Co. 2) is compound 11-19 instead of 11-1 and wherein, if applicable, component 3 (Co.
3) is compound 111-1 instead of 111-19. Table 20: Mixtures M-10241 1 to M-107800 as defined in Table 1 wherein component 2 (Co. 2) is compound II-20 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-20.
Table 21 : Mixtures M-107801 to M-1 13190 as defined in Table 1 wherein component 2 (Co. 2) is compound 11-21 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of 111-21.
Table 22: Mixtures M-1 13191 to M-1 18580 as defined in Table 1 wherein component 3 (Co. 3) is compound III-22 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-22. Table 23: Mixtures M-1 18581 to M-123970 as defined in Table 1 wherein component 3 (Co. 3) is compound III-23 instead of 11-1 and wherein, if applicable, component 3 (Co. 3) is compound 111-1 instead of III-23.
Further specific embodiments of the inventive mixtures are the following binary mixtures:
Table 22: Binary Mixtures B-1 to B-5635 comprising as active ingredients one compound I as defined and numbered in Table A as component 1 ) (Co. 1 ) and one compound Il from groups A) to F) as defined and numbered in Table B as component 2) (Co. 2).
Figure imgf000129_0001
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Figure imgf000167_0001
Further specific embodiments of the inventive mixtures are binary mixtures comprising as component 2) a compound selected from pyraclostrobin, boscalid fluoxapyroxad, chlorothalonil, metiram, ametoctradin, epoxiconazole and dimethomorph. The mixtures and compositions according to the invention are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomyce- tes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
The mixtures and compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants. Preferably the inventive mixtures and compositions are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes. The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germi- nation or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
Preferably, treatment of plant propagation materials with the inventive combination of compound I and compounds Il and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://www.bio.org/speeches/pubs/er/agrLproducts.asp). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-transtional modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties. Plants that have been modified by breeding, mutagenesis or genetic engineering, e. g. have been rendered tolerant to applications of specific classes of herbicides, such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. g. US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (see e. g. US 6,222,100, WO 01/82685, WO 00/026390, WO 97/41218, WO 98/002526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/014357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e. g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e.g. EP-A 242 236, EP-A 242 246) or oxynil herbicides (see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate-tolerant, Monsanto, U.S.A.) and LibertyLink® (glufosinate- tolerant, Bayer CropScience, Germany). Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as δ-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bi) or Cryθc; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize- RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxy- steroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ). Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of athropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda). Genetically modified plants capable to synthesize one or more insecticidal proteins are, e. g., described in the publications mentioned above, and some of which are commercially available such as YieldGard® (corn cultivars producing the CryiAb toxin), YieldGard® Plus (corn cultivars producing CryiAb and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c toxin), Herculex® RW (corn cultivars producing Cry34Ab1 , Cry35Ab1 and the enzyme Phosphinothricin-N-Acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the CryiAc toxin), Bollgard® I (cotton cultivars producing the CryiAc toxin), Bollgard® Il (cotton cultivars producing CryiAc and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (e. g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CryiAb toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CryiAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme). Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants. Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health- promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape, DOW Agro Sciences, Canada). Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato, BASF SE, Germany).
The inventive mixtures and compositions are particularly suitable for controlling the following plant diseases:
Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alternata), tomatoes (e. g. A. solani or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.) on corn (e. g. D. maydis), cereals (e. g. B. sorokiniana: spot blotch), rice (e. g. B. oryzae) and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce;
Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn, rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum
(teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. crucife- rarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Liber- tella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani on soybeans and F. verticillioides on corn; Gaeumannomyces graminis (take- all) on cereals (e. g. wheat or barley) and corn; Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; lsariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica); Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad-leaved trees (e. g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and there- by transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleo- morph: Tapesia yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or .rotbrenner', anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, and asparagus (e. g. P. asparagi); Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphani- dermatum); Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Uro- cystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae); Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes. The inventive mixtures and compositions are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials. The term "protection of materials" is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, colling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria. As to the protection of wood and other materials, the particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichorma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
In particular, the mixtures and compositions of the present invention are effective against plant pathogens in speciality crops such as vine, fruits, hop, vegetables and tabacco - see the above list.
Plant propagation materials may be treated with the mixtures and compositions of the invention prophylactically either at or before planting or transplanting.
The present invention also relates to a pesticidal agent comprising at least one solid or liquid carrier and a composition as described herein.
The compound I and compounds II, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The composition type depends on the particular intended purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention.
Examples for composition types are suspensions (SC, OD, FS), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, DP, DS) or granules (GR, FG, GG, MG), which can be water-soluble or wettable, as well as gel formulations for the treatment of plant propagation materials such as seeds (GF).
Usually the composition types (e. g. SC, OD, FS, WG, SG, WP, SP, SS, WS, GF) are employed diluted. Composition types such as DP, DS, GR, FG, GG and MG are usually used undiluted.
The compositions are prepared in a known manner (cf. US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, S. 8-57 und ff. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: Weed Control as a Science (J. Wiley & Sons, New York, 1961 ), Hance et al.: Weed Control Handbook (8th Ed., Blackwell Scientific, Oxford, 1989) and Mollet, H. and Grubemann, A.: Formulation technology (Wiley VCH Verlag, Weinheim, 2001 ).
The agrochemical compositions may also comprise auxiliaries which are customary in agrochemical compositions. The auxiliaries used depend on the particular application form and active substance, respectively.
Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents, anti- foaming agents, if appropriate colorants and tackifiers or binders (e. g. for seed treatment formulations).
Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols, ketones such as cyclohexanone and gamma-butyrolactone, fatty acid dimethylamides, fatty acids and fatty acid esters and strongly polar solvents, e. g. amines such as N-methylpyrrolidone.
Solid carriers are mineral earths such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
Suitable surfactants (adjuvants, wtters, tackifiers, dispersants or emulsifiers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsoulfonic acid (Borresperse® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Morwet® types, Akzo Nobel, U.S.A.), dibutylnaphthalene- sulfonic acid (Nekal® types, BASF, Germany), and fatty acids, alkylsulfonates, alkyl- arylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, furthermore condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxy-ethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearyl- phenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and proteins, denatured proteins, polysaccharides (e. g. methylcellulose), hydrophobically modified starches, polyvinyl alcohols (Mowiol® types, Clariant, Switzer- land), polycarboxylates (Sokolan® types, BASF, Germany), polyalkoxylates, polyvinyl- amines (Lupasol® types, BASF, Germany), polyvinylpyrrolidone and the copolymers therof.
Examples for thickeners (i. e. compounds that impart a modified flowability to compositions, i. e. high viscosity under static conditions and low viscosity during agitation) are polysaccharides and organic and anorganic clays such as Xanthan gum (Kelzan®, CP Kelco, U.S.A.), Rhodopol® 23 (Rhodia, France), Veegum® (RT. Vanderbilt, U.S.A.) or Attaclay® (Engelhard Corp., NJ, USA).
Bactericides may be added for preservation and stabilization of the composition. Examples for suitable bactericides are those based on dichlorophene and benzyl- alcohol hemi formal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide® MBS from Thor Chemie).
Examples for suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Examples for anti-foaming agents are silicone emulsions (such as e. g. Silikon®
SRE, Wacker, Germany or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and mixtures thereof.
Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples to be mentioned und the designations rhodamin B, C. I. pigment red 1 12, C. I. solvent red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Examples for tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose®, Shin-Etsu, Japan).
Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the compound I and compounds Il with at least one solid carrier. Granules, e. g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers. Examples for composition types are:
1. Composition types for dilution with water i) Water-soluble concentrates (SL, LS)
10 parts by weight of active compound(s) are dissolved in 90 parts by weight of water or in a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active substance dissolves upon dilution with water. In this way, a composition having a content of 10% by weight of active substance is obtained. ii) Dispersible concentrates (DC)
20 parts by weight of of active compound(s) are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, e. g. polyvinylpyrrolidone. Dilution with water gives a dispersion. The active substance content is 20% by weight. iii) Emulsifiable concentrates (EC)
15 parts by weight of a of active compound(s) are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The composition has an active substance content of 15% by weight. iv) Emulsions (EW, EO, ES)
25 parts by weight of a of active compound(s) are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The composition has an active substance content of 25% by weight. v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20 parts by weight of of active compound(s) are comminuted with addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. The active substance content in the composition is 20% by weight. vi) Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of of active compound(s) are ground finely with addition of 50 parts by weight of dispersants and wetting agents and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance. The composition has an active substance content of 50% by weight. vii) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)
75 parts by weight of of active compound(s) are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetting agents and silica gel. Dilution with water gives a stable dispersion or solution of the active substance. The active substance content of the composition is 75% by weight. viii) Gel (GF)
In an agitated ball mill, 20 parts by weight of of active compound(s) are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance, whereby a composition with 20% (w/w) of active substance is obtained.
2. Composition types to be applied undiluted ix) Dustable powders (DP, DS)
5 parts by weight of of active compound(s) are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable composition having an active substance content of 5% by weight, x) Granules (GR, FG, GG, MG)
0.5 parts by weight of of active compound(s) is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted having an active substance content of 0.5% by weight, xi) ULV solutions (UL)
10 parts by weight of of active compound(s) are dissolved in 90 parts by weight of an organic solvent, e. g. xylene. This gives a composition to be applied undiluted having an active substance content of 10% by weight.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
Water-soluble concentrates (LS), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES) emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. These compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted. The compositions in question give, after two-to- tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before sowing. Methods for applying or treating agrochemical compounds and compositions thereof, respectively, on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting, dusting and soaking application methods of the propagation material. In a preferred embodiment, the compounds or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
In a preferred embodiment, a suspension-type (FS) composition is used for seed treatment. Typcially, a FS composition may comprise 1-800 g/l of active substance, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
The active substances can be used as such or in the form of their compositions, e. g. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading, brushing, immersing or pouring. The application forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active substances according to the invention.
Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1 % by weight of active substance.
The active substances may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives.
When employed in plant protection, the amounts applied are, depending on the kind of effect desired, between 0.01 and 2.0 kg of active substance per ha.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 1 to 1000 g, preferably from 5 to 100 g, per 100 kilogram of seed are generally required.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are, e. g., 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, herbicides, bactericides, other fungicides and/or pesticides may be added to the active substances or the compositions comprising them, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
Adjuvants which can be used are in particular organic modified polysiloxanes such as Break Thru S 240®; alcohol alkoxylates such as Atplus 245®, Atplus MBA 1303®, Plurafac LF 300® and Lutensol ON 30®; EO/PO block polymers, e. g. Pluronic RPE 2035® and Genapol B®; alcohol ethoxylates such as Lutensol XP 80®; and dioctyl sulfosuccinate sodium such as Leophen RA®.
The compositions according to the invention can, in the use form as fungicides, also be present together with other active substances, e. g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers, as pre-mix or, if appropriate, not until immeadiately prior to use (tank mix).
According to this invention, applying compound I together with a compound Il is to be understood to denote, that a compound I and at least one compound Il occur simultaneously at the site of action (i.e. the harmful fungi to be controlled or their habitats such as infected plants, plant propagation materials, particularly seeds, surfaces, materials or the soil as well as plants, plant propagation materials, particularly seeds, soil, surfaces, materials or rooms to be protected from fungal attack) in an effective amount. This can be obtained by applying compound I and compound Il simultaneously, either jointly (e. g. as tank-mix) or separately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the present invention.
In the binary mixtures and compositions according to the invention the weight ratio of compound I and compound Il generally depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4: 1.
Any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the compound I.
In the ternary mixtures, i.e. compositions according to the invention comprising one compound I (component 1 ) and a compound Il (component 2) and a compound III (component 3), e. g. two active substances from groups A) to I), the weight ratio of component 1 ) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4:1 , and the weight ratio of component 1 ) and component 3) usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4:1.
In the mixtures and compositions, the compound I/compound ll/compound III ratio is advantageously chosen so as to produce a synergistic effect.
The term "synergstic effect" is understood to refer in particular to that defined by Colby's formula (Colby, S. R., "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, ^5, pp. 20-22, 1967).
The term "synergistic effect" is also understood to refer to that defined by application of the Tammes method, (Tammes, P. M. L., "Isoboles, a graphic representation of synergism in pesticides", Netherl. J. Plant Pathol. 70, 1964). The components can be used individually or already partially or completely mixed with one another to prepare the composition according to the invention. It is also possible for them to be packaged and used as combination such as a kit of parts.
In one embodiment of the invention, the kits may include one or more, including all, components that may be used to prepare a subject agrochemical composition. E. g., kits may include one or more fungicide component(s) and/or an adjuvant component and/or a insecticide component and/or a growth regulator component and/or a herbicde. One or more of the components may already be combined together or pre- formulated. In those embodiments where more than two components are provided in a kit, the components may already be combined together and as such are packaged in a single container such as a vial, bottle, can, pouch, bag or canister. In other embodiments, two or more components of a kit may be packaged separately, i. e., not pre-formulated. As such, kits may include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical composition. In both forms, a component of the kit may be applied separately from or together with the further components or as a component of a combination composition according to the invention for preparing the composition according to the invention. The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank or a spray plane. Here, the agrochemical composition is made up with water and/or buffer to the desired application concentration, it being possible, if appropriate, to add further auxiliaries, and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 50 to 500 liters of the ready-to-use spray liquor are applied per hectare of agricultural useful area, preferably 100 to 400 liters.
According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate (tank mix).
In a further embodiment, either individual components of the composition according to the invention or partially premixed components may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate (tank mix). In a further embodiment, either individual components of the composition according to the invention or partially premixed components can be applied jointly (e. .g. after tankmix) or consecutively.
The fungicidal action of the compositions according to the invention can be shown by the tests described below.
The active compounds, separately or jointly, are prepared as a stock solution comprising 25 mg of active compound which is made up to 10 ml using a mixture of acetone and/or DMSO and the emulsifier Uniperol® EL (wetting agent having an emulsifying and dispersing action based on ethoxylated alkylphenols) in a ratio by volume of solvent/emulsifier of 99:1. The mixture is then made up to 100 ml with water. This stock solution is diluted with the solvent/em ulsifier/water mixture described to give the concentration of active compound stated below.
The visually determined percentages of infected leaf areas are converted into efficacies in % of the untreated control. The efficacy (E) is calculated as follows using Abbot's formula: E = (1 - α/β) - 100 α corresponds to the fungicidal infection of the treated plants in % and β corresponds to the fungicidal infection of the untreated (control) plants in %
An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected.
The expected efficacies of active compound combinations were determined using Colby's formula (Colby, S. R. "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds, ^5, pp. 20-22, 1967) and compared with the observed efficacies. Colby's formula: E = x + y - x -y/100
E expected efficacy, expressed in % of the untreated control, when using the mixture of the active compounds A and B at the concentrations a and b x efficacy, expressed in % of the untreated control, when using the active compound A at the concentration a y efficacy, expressed in % of the untreated control, when using the active compound B at the concentration b. Microtests
The active compounds were formulated separately as a stock solution having a concentration of 10000 ppm in dimethyl sulfoxide.
The product orysastrobin was used as commercial finished formulation and diluted with water to the stated concentration of the active compound. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of the respective pathogen in the respective nutrient medium was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
The measured parameters were compared to the growth of the active compound- free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. These percentages were converted into efficacies. The expected efficacies of active compound mixtures were determined using
Colby's formula [R. S. Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared with the observed efficacies.
Use example 1. Activity against the late blight pathogen Phytophthora infestans
A spore suspension of Phytophtora infestans containing a pea juice-based aqueous nutrient medium was used. Table 1)1 A: Results concerning binary mixtures
Figure imgf000183_0001
Figure imgf000184_0001
Table 1)1 B: Results concernin ternar mixtures
Figure imgf000184_0002
Figure imgf000185_0001
Figure imgf000186_0001
Use example 2. Activity against the grey mold Botrytis cinerea
A spore suspension of Botrci cinerea in an aqueous biomalt solution was uesd. Table 1)2 A: Results concernin binar mixtures
Figure imgf000186_0002
Figure imgf000187_0001
Figure imgf000188_0001
Figure imgf000189_0001
Use example 3. Activity against rice blast Pyricularia oryzae
A spore suspension of Pyricularia oryzae in an aqueous biomalt solution was used. Table 1)3 A: Results concernin binar mixtures
Figure imgf000189_0002
Figure imgf000190_0001
Figure imgf000191_0001
Use example 4. Activity against leaf blotch pathogen Septoria tritici
A spore suspension of Septoria tritici in an aqueous biomalt solution was used. Table 1)4 A: Results concerning binary mixtures
Figure imgf000191_0002
Figure imgf000192_0001
Table 1)4 B: Results concernin ternar mixtures
Figure imgf000193_0001
Figure imgf000194_0001
Figure imgf000195_0001
Figure imgf000196_0001

Claims

Claims
1. A mixture, comprising as active compounds
1 ) at least one heteroaromatic sulfonamide compound of the formula I
Figure imgf000197_0001
where:
X is N or CH or C-R1;
n indicates the number of substituents R1 on the pyridine or pyrimidine ring and n is 0, 1 , 2 or 3;
R1 is halogen, CN, NO2, OH, SH, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alk- oxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkyl- sulfinyl, Ci-C4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkyl- sulfonyl, amino, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, Ci-C4-alkoxy- Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Cs-Cs-cycloalkyl or Ci-C4-alkyl-C3-C8-cycloalkyl; and/or
two radicals R1 that are bound to adjacent carbon atoms of the pyridine or pyrimine ring may form together with said carbon atoms a fused benzene ring, a fused saturated or partially unsaturated 5-, 6-, or 7- membered carbocycle or a fused 5-, 6-, or 7-membered heterocycle containing 1 , 2, or 3 heteroatoms selected from the group consisting of
2 nitrogen, 1 oxygen and 1 sulfur atoms as ring members, it being possible for the fused ring to carry 1 or 2 radicals selected from the group consisting of halogen, Ci-C4-alkyl, halomethyl, Ci-C4-alkoxy or halo- methoxy,
it being possible for n = 2, 3 or 4 that R1 are identical or different;
R2 is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl,
Cs-Cs-cycloalkyl, Ci-C4-alkyl-C3-C8-cycloalkyl or benzyl wherein the phenyl moiety of benzyl is unsubstituted or carries 1 , 2, 3, 4, or 5 substituents selected from the group consisting of CN, halogen, Ci-C4-alk- yl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, (Ci-C4-alkoxy)car- bonyl and di(Ci-C4-alkyl)aminocarbonyl;
m indicates the number of substituents R3 on the phenyl ring and m is 0,
1 , 2, 3 or 4; R3 is halogen, CN, NO2, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy, it being possible for m = 2, 3 or 4 that R3 are identical or different;
Y is a divalent group selected from -0-, Ci-C4-alkanediyl, -O-CH2-,
-CH2-O-, -C(NOR")-, -S-, -S(=0)-, -S(=0)2- and -N(R")-, wherein R" is hydrogen or Ci-C4-alkyl and wherein the Ci-C4-alkanediyl moiety is un- substituted or carries 1 or 2 substituents selected from the group con- sisting of oxo, CN, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy;
Het is a 5- or 6-membered heteroaromatic radical, wherein the ring member atoms of the heteroaromatic radical include, besides carbon atoms 1 , 2, 3 or 4 nitrogen atoms, or 1 oxygen atom and O, 1 or 2 nitrogen atoms or 1 sulfur atom and O, 1 or 2 nitrogen atoms and wherein the heteroaromatic radical is unsubstituted or carries 1 , 2, 3 or 4 identical or different substituents Ra, wherein two radicals Ra that are bound to adjacent ring member atoms may form a fused 5- or 6-membered carbo- cycle or heterocycle, wherein the fused carbocycle or heterocycle is unsubstituted or carries 1 , 2, 3 or 4 identical or different substituents Rb;
Ra is halogen, CN, NO2, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio,
Ci-C4-haloalkylthio, Ci-C4-alkylsulfinyl, Ci-C4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, amino, Ci-C4-alkyl- amino, di(Ci-C4-alkyl)amino, Ci-C4-alkoxy-Ci-C4-alkyl,
a radical C(=O)R, wherein R is H, Ci-C4-alkyl, Ci-C4-haloalkyl,
C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-alkoxy, Ci-C4-alkoxy- Ci-C4-alkoxy, Ci-C4-haloalkoxy, amino, Ci-C4-alkylamino or di(Ci-C4-alkyl)amino,
a radical CR'(=NOR"), wherein R' is H or Ci-C4-alkyl, and R" is
Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl or Ci-C4-alkoxy-Ci-C4-alkyl,
phenyl, pyridinyl, pyrimidinyl, phenoxy or phenoxyalkyl, where the five last mentioned radicals are unsubstituted or carry 1 , 2, 3 or 4 identical or different substituents Rc;
Rb and Rc independently of each other are selected from halogen, CN, NO2, OH, SH, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
and the N-oxides and the agriculturally acceptable salts of the compounds of the formula I;
and
2) one active compound Il selected from groups A) to I):
A) strobilurins azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb, trifloxystrobin, 2-(2-(6-(3-chloro-2-methyl-phenoxy)-5-fluoro-pyrimidin-4-yl- oxy)-phenyl)-2-methoxyimino-N-methyl-acetamide, 3-methoxy-2-(2-(N-(4- methoxy-phenyl)-cyclopropane-carboximidoylsulfanylmethyl)-phenyl)-acrylic acid methyl ester, methyl (2-chloro-5-[1 -(3-methylbenzyloxyimino)ethyl]- benzyl)carbamate and 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylidene- aminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide; B) carboxamides
- carboxanilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, car- boxin, fenfuram, fenhexamid, flutolanil, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyr- azole-4-carboxamide (penflufen), penthiopyrad, sedaxane, tecloftalam, thifluz- amide, tiadinil, 2-amino-4-methyl-thiazole-5-carboxanilide, 2-chloro-N-(1 ,1 ,3- trimethyl-indan-4-yl)-nicotinamide, N-(3',4',5'-trifluorobiphenyl-2-yl)-3-difluoro- methyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(4'-trifluoromethylthiobi- phenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide and N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-car- boxamide;
- carboxylic morpholides: dimethomorph, flumorph, pyrimorph;
- benzoic acid amides: flumetover, fluopicolide, fluopyram, zoxamide, N-(3-ethyl-3,5,5-trimethyl-cyclohexyl)-3-formylamino-2-hydroxy-benzamide; - other carboxamides: carpropamid, dicyclomet, mandiproamid, oxytetracy- clin, silthiofarm and N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide; C) azoles
- triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difeno- conazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, flu- quinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipcona- zole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, pencona- zole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetra- conazole, triadimefon, triadimenol, triticonazole, uniconazole, 1 -(4-chloro- phenyl)-2-([1 ,2,4]triazol-1 -yl)-cycloheptanol;
- imidazoles: cyazofamid, imazalil, pefurazoate, prochloraz, triflumizol;
- benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole; - others: ethaboxam, etridiazole, hymexazole and 2-(4-chloro-phenyl)-
N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;
D) heterocyclic compounds
- pyridines: fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isox- azolidin-3-yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine, 2,3,5,6-tetra-chloro-4-methanesulfonyl-pyridine, 3,4,5-trichloropyri- dine-2,6-di-carbonitrile, N-(1 -(5-bromo-3-chloro-pyridin-2-yl)-ethyl)-2,4-di- chloronicotinamide, N-[(5-bromo-3-chloro-pyridin-2-yl)-methyl]-2,4-dichloro- nicotinamide; pyrimidines: bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, me- panipyrim, nitrapyrin, nuarimol, pyrimethanil; piperazines: triforine;
- pyrroles: fenpiclonil, fludioxonil;
- morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph; - piperidines: fenpropidin;
- dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin;
- non-aromatic 5-membered heterocycles: famoxadone, fenamidone, flutianil, octhilinone, probenazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-di- hydro-pyrazole-1 -carbothioic acid S-allyl ester; - others: acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S, captafol, captan, chinomethionat, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, fenoxanil, Folpet, oxolinic acid, piperalin, pro- quinazid, pyroquilon, quinoxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo- 3-propylchromen-4-one, 5-chloro-1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl- 1 H-benzoimidazole and 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-yl- amine;
E) carbamates
- thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasul- phocarb, metiram, propineb, thiram, zineb, ziram; - carbamates: benthiavalicarb, diethofencarb, iprovalicarb, propamocarb, propamocarb hydrochlorid, valiphenal and N-(1 -(1-(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
F) other active substances
- guanidines: guanidine, dodine, dodine free base, guazatine, guazatine- acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate);
- antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, polyoxine, validamycin A; nitrophenyl derivates: binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecnazen, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;
- sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane; - organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, ipro- benfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl;
- organochlorine compounds: chlorothalonil, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pencycuron, pentachlorphenole and its salts, phthalide, quintozene, thiophanate-methyl, tolylfluanid, N-(4-chloro- 2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
- inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
- others: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamin, metra- fenone, mildiomycin, oxin-copper, prohexadione-calcium, spiroxamine, tolylfluanid, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro- phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl-phen- oxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro- 3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl forma- midine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)- N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2-methyl-4-(3-trimethyl- silanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, 2-{1 -[2-(5-methyl- S-trifluoromethyl-pyrazole-i -yO-acetyO-piperidin^-ylJ-thiazole^-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1 -yl)-amide, 2-{1 -[2-(5-methyl- S-trifluoromethyl-pyrazole-i -yO-acety^-piperidin^-ylJ-thiazole^-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1 -yl-amide, acetic acid
6-tert.-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester and N-methyl- 2-{1 -[(5-methyl-3-trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}-N- [(1 R)-1 ,2,3,4-tetrahydronaphthalen-1 -yl]-4-thiazolecarboxamide. G) growth regulators abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flu- metralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, pro- hexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapen- thenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid , trinexapac- ethyl and uniconazole; H) herbicides
- acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproani- lide, pethoxamid, pretilachlor, propachlor, thenylchlor; - amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate;
- aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop, fluazi- fop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
- Bipyridyls: diquat, paraquat; - (thio)carbamates: asulam, butylate, carbetamide, desmedipham, dime- piperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate;
- cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, seth- oxydim, tepraloxydim, tralkoxydim; - dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin;
- diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fome- safen, lactofen, oxyfluorfen; hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil; - imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, ima- zaquin, imazethapyr;
- phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
- pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate; - pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, flu- roxypyr, picloram, picolinafen, thiazopyr;
- sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfo- sulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfu- ron, tritosulfuron, 1 -((2-chloro-6-propyl-imidazo[1 ,2-b]pyridazin-3- yl)sulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea; - triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazi- none, metamitron, metribuzin, prometryn, simazine, terbuthylazine, ter- butryn, triaziflam;
- ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, methabenzthiazuron,tebuthiuron; - other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam- methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, or- tho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, py- roxasulfone, pyroxsulam; - others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone,benfluresate, benzofenap, bentazone, benzobicyclon, bro- macil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cini- don-ethlyl, chlorthal, cinmethylin, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, Ie- nacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl ar- sonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyra- zolynate, quinoclamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, te- furyltrione, tembotrione, thiencarbazone, topramezone, 4-hydroxy-3-[2-(2- methoxy-ethoxymethyl)-6-trifluoromethyl-pyridine-3-carbonyl]-bicyclo- [3.2.1]oct-3-en-2-one, (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluo- romethyl-3,6-dihydro-2H-pyrimidin-1 -yl)-phenoxy]-pyridin-2-yloxy)-acetic acid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-pyπmidine-4-carboxylic acid methyl ester, 6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin- 4-ol, 4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-
2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethyl- amino-2-fluoro-phenyl)-pyridine-2-carboxylic acid methyl ester. I) insecticides
- organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlor- pyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicroto- phos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
- carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbo- furan, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate; - pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cyper- methrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, delta- methrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, si- lafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin;
- insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlor- fluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflu- muron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, dio- fenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spi- rodiclofen, spiromesifen, spirotetramat; nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefu- ran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1 -(2-chloro-thiazol-5-ylmethyl)-2-nitπmino-3,5-dimethyl-[1 ,3,5]triazinane;
- GABA antagonist compounds: endosulfan, ethiprole, fipronil, vaniliprole, pyra- fluprole, pyriprole, 5-amino-1 -(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl- 1 H-pyrazole-3-carbothioic acid amide;
- macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, Ie- pimectin, spinosad, spinetoram;
- mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim; - METI Il and III compounds: acequinocyl, fluacyprim, hydramethylnon;
- Uncouplers: chlorfenapyr;
- oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide, propargite; moulting disruptor compounds: cryomazine; - mixed function oxidase inhibitors: piperonyl butoxide;
- sodium channel blockers: indoxacarb, metaflumizone;
- others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thiocyclam, flubendiamide, chlorantraniliprole, cyazypyr (HGW86), cyeno- pyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, and pyrifluquinazon; in a synergistically effective amount.
2. A mixture according to claim 1 , comprising a compound I and a compound Il in a weight ratio of from 100:1 to 1 :100.
3. A mixture, comprising as active compounds
1 ) at least one heteroaromatic sulfonamide compound of the formula I
Figure imgf000204_0001
where:
X is N or CH or C-R1
n indicates the number of substituents R1 on the pyridine or pyrimidine ring and n is 0, 1 , 2 or 3;
R1 is halogen, CN, NO2, OH, SH, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alk- oxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkyl- sulfinyl, Ci-C4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkyl- sulfonyl, amino, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, Ci-C4-alkoxy- Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Cs-Cs-cycloalkyl or Ci-C4-alkyl-C3-C8-cycloalkyl; and/or
two radicals R1 that are bound to adjacent carbon atoms of the pyridine or pyrimine ring may form together with said carbon atoms a fused benzene ring, a fused saturated or partially unsaturated 5-, 6-, or 7- membered carbocycle or a fused 5-, 6-, or 7-membered heterocycle containing 1 , 2, or 3 heteroatoms selected from the group consisting of 2 nitrogen, 1 oxygen and 1 sulfur atoms as ring members, it being pos- sible for the fused ring to carry 1 or 2 radicals selected from the group consisting of halogen, Ci-C4-alkyl, halomethyl, Ci-C4-alkoxy or halo- methoxy,
it being possible for n = 2, 3 or 4 that R1 are identical or different;
R2 is hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, Cs-Cs-cycloalkyl, Ci-C4-alkyl-C3-C8-cycloalkyl or benzyl wherein the phenyl moiety of benzyl is unsubstituted or carries 1 , 2, 3, 4, or 5 sub- stituents selected from the group consisting of CN, halogen, Ci-C4-alk- yl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, (Ci-C4-alkoxy)car- bonyl and di(Ci-C4-alkyl)aminocarbonyl;
m indicates the number of substituents R3 on the phenyl ring and m is 0,
1 , 2, 3 or 4;
R3 is halogen, CN, NO2, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy, it being possible for m = 2, 3 or 4 that R3 are identical or different;
Y is a divalent group selected from -O-, Ci-C4-alkanediyl, -O-CH2-,
-CH2-O-, -C(NOR")-, -S-, -S(=O)-, -S(=O)2- and -N(R")-, wherein R" is hydrogen or Ci-C4-alkyl and wherein the Ci-C4-alkanediyl moiety is unsubstituted or carries 1 or 2 substituents selected from the group consisting of oxo, CN, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy;
Het is a 5- or 6-membered heteroaromatic radical, wherein the ring member atoms of the heteroaromatic radical include, besides carbon atoms 1 , 2, 3 or 4 nitrogen atoms, or 1 oxygen atom and 0, 1 or 2 nitrogen at- oms or 1 sulfur atom and 0, 1 or 2 nitrogen atoms and wherein the heteroaromatic radical is unsubstituted or carries 1 , 2, 3 or 4 identical or different substituents Ra, wherein two radicals Ra that are bound to adjacent ring member atoms may form a fused 5- or 6-membered carbocycle or heterocycle, wherein the fused carbocycle or heterocycle is unsubstituted or carries 1 , 2, 3 or 4 identical or different substituents
Ra is halogen, CN, NO2, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio,
Ci-C4-haloalkylthio, Ci-C4-alkylsulfinyl, Ci-C4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, amino, Ci-C4-alkyl- amino, di(Ci-C4-alkyl)amino, Ci-C4-alkoxy-Ci-C4-alkyl,
a radical C(=O)R, wherein R is H, Ci-C4-alkyl, Ci-C4-haloalkyl,
C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-alkoxy, Ci-C4-alkoxy- Ci-C4-alkoxy, Ci-C4-haloalkoxy, amino, Ci-C4-alkylamino or di(Ci-C4-alkyl)amino,
a radical CR'(=NOR"), wherein R' is H or Ci-C4-alkyl, and R" is
Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl or Ci-C4-alkoxy-Ci-C4-alkyl,
phenyl, pyridinyl, pyrimidinyl, phenoxy or phenoxyalkyl, where the five last mentioned radicals are unsubstituted or carry 1 , 2, 3 or 4 identical or different substituents Rc;
Rb and Rc independently of each other are selected from halogen, CN,
NO2, OH, SH, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
and the N-oxides and the agriculturally acceptable salts of the compounds of the formula I;
and
2) one active compound Il selected from groups A) to I):
A) strobilurins azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb, trifloxystrobin, 2-(2-(6-(3-chloro-2-methyl-phenoxy)-5-fluoro-pyrimidin-4-yl- oxy)-phenyl)-2-methoxyimino-N-methyl-acetamide, 3-methoxy-2-(2-(N-(4- methoxy-phenyl)-cyclopropane-carboximidoylsulfanylmethyl)-phenyl)-acrylic acid methyl ester, methyl (2-chloro-5-[1 -(3-methylbenzyloxyimino)ethyl]- benzyl)carbamate and 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylidene- aminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide;
B) carboxamides carboxanilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, car- boxin, fenfuram, fenhexamid, flutolanil, furametpyr, isopyrazam, isotianil, kiralaxyl, mepronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyr- azole-4-carboxamide (penflufen), penthiopyrad, sedaxane, tecloftalam, thifluz- amide, tiadinil, 2-amino-4-methyl-thiazole-5-carboxanilide, 2-chloro-N-(1 ,1 ,3- trimethyl-indan-4-yl)-nicotinamide, N-(3',4',5'-trifluorobiphenyl-2-yl)-3-difluoro- methyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(4'-trifluoromethylthiobi- phenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide and N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-car- boxamide;
- carboxylic morpholides: dimethomorph, flumorph, pyrimorph; benzoic acid amides: flumetover, fluopicolide, fluopyram, zoxamide, N-(3-ethyl-3,5,5-trimethyl-cyclohexyl)-3-formylamino-2-hydroxy-benzamide; - other carboxamides: carpropamid, dicyclomet, mandiproamid, oxytetracy- clin, silthiofarm and N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide; C) azoles
- triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difeno- conazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, flu- quinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipcona- zole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, pencona- zole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetra- conazole, triadimefon, triadimenol, triticonazole, uniconazole, 1 -(4-chloro- phenyl)-2-([1 ,2,4]triazol-1 -yl)-cycloheptanol; imidazoles: cyazofamid, imazalil, pefurazoate, prochloraz, triflumizol; benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole;
- others: ethaboxam, etridiazole, hymexazole and 2-(4-chloro-phenyl)- N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide; D) heterocyclic compounds pyridines: fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isox- azolidin-3-yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine, 2,3,5,6-tetra-chloro-4-methanesulfonyl-pyridine, 3,4,5-trichloropyri- dine-2,6-di-carbonitrile, N-(1 -(5-bromo-3-chloro-pyridin-2-yl)-ethyl)-2,4-di- chloronicotinamide, N-[(5-bromo-3-chloro-pyridin-2-yl)-methyl]-2,4-dichloro- nicotinamide;
- pyrimidines: bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, me- panipyrim, nitrapyrin, nuarimol, pyrimethanil;
- piperazines: triforine; - pyrroles: fenpiclonil, fludioxonil; morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph;
- piperidines: fenpropidin; - dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin;
- non-aromatic 5-membered heterocycles: famoxadone, fenamidone, flutianil, octhilinone, probenazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-di- hydro-pyrazole-1 -carbothioic acid S-allyl ester; - others: acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S, captafol, captan, chinomethionat, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, fenoxanil, Folpet, oxolinic acid, piperalin, pro- quinazid, pyroquilon, quinoxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo- 3-propylchromen-4-one, 5-chloro-1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl- 1 H-benzoimidazole and 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-yl- amine;
E) carbamates
- thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasul- phocarb, metiram, propineb, thiram, zineb, ziram; - carbamates: benthiavalicarb, diethofencarb, iprovalicarb, propamocarb, propamocarb hydrochlorid, valiphenal and N-(1 -(1-(4-cyano-phenyl)- ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
F) other active substances
- guanidines: guanidine, dodine, dodine free base, guazatine, guazatine- acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate);
- antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, polyoxine, validamycin A;
- nitrophenyl derivates: binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecnazen, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;
- sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane;
- organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, ipro- benfos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl; - organochlorine compounds: chlorothalonil, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pencycuron, pentachlorphenole and its salts, phthalide, quintozene, thiophanate-methyl, tolylfluanid, N-(4-chloro- 2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
- inorganic active substances: Bordeaux mixture, copper acetate, copper hy- droxide, copper oxychloride, basic copper sulfate, sulfur;
- others: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamin, metra- fenone, mildiomycin, oxin-copper, prohexadione-calcium, spiroxamine, tolylfluanid, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro- phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl-phen- oxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro-
3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)- N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2-methyl-4-(3-trimethyl- silanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, 2-{1 -[2-(5-methyl- S-trifluoromethyl-pyrazole-i -yO-acetyO-piperidin^-ylJ-thiazole^-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1 -yl)-amide, 2-{1 -[2-(5-methyl- S-trifluoromethyl-pyrazole-i -yO-acetyO-piperidin^-ylJ-thiazole^-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1 -yl-amide, acetic acid
6-tert.-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester and N-methyl- 2-{1 -[(5-methyl-3-trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}-N- [(1 R)-1 ,2,3,4-tetrahydronaphthalen-1 -yl]-4-thiazolecarboxamide. G) growth regulators abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flu- metralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, pro- hexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapen- thenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid , trinexapac- ethyl and uniconazole; H) herbicides
- acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamide, naproani- lide, pethoxamid, pretilachlor, propachlor, thenylchlor;
- amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate; - aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop, fluazi- fop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
- Bipyridyls: diquat, paraquat;
(thio)carbamates: asulam, butylate, carbetamide, desmedipham, dime- piperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate;
- cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, seth- oxydim, tepraloxydim, tralkoxydim;
- dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin; - diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fome- safen, lactofen, oxyfluorfen;
- hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil;
- imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, ima- zaquin, imazethapyr; - phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D),
2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop; pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate; pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, flu- roxypyr, picloram, picolinafen, thiazopyr;
- sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfo- sulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfu- ron, tritosulfuron, 1 -((2-chloro-6-propyl-imidazo[1 ,2-b]pyridazin-3- yl)sulfonyl)-3-(4,6-dimethoxy-pyrimidin-2-yl)urea; - triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazi- none, metamitron, metribuzin, prometryn, simazine, terbuthylazine, ter- butryn, triaziflam; ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, methabenzthiazuron,tebuthiuron; - other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam- methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, or- tho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, py- roxasulfone, pyroxsulam; - others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone,benfluresate, benzofenap, bentazone, benzobicyclon, bro- macil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cini- don-ethlyl, chlorthal, cinmethylin, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, Ie- nacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl ar- sonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyra- zolynate, quinoclamine, saflufenacil, sulcotrione, sulfentrazone, terbacil, te- furyltrione, tembotrione, thiencarbazone, topramezone, 4-hydroxy-3-[2-(2- methoxy-ethoxymethyO-θ-trifluoromethyl-pyridine-S-carbonyO-bicyclo- [3.2.1]oct-3-en-2-one, (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluo- romethyl-3,6-dihydro-2H-pyrimidin-1 -yl)-phenoxy]-pyridin-2-yloxy)-acetic acid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin- 4-ol, 4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine- 2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethyl- amino-2-fluoro-phenyl)-pyridine-2-carboxylic acid methyl ester.
I) insecticides
- organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlor- pyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicroto- phos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon;
- carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbo- furan, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate; - pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cyper- methrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, delta- methrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, si- lafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin; insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlor- fluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflu- muron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, dio- fenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spi- rodiclofen, spiromesifen, spirotetramat;
- nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefu- ran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1 -(2-chloro-thiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1 ,3,5]triazinane;
- GABA antagonist compounds: endosulfan, ethiprole, fipronil, vaniliprole, pyra- fluprole, pyriprole, 5-amino-1 -(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl- 1 H-pyrazole-3-carbothioic acid amide; macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, Ie- pimectin, spinosad, spinetoram; mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
- METI Il and III compounds: acequinocyl, fluacyprim, hydramethylnon;
- Uncouplers: chlorfenapyr; - oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide, propargite;
- moulting disruptor compounds: cryomazine;
- mixed function oxidase inhibitors: piperonyl butoxide;
- sodium channel blockers: indoxacarb, metaflumizone; - others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thiocyclam, flubendiamide, chlorantraniliprole, cyazypyr (HGW86), cyeno- pyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, and pyrifluquinazon; and
3) at least one further active compound III selected from groups A) to I) as de- fined above.
4. A mixture according to claim 3 comprising components 1 , 2 and 3 in a synergisti- cally effective amount.
5. A mixture according to any of claims 3 to 4, comprising a compound I and a compound Il in a weight ratio of from 100:1 to 1 :100, and a compound I and compound III in a weight ratio of from 100:1 to 1 :100.
6. A mixture according to any of claims 1 to 5 comprising at least one compound I, wherein X is N or CH.
7. A mixture according to any of claims 1 to 6 comprising at least one compound I, wherein R1 is selected from Ci-C4-alkyl and Ci-C4-alkoxy.
8. A mixture according to any of claims 1 to 7 comprising at least one compound I, wherein R2 is hydrogen.
9. A mixture according to any of claims 1 to 8 comprising at least one compound I, wherein the moiety Het-Y is located on the phenyl ring in the para-position with respect to the sulfonyl group and Y is -O-.
10. A mixture according to any of claims 1 to 9 comprising at least one compound I, wherein Het is selected from pyridinyl, pyrimidinyl, thiophenyl and pyrazolyl, wherein the aforementioned 4 heteroaromatic radicals carry 0, 1 or 2 radicals Ra selected from F, Cl, Br, CH3 and CF3.
1 1 . A mixture according to any of claims 1 to 10 comprising at least one compound I, wherein X is N or CH, n is 0, 1 or 2, R1 is CH3 or OCH3, R2 is hydrogen, the moiety Het-Y is located on the phenyl ring in the para-position with respect to the sul- fonyl group, Y is -O-, m is 0 or 1 , R3 is CH3 or F, Het is selected from pyridin-2-yl, pyridin-4-yl and pyrimidin-2-yl, wherein the aforementioned 3 heteroaromatic radicals carry 1 or 2 radicals Ra selected from Cl, Br, CH3 and CF3.
12. A mixture according to any of claims 3 to 1 1 , comprising as compounds Il and III fungicidal compounds selected from the groups A), B), C), D) and F).
13. A mixture according to any of claims 3 to 12, comprising as components 2) and 3) at least two compounds selected from epoxiconazole, metconazole, tebucon- azole, triticonazole, prothioconazol, difenoconazole, cyproconazole, kresoxim- methyl, pyraclostrobin, azoxystrobin, trifloxystrobin, dimoxystrobin, orysastrobin, fluoxastrobin, dimethomorph, 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidin- 7-ylamine, pyrimethanil, metalaxyl, fenpropimorph, mancozeb, metiram, thio- phanate-methyl, chlorothalonil, metrafenon, bixafen, boscalid, Λ/-(3',4',5'-trifluoro- biphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, sedaxane, isopyrazam, fluopyram, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro- 1 H-pyrazole-4-carboxamide (penflufen), penthiopyrad, N-Methyl-2-{1 -[(5-methyl- 3-trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}-N-[(1 R)-1 ,2,3,4-tetra- hydronaphthalen-1 -yl]-4-thiazolecarboxamide, mandipropamide, iprovalicarb, benthiovalicarb, copper salts, sulphur and dithianon.
14. A binary mixture according to any of claims 1 and 2 and any of claims 6 to 1 1 , comprising as compound Il a fungicidal compound selected from the groups A), B), C), D) and F).
15. A binary mixture according to any claims 1 and 2 and any of claim 6 to 1 1 and 14, comprising as compound Il a fungicidal compound selected from epoxicona- zole, metconazole, tebuconazole, triticonazole, prothioconazol, difenoconazole, cyproconazole, kresoxim-methyl, pyraclostrobin, azoxystrobin, trifloxystrobin, dimoxystrobin, orysastrobin, fluoxastrobin, dimethomorph, 5-ethyl-6-octyl- [1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-ylamine, pyrimethanil, metalaxyl, fenpropimorph, mancozeb, metiram, thiophanate-methyl, chlorothalonil, metrafenon, bixafen, boscalid, Λ/-(3',4',5'-trifluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole- 4-carboxamide, sedaxane, isopyrazam, fluopyram, N-(2-(1 ,3-dimethyl-butyl)- phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide (penflufen), penthiopyrad, N-Methyl-2-{1 -[(5-methyl-3-trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]- piperidin-4-yl}-N-[(1 R)-1 ,2,3,4-tetrahydronaphthalen-1 -yl]-4-thiazolecarboxamide, mandipropamide, iprovalicarb, benthiovalicarb, copper salts, sulphur and di- thianon.
16. A binary mixture comprising as active compounds 1 ) at least one compound I as defined in any of claims 1 and 2 and 6 to 1 1 and 2) N-Methyl-2-{1 -[(5-methyl-3- trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}-N-[(1 R)-1 ,2,3,4-tetrahydro- naphthalen-1 -yl]-4-thiazolecarboxamide.
17. An agrochemical composition, comprising a solvent or solid carrier and a mixture according to any of claims 1 to 16.
18. A method for controlling phytopathogenic harmful fungi, comprising treating the fungi, their habitat or the seed, the soil or the plants to be protected against fungal attack with an effective amount of the compound I and the compound Il and the compound III as defined in any one of claims 3 to 13 or of the composition according to claim 17.
19. Seed comprising the mixture according to any one of claims 1 to 16 in an amount of from 1 g to 1000 g active compounds per 100 kg of seed.
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